JP2000072841A - Polyurethane-based elastic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject elastic fiber consisting of a polyurethane obtained by polymerizing a high molecular polyol, an organic polyisocyanate and a chain extender, and excellent in endurance such as a light fastness, chlo rine resistance, hot water resistance or the like. SOLUTION: This polyurethane-based elastic fiber is obtained from a polyurethane obtained by polymerizing (A) a high molecular polyol, (B) an organic polyisocyanate and (C) a chain extender. As the component (A), a vinylic polymer having terminal hydroxyl group, 500-50,000 average molecular weight and 1.5-2.6 mean functional value, and obtained by a living radical polymerization, preferably by an atomic transfer radical polymerization using a copper complex as a catalyst, is used. The monomers constituting the vinylic polymer preferably contains a (meth)acrylic monomer, an aromatic vinylic monomer or the like, as essential components. The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of the vinylic polymer is preferably <1.8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane-based elastic fiber having excellent durability such as light resistance, chlorine resistance and hot water resistance.

[0002]

2. Description of the Related Art Polyurethane elastic fibers have hitherto been produced mainly by wet or dry spinning. In other words, this fiber having a polyurethane urea structure has excellent properties of elasticity and elongation recovery, but has extremely high chlorine resistance and light resistance because polyether diol is used as a soft segment component. Is a disadvantage. Poor chlorine resistance impairs the elasticity of swimwear due to chlorine for pool sterilization, and bleaching dirt on underwear using polyurethane elastic yarn with chlorine bleach causes significant embrittlement and makes it impossible to wear Also, there has been a problem that long-term home washing causes embrittlement due to chlorine in tap water. As a method of improving chlorine resistance, for example, a method of adding magnesium oxide or aluminum oxide (Japanese Patent Publication No.
-35283) and a method of adding zinc oxide (Japanese Patent Publication Sho 60)
However, these metal oxides are difficult to disperse evenly in the dope for dry (wet) spinning, and as a result, unevenness occurs in the chlorine resistance of the obtained elastic yarn, or spinning is performed. There is a drawback that the adhesive is easily adhered to the base and as a result, the yarn is apt to be broken, that is, the productivity is significantly reduced. Furthermore, since these metal oxides fall off during a post-processing step such as dyeing (for example, when passing through a treatment bath), there is a problem that desired chlorine resistance cannot be obtained. With respect to light resistance, if this property is poor, yellowing due to light and elongation and elongation recovery inherent in the elastic yarn will not develop over time. As a method of improving light resistance, a method of adding a benztriazole-based, benzphenone-based, salicylic acid-based ultraviolet absorber or the like is conventionally known. The problems of solubility in fibers, adhesion to the spinneret, breakage of yarns, and the fact that these additives are very expensive are factors in increasing the cost of urethane elastic yarns. On the other hand, production by the melt spinning method has recently been increasing due to low cost and good transparency. However,
As a drawback, the polyurethane elastic yarn obtained by the melt spinning method has inferior heat resistance and hot water resistance as compared with the elastic yarn obtained by the dry spinning method. For example, it has been pointed out that those produced using polyester diol are inferior in hot water resistance, alkali resistance, and mold resistance.

[0003]

That is, an object of the present invention is to solve the above-mentioned problems of the prior art and to provide a polyurethane-based elastic fiber having excellent durability such as light resistance, chlorine resistance and hot water resistance. It is in.

[0004]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have surprisingly found that a vinyl polymer having a hydroxyl group at a terminal and produced by living radical polymerization, particularly a (meth) acrylic polymer. It has been found that by using a polymer, a polyurethane elastic fiber excellent in light resistance, chlorine resistance and hot water resistance can be obtained.

That is, the present invention relates to an elastic fiber comprising a polyurethane obtained by polymerizing a polymer polyol, an organic polyisocyanate and a chain extender, wherein the polymer polyol is a vinyl polymer having a hydroxyl group at a terminal. It is a polyurethane-based elastic fiber characterized by using (I). The monomers constituting the polymer (I) are not limited, but include (meth) acrylic monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. It is preferable that at least one monomer selected from the group consisting of
(Meth) acrylic monomers are preferred, acrylate monomers are more preferred, and butyl acrylate monomers are particularly preferred.

[0006] The average molecular weight of the polymer (I) is not limited, but is preferably from 500 to 50,000. The average functionality of the polymer (I) may be, but is not limited to, 1.5
~ 2.6 is preferred. The polymer (I) is produced by living radical polymerization, and is preferably produced by atom transfer radical polymerization, and among them, atom transfer radical polymerization using a copper complex as a catalyst is preferred.

The value of the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (I) measured by gel permeation chromatography is not limited, but is less than 1.8. It is preferred that Although not limited, the main chain of the polymer (I) preferably contains no sulfur atom.

The polymer (I) is produced by various methods such as a method of producing a vinyl polymer by living radical polymerization and further reacting the vinyl polymer with a compound having both a polymerizable alkenyl group and a hydroxyl group.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an elastic fiber comprising a polyurethane obtained by polymerizing a polymer polyol, an organic polyisocyanate, and a chain extender, wherein the polymer polyol has a hydroxyl group-terminated vinyl. A polyurethane-based elastic fiber characterized by using the polymer (I).

First, the polymer (I) will be described below. << Polymer (I) >> The molecular weight of the polymer (I) of the present invention is not limited.
Those having about 00 to 10000 are preferable, and especially 500 to
A viscous liquid having a fluidity of about 8000 is preferable from the viewpoint of easy handling.

The average functionality of the polymer (I) of the present invention is 1.
A range of 5 to 2.6, preferably 1.8 to 2.3 is good.
Here, "average functionality" means the average number of active hydrogen atoms per molecule. Such an active hydrogen atom is associated with a hydroxyl group in the case of a polyol. When a vinyl polymer having a hydroxyl group at the terminal having an average functionality outside these ranges is used, good processability and physical properties may not be obtained. In particular, the spinning stability is reduced, and the mechanical properties and productivity of the fiber may be reduced.

The polymer (I) of the present invention has a molecular weight distribution, that is, gel permeation chromatography (G
It has a feature that the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by the method (PC) is narrow. The value of the molecular weight distribution is less than 1.8, preferably 1.7 or less, more preferably 1.6 or less;
It is particularly preferably at most 1.5, particularly preferably at most 1.4, most preferably at most 1.3.
In the GPC measurement in the present invention, although not particularly limited, usually, chloroform is used as a mobile phase, and the measurement is performed using a polystyrene gel column. The number average molecular weight and the like can be determined in terms of polystyrene. The narrower the molecular weight distribution, the lower the viscosity even with the same number average molecular weight, and the easier the handling.

The vinyl monomer used for producing the main chain of the polymer (I) of the present invention is not particularly limited, and various types can be used. For example, (Meta)
Acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate,
Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, (meth) acrylic acid- n-hexyl, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, nonyl (meth) acrylate ) Decyl acrylate,
Dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth)
2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate , 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, (meth)
2-perfluoroethyl acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, (meth) acryl (Meth) acrylic monomers such as 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate; styrene, vinyltoluene, α-methyl Styrene monomers such as styrene, chlorostyrene, styrene sulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane Monomer; anhydrous Maleic acid, maleic acid, monoalkyl esters and dialkyl esters of maleic acid;
Fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide,
Maleimide monomers such as hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; vinyl monomers having a nitrile group such as acrylonitrile and methacrylonitrile; vinyl monomers having an amide group such as acrylamide and methacrylamide; Vinyl acetates such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride; Allyl alcohol and the like can be mentioned. These may be used alone or a plurality of them may be copolymerized. Among these monomers, meta (acryl) -based monomers, acrylonitrile-based monomers, aromatic vinyl-based monomers, fluorine-containing vinyl-based monomers and silicon-containing vinyl-based monomers are preferable from the viewpoint of the physical properties of the product. More preferred are acrylate-based monomers and methacrylate-based monomers, and even more preferred is butyl acrylate. In the present invention, these preferable monomers may be copolymerized with other monomers. In such a case, it is preferable that these preferable monomers are contained in a weight ratio of 40%. In the above expression format, for example, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

As described above, the vinyl monomer used in the present invention may have a functional group such as a hydroxyl group, a carboxyl group, or an amino group in the molecule. It is preferred that the polymer has a hydroxyl group only at the terminal of the polymer without using. For example, when transparency, weather resistance, water resistance, and the like are required, the vinyl monomer preferably contains a (meth) acrylic acid monomer as a main component. In this case, for the entire vinyl monomer,
It is preferable that the content of the (meth) acrylic acid-based monomer is 40% by weight or more.

