JP3329856B2 - Polyurethane elastic fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to polyurethane elastic fibers. More specifically, the present invention relates to a polyurethane elastic fiber which has a low unwinding property and a good unwinding property because the spinneret is less contaminated when the polyurethane elastic fiber is produced by melt spinning.

The polyurethane elastic fiber provided by the present invention has abrasion resistance, lubricity, water repellency, etc. while maintaining the inherent strength, elongation, elongation recovery, etc. of polyester or polycarbonate polyurethane elastic fibers. And has excellent surface properties, and thus is excellent in melt spinnability.

[0003]

2. Description of the Related Art As a means for permanently imparting unique surface characteristics such as water repellency and surface smoothness to a polyurethane resin,
Polysiloxane chains produced by using a polysiloxane compound having one or two hydroxyl groups in the molecule in a urethanization reaction between a polymer diol such as polyester diol and polycarbonate diol, an organic diisocyanate, and a chain extender. Modified polyurethanes have been proposed. (JP-A-62-195389, JP-A-63-286466, and JP-A-64-286466)
43520, JP-A-2-60935, etc.). Such a modified polyurethane has a polysiloxane chain as a kind of soft segment or as a side chain branched from a hard segment.

[0004]

According to the study of the present inventors, modified polyurethane having the above-mentioned known polysiloxane chain as a kind of soft segment and modified polyurethane having a polysiloxane chain as a side chain branched from a hard segment are disclosed. In order to improve the effect of improving surface properties such as water repellency and surface smoothness, the proportion of polysiloxane chains is increased, and the resulting polyurethane elastic fiber is reduced in strength, elongation and elongation recovery. Was found to be significant.

An object of the present invention is to improve the abrasion resistance, lubricity, water repellency and the like while maintaining strength, elongation, elongation recovery, etc. Therefore, it is an object of the present invention to provide a polyurethane elastic fiber which is excellent in melt spinning properties such as few thread breaks and good unwinding property.

[0006]

According to the present invention, the above object has been achieved in that the main chain is mainly composed of (a) a structural unit (I-1) and / or a compound represented by the following formula (7). Structural unit (I-2) shown below, structural unit (II-1) shown below, and structural unit (III-
1) or structural unit (III-2) represented by Chemical formula 11, and comprises structural units (I-1), (I-2), (II-1), and (III-
1) and (III-2) form an ester bond and / or a carbonate bond and are mutually bonded to form a structural unit
The silicon atoms derived from (III-1) and (III-2) are added to a concentration of 0.
From 25 to 25% by weight of a polysiloxane having a hydroxyl group at both ends of the main chain, and having a number average molecular weight of 500 to 10,000. (B) a structural unit (IV) represented by the following formula (12); (c) a structural unit (V) represented by the following formula: d) substantially comprising a structural unit (I-2) represented by the following chemical formula 8 and / or a structural unit (I-3) represented by the following chemical formula 9 and a structural unit (II-2) shown below, I-2), (I
-3) and (II-2) form an ester bond and / or a carbonate bond and are mutually bonded, have hydroxyl groups at both ends of the main chain, and have a number average molecular weight of 50
A polymer diol unit [a] comprising a polymer diol unit [a] obtained by removing one hydrogen atom in each of hydroxyl groups located at both ends of the main chain from a polymer diol having a molecular weight of 0 to 10,000. And the sum of the molar percentage of the high molecular weight diol unit [d] and the molar percentage of the structural unit (V) is substantially equal to the molar percentage of the structural unit (IV).
This is achieved by providing an elastic fiber made of polyurethane having a weight percentage of (V) of 30% by weight or less and containing 0.01 to 20% by weight of silicon atoms.

[0007]

Embedded image (In the chemical formula 7, R ¹ represents a divalent hydrocarbon group.)

[0008]

Embedded image

[0009]

Embedded image (In the chemical formula 9, R ² represents a divalent hydrocarbon group.)

—OR ³ —O— (II-1) (wherein R ³ represents a divalent hydrocarbon group)

—OR ⁴ —O— (II-2) (wherein R ⁴ represents a divalent hydrocarbon group)

[0012]

Embedded image (Wherein, R ⁵ represents an alkanetriyl group having 3 to 6 carbon atoms, R ⁶ represents an alkylene group, R ⁷ , R ⁸ , R ⁹ , R
¹⁰ and R ¹¹ each represent an alkyl group or an aryl group having 1 to 6 carbon atoms, and m represents a number of 5 to 70)

[0013]

Embedded image (Wherein R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R
¹¹ and m are as defined above)

[0014]

Embedded image (In the formula 12, R ¹² represents a divalent organic group.)

-A- (V) (where A is a molecular weight of 400 containing two active hydrogen atoms)
2 in which the two active hydrogen atoms are removed from the following compound
Represents a valent organic group)

The divalent hydrocarbon group R in the structural unit (I-1)
Examples of the divalent hydrocarbon group R ^{2 in 1} and the structural unit (I-3) include an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group. Having 2 to 1 carbon atoms
An alkylene group of 2; having 6 to 6 carbon atoms, such as an o-phenylene group, an m-phenylene group, a p-phenylene group, and a naphthylene group;
And an arylene group having 10; a cycloalkanediyl group having 5 to 10 carbon atoms such as 1,4-cyclohexylene.