When water repellency, oil repellency, stain resistance and the like are required, it is preferable to use a fluorine-containing vinyl monomer. In this case, for the entire vinyl monomer,
It is preferable that the fluorine-containing monomer is contained in an amount of 10% by weight or more. When adhesion with inorganic materials and stain resistance are required, it is preferable to use a silicon-containing vinyl monomer. In this case, it is preferable that the silicon-containing monomer is contained in an amount of 10% by weight or more based on the whole vinyl-based monomer. <Living radical polymerization> The polymer (I) of the present invention is produced by a living radical polymerization method. Hereinafter, the living radical polymerization method will be described.

Living radical polymerization is radical polymerization in which the activity of the polymerization terminal is maintained without loss. In a narrow sense, living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the activated one is in an equilibrium state. . The definition in the present invention is also the latter. Living radical polymerization has been actively studied in recent years by various groups. Examples thereof include a cobalt porphyrin complex (J. Am. Chem. Soc. 199).
No. 4,116,7943) and those using a radical scavenger such as a nitroxide compound (Macromolecule)
es, 1994, 27, 7228), atom transfer radical polymerization using an organic halide or the like as an initiator and a transition metal complex as a catalyst (Atom Transfer Radica).
l Polymerization). In the present invention, which method is used is not particularly limited, but atom transfer radical polymerization is preferable in terms of easy control. Atom transfer radical polymerization is carried out using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a transition metal as a central metal as a catalyst. (For example, Matyjaszewsk
i. Am. Chem. Soc. 1995, 11
7,5614, Macromolecules 199
5, 28, 7901, Science 1996, 27
2,866, WO96 / 30421 and W
O97 / 18247, or Sawamoto et al., M
acromolecules 1995, 28, 172
1). According to these methods, the polymerization rate is generally very high, and the polymerization proceeds in a living manner, and the molecular weight distribution is narrow (that is, Mw /
(Mn value is about 1.1 to 1.5) polymer is obtained,
The molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

In the present invention, there is no particular limitation on which method is used, but atom transfer radical polymerization is preferred from the viewpoint of easy control. First, a method using a radical scavenger such as a nitroxide compound will be described. In this polymerization, a stable nitroxy free radical (= NO) is generally used as a radical capping agent. Examples of such compounds include, but are not limited to, 2,2,6,6-substituted-1-piperidinyloxy radical and 2,2,5,5-substituted-1-pyrrolidinyloxy radical. Nitroxy free radicals from cyclic hydroxyamines are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group and an ethyl group is suitable.
Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-
Piperidinyloxy radical (TEMPO), 2,2
6,6-tetraethyl-1-piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-
Piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1,1,
3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical and the like. Instead of the nitroxy free radical, a stable free radical such as galvinoxyl free radical may be used.

The above radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator, and the polymerization of the addition-polymerizable monomer proceeds. The combination ratio of both is not particularly limited, but 0.1 to 10 mol of the radical initiator is appropriate for 1 mol of the radical capping agent.

As the radical generator, various compounds can be used, but a peroxide capable of generating a radical under polymerization temperature conditions is preferable. Examples of the peroxide include, but are not limited to, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; diisopropyl peroxydicarbonate; Peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyoctoate, t-
There are alkyl peresters such as butyl peroxybenzoate. Particularly, benzoyl peroxide is preferred. Further, a radical generator such as a radical-generating azo compound such as azobisisobutyronitrile may be used instead of the peroxide.

Macromolecules 199
As reported in US Pat. No. 5,28,2993, instead of using a radical capping agent and a radical generator together,
An alkoxyamine compound as shown below may be used as an initiator.

[0021]

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When an alkoxyamine compound is used as an initiator, if the compound has a functional group such as a hydroxyl group as shown in the above figure, a polymer having a functional group at the terminal can be obtained. When this is used in the method of the present invention, a star polymer having a functional group at a terminal can be obtained. Polymerization conditions such as a monomer, a solvent, and a polymerization temperature used in the polymerization using the radical scavenger such as the nitroxide compound are not limited, but may be the same as those used for atom transfer radical polymerization described below.

Next, a more preferred atom transfer radical polymerization as the living radical polymerization of the present invention will be described. In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, an ester compound having a halogen at the α-position or a compound having a halogen at the benzyl position), or a halogen compound It is preferable to use a sulfonyl compound as an initiator. The transition metal complex used as a catalyst for the living radical polymerization is not particularly limited, and preferred are 7, 8, 9, 10, 11
More preferred group III transition metal complexes include complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Among them, a copper complex is preferable. Specific examples of the monovalent copper compound include:
Examples include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate and the like. When a copper compound is used, 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-
A ligand such as a polyamine such as aminoethyl) amine is added. Tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, aluminum alkoxides are added as an activator. Furthermore, bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ ) ₂ ) and bistriphenylphosphine complex of divalent nickel (NiCl ₂ (P
Ph _{3) 2),} and a divalent bis tributylphosphine complex nickel _{(NiBr 2 (PBu 3) 2} ) are also suitable as catalysts.

In this polymerization method, usually, an organic halide or a sulfonyl halide compound is used as an initiator. For example, C ₆ H ₅ —CH ₂ X, C ₆ H ₅ —C (H) (X) CH ₃ , C _{6
H 5 -C (X) (CH} 3) 2 ( where in the above formula, C ₆ H ₅ is a phenyl group, X is chlorine, bromine or ^{iodine,) R 13 -C (H)} (X) -CO 2 R ¹⁴ , R ¹³ -C (CH ₃ )
^{_{(X) -CO 2 R 14,}} R 13 -C (H) (X) -C (O)
^{R 14, R 13 -C (CH} 3) (X) -C (O) R 14, ( wherein, R ¹³ and R ¹⁴ are the same or different, is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms , an aryl group or an aralkyl group, X is chlorine, bromine or ^{_{iodine) R 13 -C 6 H 4 -SO}} 2 X ( wherein, R ¹³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, Or an aralkyl group, and X is chlorine, bromine, or iodine).

One method for obtaining the polymer (I) of the present invention having two or more hydroxyl groups in one molecule is as follows.
It is preferred to use an organic halide or a sulfonyl halide compound having one or more starting points as the initiator. To give a concrete example,

[0026]

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[0027]

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And the like. There are no particular restrictions on the vinyl monomer used in this polymerization, and any of those already exemplified can be suitably used. This polymerization can be carried out without solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene; acetone ,
Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ethyl acetate Butyl acetate and the like; and ester solvents such as ethylene carbonate and propylene carbonate. These can be used alone or 2
A mixture of more than one species can be used. The polymerization can also be carried out in an emulsion system or a system using a supercritical fluid CO ₂ as a medium.

This polymerization can be carried out at room temperature to 200 ° C., preferably at 50 to 150 ° C. <Introduction of Terminal Functional Group> Examples of the method for introducing a hydroxyl group into the terminal of the polymer (I) of the present invention include the following methods, but are not limited to these methods.

(A) When synthesizing a vinyl polymer by radical polymerization, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule as shown in the following general formula 1 is used as a second monomer. How to react. ^{_{H 2 C = C (R 1}} ) -R 2 -R 3 -OH (1) ( wherein, R ¹ represents a hydrogen or a methyl group, R ² is -C (O) O
- (ester group), or o-, m-, p-phenylene group, R ³ may also be a direct bond, or contain one or more ether bonds with a divalent organic group having 1 to 20 carbon atoms) There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule. After completion of the above reaction, the reaction is preferably carried out as a second monomer.

The compound having a polymerizable alkenyl group of the present invention refers to a compound in a living radical polymerization system
A compound capable of forming a so-called block copolymer by adding two or more to the living terminal of the polymer. When a compound having both a polymerizable alkenyl group and a hydroxyl group is used, for example, a polymer having a plurality of hydroxyl groups at terminals can be obtained. (B) A method of reacting a compound having both an alkenyl group and a hydroxyl group with low polymerizability in one molecule as shown in the following general formula 2 when synthesizing a vinyl polymer by radical polymerization. H ₂ C ＝ C (R ⁴ ) —R ⁵ —OH (2) In the above formula, R ⁵ is an alkyl group having 1 to 20 carbon atoms or a general formula 3: —C (R ⁷ ) ₂ —R ⁶ — C (R ⁷ ) _2- (3) (In the above formula, R ⁶ is an oxygen atom, a nitrogen atom or an organic group having 1 to 20 carbon atoms, and R ⁷ is a hydrogen atom or a methyl group and may be the same or different. Good), and R ⁴ is a hydrogen atom or a methyl group. The compound having a low polymerizable alkenyl group of the present invention refers to a polymer having a low polymerizability in a living radical polymerization system. A compound having a relatively low radical polymerization activity such that only one molecule can undergo an addition reaction with a living terminal. When a compound having both an alkenyl group and a hydroxyl group having low polymerizability is used, a polymer having one hydroxyl group introduced into a terminal can be obtained.

(C) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a simple metal such as zinc or an organometallic compound, followed by an aldehyde. Kind,
Or a method of reacting ketones. (D) at least one highly reactive carbon-halogen bond
In the vinyl polymer having one or more compounds, for example, a compound represented by general formula 4 or 5
And reacting an oxyanion or a carboxylate anion having a hydroxyl group as described in (1) to replace halogen. M ⁺ O ^-- R ⁸ -OH (4) (wherein, R ⁸ is a divalent alkyl group having 1 to 20 carbon atoms, a divalent aryl group having 6 to 20 carbon atoms, or 7 to 2 carbon atoms)
A divalent aralkyl group of 0, which may contain one or more ether bonds, M ⁺ is an alkali metal ion or a quaternary ammonium ion) M ⁺ OC (O) —R ⁸ —OH (5) , R ⁸ and M ⁺ are the same as described above.) (E) At least one highly reactive carbon-halogen bond
A method in which a halogenated group is reacted with a vinyl-based polymer having a hydroxyl group and a stabilized carbanion having a hydroxyl group as shown in the general formula 8. ^{M + C - (R 15)} (R 16) -R 17 -OH (8) ( wherein, R ^15, R ¹⁶ are both carbanion C ^- or an electron withdrawing group stabilizing, or one of the electronic On the other hand withdrawing group is hydrogen or an alkyl group having 1 to 10 carbon atoms or a phenyl group .R ¹⁷ is a direct bond, or carbon atoms, 1
Represents a divalent organic group of from 10 to 10, and may contain one or more ether bonds. M ⁺ as an alkali metal ion or an quaternary ammonium ion,) an electron withdrawing group _{^{R 15, R 16, -CO 2}} R, -C
Those having the structure of (O) R and -CN are particularly preferred.

(F) Hydrolysis of a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond or reaction with a hydroxyl group-containing compound by a method described in, for example, JP-A-4-132706. By introducing a hydroxyl group into the terminal. (G) A method using a compound having a hydroxyl group as an initiator of atom transfer radical polymerization for producing the polymer (I).

(H) A method of coupling the other end of the polymer having a hydroxyl group to one end obtained by the above method. And the like. In the present invention, a living radical polymerization method is used as a polymerization method. Preferably, a polymerization method is used.

Hereinafter, each of the above methods will be described in detail. The method (A) is a method in which a polymer is produced by living radical polymerization, and a compound having both a polymerizable alkenyl group and a hydroxyl group is reacted as a second monomer. In the above-mentioned polymerization, the polymerization terminal maintains the polymerization activity, and the polymerization proceeds again when a vinyl monomer is newly added. Therefore, when a vinyl monomer having both a polymerizable alkenyl group and a hydroxyl group is added, a radical addition reaction occurs in the polymerization active alkenyl group portion, the hydroxyl group remains as it is, and a (meth) acrylic polymer having a hydroxyl group at a terminal. Is obtained. Such a second monomer may be added together with a catalyst and then newly reacted after the first polymerization is completed and the polymer is isolated,
The reaction may be performed by adding in-situ during the polymerization. In the latter case, the higher the monomer conversion in the first polymerization, the better, preferably 80% or more. If it is at most 80%, the hydroxyl groups will be distributed not at the molecular terminals but at the side chains, which will impair the mechanical properties of the cured product.

At this time, the compound having both the polymerizable alkenyl group and the hydroxyl group may be added in an amount equal to the number of polymerization terminals (almost equal to the number of starting points of the initiator because it is living polymerization). In principle, one hydroxyl group is introduced into each terminal in principle, but in order to surely introduce hydroxyl groups into all terminals, an excess amount, specifically, the number of terminals is limited. Although not performed, it is preferable to use 1 to 5 times. If it is used more than 5 times, hydroxyl groups may be introduced into the terminal of the polymer at high density.

The compound having both a polymerizable alkenyl group and a hydroxyl group is not particularly limited. For example, the compound represented by the general formula 1 H ₂ C 2C (R ¹ ) -R ² -R ³ -OH (1) R ¹ is hydrogen or methyl, R ² is —C (O) O
- (ester group), or o-, m-, p-phenylene group, R ³ may also be a direct bond, or contain one or more ether bonds with a divalent organic group having 1 to 20 carbon atoms) The compound shown by these is mentioned. When R ² is an ester group, it is a (meth) acrylate compound, and when R ² is a phenylene group, it is a styrene compound. R ³ in the general formula 1 represents an alkylene group such as methylene, ethylene and propylene, a phenylene group such as o-, m- and p-phenylene group, an aralkyl group such as benzyl group, and —CH ₂ CH ₂ —.
O-CH ₂ CH ₂ - or -OCH ₂ CH ₂ - alkylene group containing an ether bond and the like.

Among them, H ₂ C ＝ C (H) C (O) O (CH ₂ ) _n -OH and H ₂ C =
_{C (CH 3) C (O} ) O (CH 2) n -OH, ( in each formula above, n represents an integer of 1 to _{20) H 2 C = C (H} ) C (O) O (CH 2) _n -O- (CH _{2)
m OH, H 2 C = C} (CH 3) C (O) O (CH 2) n -O
_{- (CH 2) m -OH,} ( in each formula above, n, m is an integer of 1~20) o-, m-, p- H 2 C = CH-C 6 H 4 - (CH 2) n −
OH, o-, m-, p- H 2 C = C (CH 3) -C 6 H 4 -
(CH _{2) n} -OH, (in the above formulas, n 0-20 integer) o-, m-, p-H 2 C = CH-C 6 H 4 -O (CH 2) n
-OH, o-, m-, p- H 2 C = C (CH 3) -C 6 H 4
—O (CH ₂ ) _n —OH, where n is an integer of 1 to 20, is preferred.

The method (B) is a method of producing a polymer by living radical polymerization and further reacting a compound having both an alkenyl group and a hydroxyl group with low polymerizability.
Such compounds do not polymerize, but can react with only about one molecule with the growing end of living radical polymerization, resulting in the introduction of a hydroxyl group at the end.

The compound having an alkenyl group having low polymerizability is selected from the compounds represented by the general formula 2. Formula 2: H ₂ C ＝ C (R ⁴ ) —R ⁵ —OH (2) In the above formula, R ⁵ is an alkylene group having 1 to 20 carbon atoms or Formula 3: —C (R ⁷ ) ₂ -R ⁶ -C (R ⁷ ) _2- (3) (In the above formula, R ⁶ is an oxygen atom, a nitrogen atom or an organic group having 1 to 20 carbon atoms, and R ⁷ is a hydrogen atom or a methyl group, and R ⁴ is a hydrogen atom or a methyl group. In the general formula 2, specific examples of R ⁵ include — (CH ₂ ) _n
- (n is an integer of 1 to _{20), - CH (CH 3)} -, -C
_{H (CH 2 CH 3) -} , - C (CH 3) 2 -, - C (C
_{H 3) (CH 2 CH 3} ) -, - C (CH 2 CH 3) 2 -, -
_{CH 2 CH (CH 3) -} , - (CH 2) n -O-CH 2 -,
(N is 1 to 19 _{integer), - CH (CH 3)} -O-CH 2
_{-, - CH (CH 2 CH} 3) -O-CH 2 -, - C (C
_{H 3) 2 -O-CH 2} -, - C (CH 3) (CH 2 CH 3) -
_{O-CH 2 -, - C} (CH 2 CH 3) 2 -O-CH 2 -, -
(CH ₂ ) _n —O— (CH ₂ ) _m − (m and n are integers of 1 to 19, provided that 2 ≦ m + n ≦ 2
0),-(CH ₂ ) _n -C (O) O- (CH ₂ ) _m- (m and n are integers of 1 to 19, provided that 2 ≦ m + n ≦ 2
_{0), - (CH 2)} n -OC (O) - (CH 2) m -C
_{(O) O- (CH 2)} l -, (l is an integer of 0 to 18, m,
n is an integer of 1 to 17, provided that 2 ≦ l + m + n ≦ 18),
_{- (CH 2) n -o-,} m-, p-C 6 H 4 -, - (C
_{H 2) n -o-, m-,} p-C 6 H 4 - (CH 2) m -, (m
Is an integer of 0 to 13, n is an integer of 1 to 14, provided that 1 ≦ m
+ N ≦ 14),-(CH ₂ ) _n -o-, m-, p-C ₆ H ₄
—O— (CH ₂ ) _m —, (m is an integer of 0 to 13, n is 1 to
An integer of 14, where 1 ≦ m + n ≦ 14),-(CH ₂ ) _{n
-O-, m-, p-C 6} H 4 -O-CH (CH 3) -,
(N is an integer of 1 to _{12), - (CH 2) n} -o-, m-,
_{p-C 6 H 4 -O-} CH (CH 3) 2 -,, (n is 1 to 11 _{integer) - (CH 2) n -o-} , m-, p-C 6 H 4 -C
_{(O) O- (CH 2)} m -, (m, n is an integer from 1 to 12,
However, 2 ≦ m + n ≦ 13),-(CH ₂ ) _n -OC (O)
_{-O-, m-, p-C 6} H 4 -C (O) O- (CH 2)
_m− , (m and n are integers from 1 to 11, provided that 2 ≦ m + n ≦
_{12), - (CH 2)} n -o-, m-, p-C 6 H 4 -OC
(O) — (CH ₂ ) _m —, (m and n are integers from 1 to 12, provided that 2 ≦ m + n ≦ 13), and — (CH ₂ ) _n —C (O) O—
_{o-, m-, p-C 6} H 4 - (CH 2) m -, (m, n is 1
An integer of 1 to 11, provided that 2 ≦ m + n ≦ 12).

Specific examples of R ⁶ include the following groups. _{- (CH 2) n -CH 3} , -CH (CH 3) - (CH 2) n -
_{CH 3, -CH (CH 2 CH} 3) - (CH 2) n -CH 3, -
_{CH (CH 2 CH 3) 2} , -C (CH 3) 2 - (CH 2) n -
_{CH 3, -C (CH 3)} (CH 2 CH 3) - (CH 2) n -C
_{H 3, -C 6 H 5,} -C 6 H 5 (CH 3), - C 6 H 5 (C
_{H 3) 2, - (CH} 2) n -C 6 H 5, - (CH 2) n -C 6 H 5
(CH ₃ ), — (CH ₂ ) _n —C ₆ H ₅ (CH ₃ ) ₂ (n is an integer of 0 or more, and the total number of carbon atoms of each group is 20 or less) More specifically, 10-undecenol; Alkenyl alcohols such as 5-hexenol and allyl alcohol are exemplified.

These compounds may be allowed to react as they are at the growing terminal of living radical polymerization, but these groups may affect the polymerizing terminal or the catalyst. May be used. Examples of the protecting group include an acetyl group, a silyl group, and an alkoxy group. The amount of the compound used to introduce these hydroxyl groups is not particularly limited. Since the reactivity of the alkenyl group of these compounds is not very high, it is preferable to increase the amount added in order to increase the reaction rate. On the other hand, in order to reduce the cost, the amount added is equal to the growth terminal. It is preferable to be closer, and it is necessary to optimize it according to the situation.

In the method (C), an enolate anion is prepared by reacting a halogen-terminated vinyl polymer with a simple metal or an organometallic compound, followed by reaction with an aldehyde or a ketone. Is the way. Examples of the simple metal include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, aluminum and zinc.
Among them, zinc is particularly preferable because the generated enolate anion hardly causes side reactions such as attacking or transferring other ester groups. Specific examples of the organometallic compound include organolithium, organosodium, organopotassium, organomagnesium such as Grignard reagent, organoaluminum, organozinc and the like. To metallize halogens efficiently, organolithium,
It is preferred to use organomagnesium.

The aldehydes and ketones are not particularly limited, and various aldehydes and ketones can be used. For example, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone,
Benzophenone and the like.

A method for introducing a hydroxyl-containing substituent using zinc and aldehydes or ketones is known as Reforma.
The Tsky reaction is a particularly preferred embodiment.
Although various solvents can be used in this reaction, aprotic solvents are preferable, and among them, ether solvents such as tetrahydrofuran and diethyl ether are particularly preferable. The reaction can be carried out at room temperature to 100 ° C.

The method (D) is a method in which an oxyanion compound having a hydroxyl group is reacted with a vinyl polymer having at least one highly reactive carbon-halogen bond. Although the hydroxyl group-containing oxyanion is not limited, a compound represented by the general formula 4 can be mentioned. M ⁺ O ^-- R ⁸ -OH (4) (wherein, R ⁸ is a divalent alkyl group having 1 to 20 carbon atoms, a divalent aryl group having 6 to 20 carbon atoms, or 7 to 2 carbon atoms)
A divalent aralkyl group of 0, which may contain one or more ether bonds, M ⁺ is an alkali metal ion or a quaternary ammonium ion) M ⁺ is a counter ion of an oxyanion, and a lithium ion, a sodium ion, Alkali metal ions such as potassium ion, tetramethylammonium ion, tetraethylammonium ion, trimethylbenzylammonium ion, trimethyldodecylammonium ion,
Examples thereof include quaternary ammonium ions such as tetrabutylammonium ion and dimethylpiperidinium ion.

The oxy anion of the general formula 4 can be obtained by reacting a diol compound as a precursor thereof with a suitable base. Such precursors include the following compounds: HO— (CH ₂ ) _n —OH, where n is 2 to
Integer of 20), HO-CH (CH 3) CH 2 OH, HO-
_{CH (CH 3) CH 2 CH} 2 OH, HO-CH 2 CH (CH
_{3) CH 2 -OH, HO-} CH 2 C (CH 3) 2 CH 2 -O
_{H, HO-CH 2 C (} CH 3) (C 2 H 5) CH 2 -OH,
_{HO-CH 2 C (C 2} H 5) 2 CH 2 -OH, CH 3 CH 2 C
_{H (OH) CH 2 -OH,} CH 3 CH (OH) CH (O
_{H) CH 3, HO- (CH} 2 O) n -H (n is an integer of 1 to _{20), HO- (CH 2 CH 2} O) n -H (n is 1 to 10
HO- (CH ₂ CH (CH ₃ ) O) _n -H (n
1-6 integer), o-, m-, p- HO-C 6 H 4 -O
H, o-, m-, p- HO-C 6 H 4 - (CH 2) n OH
(N is an integer of 1 to 14), o-, m-, p-HO- (C
_{H 2) n -C 6 H 4} - (CH 2) m OH (n, n + m ≦ 14 , m is 1 to 13 integer), 3-methyl catechol, 4-methyl catechol, 2-methyl resorcinol, 4-methyl Resorcinol, 2,5-dimethylresorcinol,
Methylhydroquinone, 2,3-dimethylhydroquinone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene,
Examples thereof include 2,6-dihydroxynaphthalene, 2,2′-biphenol, 4,4′-biphenol, and 4,4′-isopropylidene diphenol. Of these,
Reactive oxyanion is optionally substituted the terminal halogen of formula 1 mild, and from that it is easily available, o-, m-, p-HO -C 6 H 4 -OH, o-, m
_{-, p-HO-C 6} H 4 - (CH 2) n OH (n is 1 to 14
Is preferably an integer. These diol compounds may be used in a molar ratio of 1 equivalent to the terminal of formula 1, but preferably 1 to 5 equivalents.

Various bases are used to extract a proton from the above compound to obtain an oxyanion of the general formula 4. These bases include: sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium tert-butoxide, potassium methoxide
tert-butoxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, sodium hydride, potassium hydride, methyllithium, ethyllithium, n-butyllithium, tert-butyllithium,
Examples thereof include lithium diisopropylamide and lithium hexamethyldisilazide. The amount of the base used is sufficient if it is used in an equivalent amount to the precursor diol, but is preferably 0.8 to 1.5 equivalents. Examples of the solvent used when preparing the oxyanion of the general formula 4 by reacting the above precursor and a base include, for example, tetrahydrofuran, dioxane, diethyl ether, dimethylformamide,
Hexamethylphosphoric triamide, ethanol, methanol, isopropyl alcohol, tert-butyl alcohol and the like are used.

By reacting a hydroxyl-containing carboxylate anion represented by the general formula 5 on a vinyl polymer having at least one highly reactive carbon-halogen bond, a vinyl polymer having a hydroxyl group at a terminal can also be obtained. Obtainable. M ⁺ OC (O) -R ⁸ -OH (5) (wherein R ⁸ and M ⁺ are the same as above) The carboxylate anion of the general formula 5 is a base suitable for a hydroxyl group-containing carboxylic acid as a precursor thereof. Can be adjusted. Such precursors include the following compounds: HO ₂ C— (CH ₂ ) _n —OH (n is an integer of 1 to 20);
_{HO 2 C-CH (OH)} CH 3, HO 2 C-CH 2 CH (O
_{H) CH 3, o-, m-} , p-HO 2 C-C 6 H 4 -OH,
_{o-, m-, p-HO 2} C- (CH 2) n -C 6 H 4 -O
H, o-, m-, p- HO 2 C-C 6 H 4 - (CH 2) n -
OH (n is 1 to 14 integer), o-, m-, p- HO 2
_{C- (CH 2) n -C 6} H 4 - (CH 2) m -OH (n, m is 1 to 13 integer, n + m ≦ 14) are exemplified.

In order to extract a proton from the above compound to obtain a carboxylate anion of the general formula 5, the base exemplified in the preparation of the oxyanion of the general formula 4 can be suitably used. When a base acts on the above-mentioned hydroxyl group-containing carboxylic acid, protons of the carboxylic acid having higher acidity are extracted, and a carboxylate anion of the general formula 5 is selectively obtained. The amount of the base used may be 1 equivalent or more with respect to the hydroxyl group-containing carboxylic acid, but is preferably 0.8 to 1.5 equivalents.

In the method (E), a vinyl-based polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group as shown in the general formula 8 to replace the halogen. How to ^{M + C - (R 15)} (R 16) -R 17 -OH (8) ( wherein, R ^15, R ¹⁶ are both carbanion C ^- or an electron withdrawing group stabilizing, or one of the electronic On the other hand withdrawing group is hydrogen or an alkyl group having 1 to 10 carbon atoms or a phenyl group .R ¹⁷ is a direct bond, or carbon atoms, 1
Represents a divalent organic group of from 10 to 10, and may contain one or more ether bonds. M ⁺ as an alkali metal ion or an quaternary ammonium ion,) an electron withdrawing group _{^{R 15, R 16, -CO 2}} R, -C
Those having the structure of (O) R and -CN are particularly preferred.

In place of these carbanions, an organic metal compound such as a Grignard reagent having a hydroxyl group or an organic zinc compound may be used. In these methods, the hydroxyl group is preferably protected by an ester group or the like. The method (F) is described in, for example, JP-A-4-14-1.
A method of introducing a hydroxyl group into a terminal by hydrolyzing or reacting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond with a hydroxyl group-containing compound by a method as shown in 32706 or the like. It is.

Method (G) is a method using a compound having a hydroxyl group as an initiator of atom transfer radical polymerization. In this case, a vinyl polymer having a hydroxyl group at one end and a halogen group at the other end is obtained. By converting the terminal halogen group of the polymer thus obtained into a hydroxyl group-containing substituent, a vinyl polymer having hydroxyl groups at both ends can be produced.

The halide having a hydroxyl group is not particularly limited, but preferably has a structure represented by the general formula 6 or 7. ^{R 9 R 10 C (X)} -R 11 -R 12 -OH (6) ( wherein, R ^9, R ¹⁰ is hydrogen or a alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms Or an aralkyl group having 7 to 20 carbon atoms, or an aralkyl group linked to each other at the other end, wherein R ¹¹ is —C (O) O— (ester group), —C (O) — (keto group), or o -, M-, p
A phenylene group, X is chlorine, bromine or iodine, R ¹²
Is a direct bond or a divalent organic group having 1 to 20 carbon atoms,
More than five may contain an ether ^{bond) HO-R 12 -C (R} 9) (X) -R 11 -R 10 (7) ( ^{wherein, R 9, R 10, R} 11, R 12, X is the same as above. As a specific example of the compound represented by the general formula 6, XCH ₂ C
_{(O) O (CH 2)} n -OH, H 3 CC (H) (X) C
_{(O) O (CH 2)} n -OH, (H 3 C) 2 C (X) C
_{(O) O (CH 2)} n -OH, CH 3 CH 2 C (H) (X)
_{C (O) O (CH 2} ) n -OH,

[0055]

Embedded image

(In each of the above formulas, X represents chlorine, bromine,
Or iodine, n represents an integer of _{1~20) XCH 2 C (O)} O (CH 2) n O (CH 2) m -OH, H 3
CC (H) (X) C (O) O (CH 2) n O (CH 2) m -
OH, (H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n O (C
_{H 2) m -OH, CH 3} CH 2 C (H) (X) C (O) O
_{(CH 2) n O (CH} 2) m -OH,

[0057]

Embedded image

(In each of the above formulas, X represents chlorine, bromine,
Or iodine, n, m is an integer of 1 to 20) o-, m-, p-XCH 2 -C 6 H 4 - (CH 2) n -O
H, o-, m-, p- CH 3 C (H) (X) -C 6 H 4 -
_{(CH 2) n -OH, o-} , m-, p-CH 3 CH 2 C
_{(H) (X) -C 6} H 4 - (CH 2) n -OH, ( in each formula above, X is chlorine, bromine or iodine,, n is 0
Integer 20) o-, m-, p- XCH 2 -C 6 H 4 - (CH 2) n -O-
_{(CH 2) m -OH, o-} , m-, p-CH 3 C (H)
_{(X) -C 6 H 4 -} (CH 2) n -O- (CH 2) m -OH,
_{o-, m-, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -
(CH ₂ ) _n —O— (CH ₂ ) _m —OH (in each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 0 to 20, and m is an integer of 1 to 20). _{m-, p-XCH 2 -C 6} H 4 -O- (CH 2) n -
_{O- (CH 2) m -OH,} o-, m-, p-CH 3 C
_{(H) (X) -C 6} H 4 -O- (CH 2) n -O- (C
_{H 2) m -OH, o-,} m-, p-CH 3 CH 2 C (H)
_{(X) -C 6 H 4 -O-} (CH 2) n -O- (CH 2) m -O
H (in each of the above formulas, X is chlorine, bromine, or iodine, and n and m are integers of 1 to 20).

Specific examples of the compound represented by the general formula 7 include:
_{HO-CH 2 C (H)} (X) -CO 2 R, HO- (C
_{H 2) 2 C (H)} (X) -CO 2 R, HO- (CH 2) 3 C
_{(H) (X) -CO 2} R, HO- (CH 2) 8 C (H)
(X) —CO ₂ R, (in each of the above formulas, X is chlorine,
Bromine or iodine, R represents an alkyl group, an aryl group having 1 to 20 carbon atoms, an aralkyl _{group) HO-CH 2 C (H} ) (X) -C 6 H 5,, HO- (CH 2)
_{2 C (H) (X)} -C 6 H 5, HO- (CH 2) 3 C (H)
(X) -C ₆ H _5, and the like.

Specific examples of the sulfonyl halide compound having a hydroxyl group include o-, m- and p-HO-.
(CH ₂ ) _n —C ₆ H ₄ —SO ₂ X (where X is chlorine, bromine or iodine, and n is an integer of 0 to 20) o-, m-, p-HO- (CH ₂ ) _N -OC ₆ H ₄ -SO
₂ X, wherein X is chlorine, bromine or iodine, and n is an integer of 1 to 20.

When a vinyl monomer is polymerized using an organic halide having a hydroxyl group or a sulfonyl halide compound as an initiator, a hydroxyl group is introduced at one end, and a polymer having a highly reactive carbon-halogen bond at the other end. Coalescence is obtained. As a method of converting the terminal halogen into a hydroxyl group, the method described above can be suitably used.

The method (H) is a method of coupling the other end of the polymer having a hydroxyl group at one end obtained by the above method. In this method, the growing terminals may be directly coupled to each other, or the generated halogen terminal may be coupled using a compound having a total of two or more identical or different functional groups which react with the terminal.

There is no particular limitation on those having a total of two or more identical or different functional groups capable of substituting a terminal halogen, but examples thereof include polyols, polyamines, polycarboxylic acids, polythiols, and salts thereof, and alkali metal sulfides. Is preferred. If these compounds are specifically exemplified, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-
Propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, 1,5- Pentanediol, 1,
4-pentanediol, 2,4-pentanediol,
1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, glycerol, 1,2,4-butanetriol, catechol, resorcinol, hydroquinone, 1,2- Dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene,
2,6-dihydroxynaphthalene, 2,2'-biphenol, 4,4'-biphenol, bis (4-hydroxyphenyl) methane, 4,4'-isopropylidenephenol, 3,3 '-(ethylenedioxy) di Phenol,
α, α'-dihydroxy-p-xylene, 1,1,1-
Tris (4-hydroxyphenyl) ethane, pyrogallol, 1,2,4-benzenetriol, and an alkali metal salt of the above polyol compound, ethylenediamine,
1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1,2-diamino-2-
Methylpropane, 1,5-diaminopentane, 2,2-
Dimethyl-1,3-propanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 4,4 '
-Methylenebis (cyclohexylamine), 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-
Phenylenediamine, α, α′-diamino-p-xylene, and alkali metal salts of the above polyamine compounds, oxalic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 7,7-heptanedicarboxylic acid, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1,10
-Decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,
4-cyclohexanedicarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-benzenetricarboxylic acid,
1,2,4,5-benzenetetracarboxylic acid and alkali metal salts of the above polycarboxylic acids, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol , 1,5-pentanedithiol, 1,6-hexanedithiol, 1,
7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2-mercaptoethylether, p-xylene-α, α′-dithiol,
Examples thereof include 2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, and alkali metal salts of the above-mentioned polythiol compounds, lithium sulfide, sodium sulfide, potassium sulfide, and the like.

When the above-mentioned polyols, polyamines, polycarboxylic acids, and polythiols are used, a basic compound is used in combination to promote the substitution reaction. Specific examples thereof include lithium, sodium, potassium, sodium carbonate, and carbonate. Potassium, sodium hydrogencarbonate, sodium methoxide, potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydride, potassium hydride and the like can be mentioned. << Polyurethane Elastic Fiber >> In the present invention, as the polymer polyol, the above-mentioned vinyl polymer having a hydroxyl group at a terminal and another polymer polyol can be used in combination. However, it is necessary to use at least 20% by weight or more of the vinyl polymer (I) having a hydroxyl group at a terminal as a high molecular polyol. If the content is less than 20% by weight, the characteristics of light resistance, chlorine resistance and hot water resistance, which are the objects of the present invention, cannot be imparted.

Examples of other high molecular polyols include dihydroxy polyesters, dihydroxy polycarbonates, dihydroxy polyethers and the like. Examples of dihydroxy polyesters include ethylene glycol, propylene glycol, 1,6-hexanediol, 1,4-butanediol, at least one of neopentyl glycols and succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, Those obtained by reacting with at least one dicarboxylic acid such as sebacic acid, β-methyladipic acid, isophthalic acid and the like can be mentioned.

Examples of the dihydroxy polycarbonates include polycaprolactone glycol. Examples of the dihydroxy polyethers include polytetramethylene glycol, polyethylene glycol, and polypropylene glycol. Examples of the organic polyisocyanate used in the present invention include known aliphatic and aromatic groups having at least two isocyanate groups in the molecule.
It is an alicyclic organic polyisocyanate. For example, as organic diisocyanates, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, toluylene diisocyanate, 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, Isophorone diisocyanate,
Examples thereof include 4,4-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated methylene diphenyl diisocyanate. Examples of the organic triisocyanate include trimethylolpropane or one obtained by adding 3 mol of tolylene diisocyanate to 1 mol of glycerin. Preferred organic isocyanates have a molecular weight of 200 to 500, and 4,4-diphenylmethane diisocyanate is particularly preferred. These organic polyisocyanates may be used alone or as a mixture.

Examples of the chain extender used in the present invention include low molecular weight compounds having a molecular weight of 400 or less and having at least two hydrogen atoms capable of reacting with an isocyanate group, ie, polyhydric alcohols and polyamines. It is. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,12 -Dodecanediol, ethoxylated hydroquinone, 1,4-cyclohexanediol, trimethylolpropane, glycerin, sorbitol and the like. Preferred polyhydric alcohols are aliphatic diols having a molecular weight of 50 to 250.

As the polyvalent amines, hydrazine, 1,1,
2-diaminoethane, 1,3-diaminopropane, 1,
4-diaminobutane, 1,5-diaminopentane, 1,
6-diaminohexane, 3,3′-dichloro-4,4 ′
-Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane and the like. These chain extenders may be used alone or as a mixture.

The polyurethane resin of the present invention can be produced by a known method. For example, a so-called "one-shot" method in which a polymer polyol, an organic polyisocyanate, a chain extender and other additives are simultaneously mixed and reacted at a high temperature. Another method is the so-called "prepolymer" method, in which a high molecular polyol is first reacted with an organic polyisocyanate to synthesize an isocyanate-terminated prepolymer, and then the prepolymer is reacted with a chain extender. Furthermore, it is also possible to use a variant of the above method, in which the chain extender is first reacted with the organic polyisocyanate and then the resulting product is reacted with the polymeric polyol.
In the production of the polyurethane resin of the present invention, a catalyst can be used as required.

The average molecular weight of the obtained polyurethane is generally 5,000 to 500,000, preferably 10,000 to 50,000.
It is in the range of 400,000. If it is smaller than 5000, the mechanical properties are poor, and if it is larger than 500,000, the spinnability is poor. The polyurethane resin thus obtained can be fiberized by a known dry spinning method, wet spinning method, or melt spinning method. Among them, the melt spinning method is a preferable spinning method from the viewpoint of quality, production cost and environment.

In an appropriate stage of the resin production and spinning process, pigments, dyes,
Needless to say, additives such as fillers, lubricants, stabilizers, antioxidants, flame retardants, antistatic agents and surface treatment agents can be used as required. The polyurethane-based elastic fiber obtained in the present invention is excellent in durability such as light resistance, chlorine resistance and hot water resistance, and as an industrial application field, is used in the field of clothing such as swimwear, lingerie, foundation, underwear, and sportswear. Pantyhose, socks such as socks, supporters, bandages, medical fields such as masks, cataplasms, taping, etc., industrial materials such as car seats, chair upholstery, packaging materials, hair nets, handicrafts etc. Field.

[0072]

EXAMPLES The present invention will be specifically described below with reference to examples.
Note that the present invention is not limited to the following embodiments. Production Example 1 Production Example of an Initiator Having a Hydroxy Group Ethylene glycol (10.9 mL, 1
95 mmol) and pyridine (3 g, 39 mmol)
2-bromopropionic acid chloride (2 mL, 3.35 g, 19.5 mmol) was added to an HF solution (10 mL) at 0 ° C.
And slowly dripped. The solution was stirred for 2 hours at the same temperature. Dilute hydrochloric acid (20 mL) and ethyl acetate (30 mL)
Was added and the two layers were separated. The organic layer was washed with dilute hydrochloric acid and brine, dried over Na ₂ SO ₄ , and the volatiles were distilled off under reduced pressure to obtain a crude product (3.07 g). The crude product was distilled under reduced pressure (70-73 ° C., 0.5 m
mHg) to give hydroxyethyl-2-bromopropionate represented by the following formula (2.14 g, 56%). H ₃ CC (H) (Br) C (O) O (CH ₂ ) ₂ —OH Production Example 2 n-butyl acrylate (11
2 mL, 100 g, 0.78 mol), the hydroxyl group-containing initiator obtained in Production Example 1 (3.07 g, 15.6 mmol)
l), cuprous bromide (2.24 g, 15.6 mmol),
2,2′-bipyridyl (4.87 g, 31.2 mmol
l), ethyl acetate (90 mL), acetonitrile (22
mL), and nitrogen bubbling was performed to remove dissolved oxygen, followed by sealing. The mixture was heated to 130 ° C. and reacted for 2 hours. The reaction vessel was returned to room temperature, and 2-hydroxyethyl methacrylate (3.92 mL, 4.06 g,
31.2 mmol) and reacted at 110 ° C. for 2 hours. The mixture was diluted with ethyl acetate (200 mL), the insolubles were filtered off, and the filtrate was washed twice with 10% hydrochloric acid and once with brine. After the organic layer was dried over Na ₂ SO ₄ , the solvent was distilled off under reduced pressure to obtain 82 g of poly (n-butyl acrylate) having a terminal hydroxyl group. The number average molecular weight of the polymer was determined to be 5100 by GPC measurement (in terms of polystyrene).
The molecular weight distribution was 1.29. The average number of hydroxyl groups per polymer molecule determined by ¹ H-NMR analysis was 2.39. The viscosity of this polymer is 25 Pa ·
s. Comparative Production Example 1 According to Production Example 3 of JP-A-6-212922, poly (n-butyl acrylate) having hydroxyl groups at both ends was synthesized. That is, a 10 stirrer and a dropping funnel were provided.
In a 0 mL three-necked flask, 2-hydroxyethyl disulfide (30.8 g, 24.4 mL, 0.2 mol)
Was added. Heat the flask to 100 ° C. and add acrylic acid
n-butyl (12.8 g, 14.32 mL, 0.1 mol
l) and AIBN (0.328 g, 0.002 mol) were added dropwise over 30 minutes. The mixture was stirred at 100 ° C. for another hour. Toluene (20 mL) was added, the mixture was allowed to stand in a separating funnel, and the lower layer was separated. The upper layer was washed three times with water and dried over Na ₂ SO ₄ , and then volatile components were distilled off under reduced pressure to obtain poly (n-butyl acrylate) having hydroxyl groups at both ends (12). .1
8g, 95%). The number average molecular weight of the polymer was 4,300, and the molecular weight distribution was 4.22, as measured by GPC (in terms of polystyrene). Production Example 3 n-butyl acrylate (5 mL, 4.47 g, 34.9 mmol) in a 30 mL pressure-resistant reaction vessel, Production Example 1
(138 mg, 0.698
mmol), cuprous bromide (100 mg, 0.698 mm
ol), 2,2′-bipyridyl (218 mg, 1.40)
mmol), ethyl acetate (4 mL), and acetonitrile (1 mL), and dissolved oxygen was removed by bubbling with nitrogen. Heating the mixture to 130 ° C.,
The reaction was performed for 2 hours. The reaction vessel was returned to room temperature, and 2-hydroxyethyl methacrylate (0.176 mL, 182
mg, 1.40 mmol) and reacted at 100 ° C. for 2 hours. Dilute the mixture with ethyl acetate (20 mL),
After filtering off insolubles, the filtrate was washed twice with 10% hydrochloric acid and once with brine. After drying the organic layer over Na ₂ SO ₄ ,
The solvent was distilled off under reduced pressure to obtain 4.44 g of poly (n-butyl acrylate) having a hydroxyl group at a terminal represented by the following formula (93% yield). The number average molecular weight of the polymer was 6100 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.3.
It was 2. According to NMR measurement, the average number of hydroxyl groups per polymer molecule was 3.3. The viscosity of this polymer was measured by an E-type viscosity system (shear rate: 1).
0 sec ^-1 at 23 ° C.).

[0073]

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Comparative Production Example 2 According to Example 1 of JP-A-5-262808, poly (n-butyl acrylate) having hydroxyl groups at both ends was synthesized. That is, 100 equipped with a stirrer and a dropping funnel
To a mL three-necked flask was added 2-hydroxyethyl disulfide (30.8 g, 24.4 mL, 0.2 mol). Heat the flask to 100 ° C. and add acrylic acid-n
-Butyl (12.8 g, 14.32 mL, 0.1 mo
l) and AIBN (0.328 g, 0.002 mol) were added dropwise over 30 minutes. The mixture was stirred at 100 ° C. for another hour. Toluene (20 mL) was added, the mixture was allowed to stand in a separating funnel, and the lower layer was separated. The upper layer was washed three times with water and dried over Na ₂ SO ₄ , and then volatile components were distilled off under reduced pressure to obtain poly (n-butyl acrylate) having hydroxyl groups at both ends (12). .1
8g, 95%). The number average molecular weight of the polymer was 4,300, and the molecular weight distribution was 4.22, as measured by GPC (in terms of polystyrene). The viscosity of this polymer was measured by an E-type viscosity system (shear rate: 10 sec ^-1 , 23
° C) was 490 poise. The average number of hydroxyl groups per polymer molecule determined by ¹ H-NMR analysis was 1.42.

The properties of the polymers obtained in Production Example 3 and Comparative Production Example 2 are summarized in Table 1.

[0076]

[Table 1]

The polymer of Production Example 3 has a lower viscosity than the polymer of Comparative Production Example 2, despite having a considerably higher number average molecular weight. Here, the advantage that the molecular weight distribution of the polymer used in the present invention is narrow is apparent, and it is considered that the composition for producing the elastic fiber of the present invention can also be reduced in viscosity. Production Example 4 N-butyl acrylate (5 mL, 4.47 g, 34.9 mmol), α, α ′ were placed in a 30 mL pressure-resistant reaction vessel.
-Dibromo-p-xylene (185 mg, 0.70 mm
ol), cuprous bromide (100 mg, 0.70 mmol)
l), 2,2′-Bipyridyl (326 mg, 2.10 m
mol), ethyl acetate (4 mL), acetonitrile (1
mL), nitrogen bubbling was performed for 10 minutes to remove dissolved oxygen, and the tube was sealed. The mixture was heated to 130 ° C. and reacted for 3 hours. The reaction vessel was returned to room temperature, and 2-hydroxyethyl methacrylate (0.352 mL, 3
64 mg, 2.80 mmol), and seal the tube.
For 2 hours. The mixture was ethyl acetate (20 mL)
And washed three times with 10% hydrochloric acid and once with brine. After the organic layer was dried over Na ₂ SO ₄ , the solvent was distilled off under reduced pressure to obtain 4.11 g of poly (n-butyl acrylate) having a hydroxyl group at a terminal represented by the following formula (82%). The number average molecular weight of the polymer was 5,900 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.45. Also ¹
According to 1 H NMR analysis, the number of hydroxyl groups per polymer molecule was 3.2 on average.

[0078]

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Production Example 5 In Production Example 3, 10 mL of n-butyl acrylate was added.
Except for using the same procedure, 6.96 g of hydroxyl-terminated poly (n-butyl acrylate) was obtained (yield: 75%). The number average molecular weight of the polymer was 8,300 as measured by GPC (in terms of polystyrene), and the molecular weight distribution was 1.3.
It was 2. According to NMR measurement, the average number of hydroxyl groups per polymer molecule was 2.2. Production Example 6 In Production Example 3, 7.5 m of n-butyl acrylate was used.
Except for using L, 5.75 g of hydroxyl-terminated poly (n-butyl acrylate) was obtained in the same manner (yield: 82%). The number average molecular weight of the polymer was 7,500 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.36. Further, according to NMR measurement, polymer 1
The average number of hydroxyl groups per molecule was 2.1. Production Example 7 n-butyl acrylate (10.94 mL, 9.78 g, 76.3 mmol) was placed in a 50 mL pressure-resistant reaction vessel.
The hydroxyl group-containing initiator obtained in Production Example 1 (301 mg,
1.53 mmol), cuprous bromide (219 mg, 1.5
3 mmol), 2,2′-bipyridyl (476 mg,
3.05 mmol), ethyl acetate (8.8 mL), and acetonitrile (2.2 mL) were charged, and dissolved oxygen was removed by bubbling with nitrogen, followed by sealing. Mix 13
The mixture was heated to 0 ° C. and reacted for 1.3 hours. The mixture was diluted with ethyl acetate (20 mL) and washed three times with 10% hydrochloric acid and once with brine. After drying the organic layer over Na ₂ SO ₄ ,
The solvent was distilled off under reduced pressure to obtain 5.23 g of poly (n-butyl acrylate) having a hydroxyl group at one end (53%).
The number average molecular weight of the polymer was 3,400 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.31.
From ¹ H NMR analysis, the average number of hydroxyl groups per polymer molecule was 1.09.

Next, 50 m provided with a stirrer and a reflux condenser.
L into the three-necked flask, the poly (n-butyl acrylate) having a hydroxyl group at one end obtained above (2.15)
g), Na ₂ S · 9H ₂ O (76.3 mg, 0.318 m)
mol) and ethanol (3 mL), and stirred at reflux temperature for 3 hours. After cooling to room temperature, ethyl acetate (5 mL) and 10% hydrochloric acid (5 mL) were added, and the two layers were separated. The organic layer was washed with 10% hydrochloric acid and brine, Na ₂
After drying over SO ₄ , volatiles were distilled off under reduced pressure to obtain 1.93 g of poly (n-butyl acrylate) having a hydroxyl group at both terminals represented by the following formula. The number average molecular weight of the polymer was determined to be 570 by GPC measurement (in terms of polystyrene).
0 and the molecular weight distribution was 1.39.

[0081]

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Production Example 8 In a 100 mL reactor, n-butyl acrylate (20
mL, 17.9 g, 0.140 mmol), diethyl 2,5-dibromoadipate (0.628 g, 1.74 m)
mol), cuprous bromide (225 mg, 1.57 mmol)
l), pentamethyldiethylenetriamine (0.328
mL, 0.272 g, 1.57 mmol) and toluene (2.0 mL), followed by freezing and degassing, followed by purging with nitrogen. The mixture was heated to 70 ° C. and reacted for 45 minutes. At this point, the conversion of the monomer was 82%.
The reaction mixture was diluted with ethyl acetate and passed through a column of activated alumina to remove the copper catalyst to obtain a poly (n-butyl acrylate) having a bromine group at the terminal represented by the following formula. The number average molecular weight of the produced polymer was 10200, and the molecular weight distribution was 1.
It was 14.

The obtained poly (n-butyl acrylate)
(5.00 g), 4-hydroxybutyric acid sodium salt (0.248 g, 1.967 mmol) were mixed in N, N-dimethylacetamide (10 mL) and mixed at 70 ° C. for 3 hours.
Stirred for hours. The reaction solution was diluted with ethyl acetate, washed with water, and then the volatiles in the organic layer were distilled off under reduced pressure to obtain a polymer having hydroxyl groups at both ends represented by the following formula. ¹ H NM
According to R measurement, the number of hydroxyl groups per polymer molecule was 1.66 on average.

[0084]

As described above, according to the present invention, it is possible to provide a polyurethane elastic fiber having extremely excellent durability such as light resistance, chlorine resistance and hot water resistance. That is, it is achieved by melt-spinning a polyurethane resin having a hydroxyl group at a terminal and produced by polymerizing a vinyl polymer, an organic polyisocyanate and a chain extender produced by living radical polymerization. As a result, it can be applied to a field that has not been used due to its poor durability in the past, or has not been expanded in the market.

Continued on the front page F-term (reference) 4J034 BA08 CA04 CA05 CA15 CB03 CB04 CB07 CC02 CC03 CC12 CC23 CC26 CC45 CC52 CC61 CC65 CC67 CD04 CD13 CE03 DA01 DA03 DA05 DB03 DB04 DB07 DB08 DD11 DF01 DF02 DF16 DF20 DF22 DP13 DP03 DP06 DP06 DP15 DP16 DP17 DP18 DP19 DP20 HA01 HA02 HA07 HA08 HB07 HC03 HC12 HC13 HC17 HC22 HC46 HC52 HC61 HC64 HC67 HC71 HC73 QA05 QA07 QB15 RA09 4L035 EE01 EE07 EE20 FF01 FF04 GG01 HH01 HH04 HH10 MH02 MH09 M04

Claims (19)

[Claims] 1. An elastic fiber comprising polyurethane obtained by polymerizing a polymer polyol, an organic polyisocyanate, and a chain extender, wherein the polymer polyol has a terminal hydroxyl group and is produced by living radical polymerization. A polyurethane-based elastic fiber characterized by using the vinyl polymer (I) to be used. 2. The monomers constituting the polymer (I) are (meth) acrylic monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers and silicon-containing vinyl monomers. The composition according to claim 1, comprising at least one monomer selected from the group consisting of: 3. The polymer (I) has an average molecular weight of 500 to 50.
The polyurethane-based elastic fiber according to claim 1 or 2, wherein 4. The polymer (I) having an average functionality of 1.5 to 2.
The polyurethane elastic fiber according to any one of claims 1 to 3, wherein the polyurethane elastic fiber is 6. 5. The polyurethane elastic fiber according to claim 1, wherein the living radical polymerization is atom transfer radical polymerization. 6. The polyurethane elastic fiber according to claim 5, wherein the atom transfer radical polymerization for producing the polymer (I) uses a copper complex as a catalyst. 7. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) of the polymer (I) measured by gel permeation chromatography is less than 1.8. The polyurethane-based elastic fiber according to any one of claims 1 to 6. 8. The polyurethane elastic fiber according to claim 1, wherein the main chain of the polymer (I) contains no sulfur atom. 9. The polymer (I) is produced by producing a vinyl polymer by living radical polymerization and further reacting it with a compound having both a polymerizable alkenyl group and a hydroxyl group. The polyurethane-based elastic fiber according to any one of claims 1 to 8. 10. The compound having both a polymerizable alkenyl group and a hydroxyl group is a compound represented by the general formula 1.
The polyurethane-based elastic fiber according to the above. ^{_{H 2 C = C (R 1}} ) -R 2 -R 3 -OH (1) ( wherein, R ¹ represents a hydrogen or a methyl group, R ² is -C (O) O
-(Ester group), or o-, m-, p-phenylene group, and R ³ may be a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds.) 11. The polymer (I) is produced by producing a vinyl polymer by living radical polymerization, and further reacting the polymer with a compound having both an alkenyl group and a hydroxyl group having low polymerizability. Claims 1 to 8
The polyurethane-based elastic fiber according to any one of the above. 12. The polyurethane elastic fiber according to claim 11, wherein the compound having both an alkenyl group and a hydroxyl group having low polymerizability is a compound represented by the general formula 2. H ₂ C ＝ C (R ⁴ ) —R ⁵ —OH (2) In the above formula, R ⁵ is an alkyl group having 1 to 20 carbon atoms or a general formula 3: —C (R ⁷ ) ₂ —R ⁶ — C (R ⁷ ) _2- (3) (In the above formula, R ⁶ is an oxygen atom, a nitrogen atom or an organic group having 1 to 20 carbon atoms, and R ⁷ is a hydrogen atom or a methyl group which may be the same or different. And R ⁴ is a hydrogen atom or a methyl group. 13. An enolate anion is prepared by reacting a vinyl polymer having a halogen group at a terminal produced by atom transfer radical polymerization with a simple metal or an organometallic compound to produce an enolate anion. The polyurethane-based elastic fiber according to any one of claims 5 to 8, characterized in that the polyurethane-based elastic fiber is produced by reacting a compound or a ketone. 14. The polyurethane elastic fiber according to claim 13, wherein the metal simple substance is zinc. 15. The polymer (I) having a halogen-terminated vinyl polymer produced by atom transfer radical polymerization, comprising a hydroxyl group-containing oxyanion represented by the general formula 4 or a hydroxyl group-containing oxyanion represented by the general formula 5 The polyurethane-based elastic fiber according to any one of claims 5 to 8, which is produced by allowing a carboxylate anion to act. M ⁺ O ^-- R ⁸ -OH (4) (wherein, R ⁸ is a divalent alkyl group having 1 to 20 carbon atoms, a divalent aryl group having 6 to 20 carbon atoms, or 7 to 2 carbon atoms)
A divalent aralkyl group of 0, which may contain one or more ether bonds, M ⁺ is an alkali metal ion or a quaternary ammonium ion) M ⁺ OC (O) —R ⁸ —OH (5) , R ⁸ and M ⁺ are the same as above) 16. The method according to claim 5, wherein the organic halide as an initiator of the atom transfer radical polymerization for producing the polymer (I) or the sulfonyl halide compound is a halide having a hydroxyl group. The polyurethane-based elastic fiber according to any one of the above. 17. The polyurethane-based elastic fiber according to claim 16, wherein the halide having a hydroxyl group is a compound represented by the general formula 6 or 7. ^{R 9 R 10 C (X)} -R 11 -R 12 -OH (6) ( wherein, R ^9, R ¹⁰ is hydrogen or a alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms Or an aralkyl group having 7 to 20 carbon atoms, or an aralkyl group linked to each other at the other end, wherein R ¹¹ is —C (O) O— (ester group), —C (O) — (keto group), or o -, M-, p
A phenylene group, X is chlorine, bromine or iodine, R ¹²
Is a direct bond or a divalent organic group having 1 to 20 carbon atoms,
More than five may contain an ether ^{bond) HO-R 12 -C (R} 9) (X) -R 11 -R 10 (7) ( ^{wherein, R 9, R 10, R} 11, R 12, X is the same as above) 18. The polymer (I) is subjected to atom transfer radical polymerization using an organic halide having a hydroxyl group or a sulfonyl halide compound as an initiator, and a vinyl having a hydroxyl group at one end and a halogen group at the other end. It is produced by producing a base polymer and further coupling the halogen terminals using a compound having a total of two or more identical or different functional groups capable of substituting the halogen group. 17. The method of claim 16, wherein:
Or the polyurethane-based elastic fiber according to 17. 19. A coupling reaction of a terminal halogen group is carried out using a compound selected from the group consisting of polyols, polyamines, polycarboxylic acids, polythiols, and salts thereof, and alkali metal sulfides. The polyurethane elastic fiber according to claim 18.