2 in the structural units (II-1) and (III-2)
Examples of the divalent hydrocarbon group R ³ and the divalent hydrocarbon group R ^{4 in the} structural unit (II-2) include an ethylene group, a propylene group, a tetramethylene group, a 2-methyltrimethylene group, and a pentamethylene group. A hexamethylene group, a 3-methylpentamethylene group, a 2,2-dimethyltrimethylene group,
Examples thereof include an alkylene group having 2 to 14 carbon atoms such as a nonamethylene group, a 2-methyloctamethylene group, and a decamethylene group.

As the alkanetriyl group R ⁵ having 3 to 6 carbon atoms in the structural units (III-1) and (III-2),
2,3-propanetriyl group,

[0019]

Embedded image (Wherein, R ¹³ represents a hydrogen atom, a methyl group or an ethyl group).

Examples of the alkylene group R ⁶ in the structural units (III-1) and (III-2) include an alkylene group having 2 to 6 carbon atoms such as an ethylene group and a trimethylene group. Examples of the alkyl group having 1 to 6 carbon atoms which may be represented by the groups R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ^{11 in the} structural units (III-1) and (III-2) include a methyl group and an ethyl group. Group,
Examples of the propyl group, isopropyl group, butyl group and the like, and the aryl group which may be represented by the groups R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ include a phenyl group, a methylphenyl group and the like having 6 carbon atoms To 8 aryl groups and the like. The groups R ⁹ in each repeating unit represented by the general formula —OSiR ⁹ R ¹⁰ — may be different from each other, and the groups R ¹⁰ may be different from each other. As a typical example of the structural unit (III-1),

[0021]

Embedded image (Wherein m is as defined above), a structural unit (III-1 ′) represented by the following formula:

Embedded image (In the formula 15, m is as defined above.)

And a structural unit (III-1 ″) represented by the following formula. A typical example of the structural unit (III-2) is
Following 16

[0023]

Embedded image (In the formula 16, m is as defined above.)

And the structural unit (III-2 ') shown below. In place of the structural unit (III-1) or the structural unit (III-2),

[0025]

Embedded image (Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and m are as defined above) or

[0026]

Embedded image (Wherein R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R
¹¹ and m are as defined above)

When the structural unit represented by the formula (1) is included, the C—O—Si portion contained therein is liable to be cut by a hydrolysis reaction, so that the surface characteristics such as abrasion resistance of the polyurethane elastic fiber are deteriorated. .

The polymer diol unit [a], which is one of the structural units constituting the polyurethane elastic fiber of the present invention, is substantially the same as the structural unit (I-1) and / or (I-
2) and the structural unit (II-1), and the structural unit (III-1) and / or (III-2). In the polymer diol unit [a], the mole of the structural unit (III-1) is used. The sum of the percentage and the molar percentage of the structural unit (III-2) is usually in the range of 0.4 to 10 mol%. The content of silicon atoms in the polymer diol unit [a] is 0.05 to 25 in that both the surface properties such as abrasion resistance, lubricity, and unwinding property and the mechanical strength of the polyurethane elastic fiber are improved.
% By weight, and 0.08 to 1%.
Preferably it is in the range of 5% by weight.

The number average molecular weight of the high molecular weight diol having a polysiloxane side chain which gives the high molecular weight diol unit [a] is 50.
It is in the range of 0 to 10,000. Number average molecular weight of 50
When it is less than 0, the cold resistance, low temperature properties and elongation of the polyurethane elastic fiber become insufficient, and when the number average molecular weight exceeds 10,000, the elongation recovery of the polyurethane elastic fiber becomes insufficient. .

The polymer diol unit [a] includes substantially the structural units (I-1), (II-1) and (I-1).
A polyester diol unit consisting of II-1) (hereinafter, such a polyester diol unit is referred to as a polymer diol unit [a-1]), substantially the structural units (I-1) and (I-1).
-2), a polyester carbonate diol unit composed of the structural unit (II-1) and the structural unit (III-1) (hereinafter, such a polyester carbonate diol unit is referred to as a polymer diol unit [a-2]), substantially Structural unit (I
-2), a polycarbonate diol unit composed of the structural unit (II-1) and the structural unit (III-1) (hereinafter, such a polycarbonate diol unit is referred to as a polymer diol unit [a-
3]), substantially structural unit (I-2), structural unit
A polycarbonate diol unit composed of (II-1) and a structural unit (III-2) (hereinafter, such a polycarbonate diol unit is referred to as a polymer diol unit [a-4])
Etc. are included.

The two organic groups R ¹² in the structural unit (IV) include divalent saturated aliphatic hydrocarbon groups such as hexamethylene group; isophoronediyl group, dicyclohexylmethane-
Divalent saturated alicyclic hydrocarbon group such as 4,4'-diyl group; diphenylmethane-4,4'-diyl group, p-phenylene group, methylphenylene group, 1,5-naphthylene group, xylene-α, A divalent aromatic hydrocarbon group such as an α'-diyl group is preferred. Particularly preferred is a dicyclohexylmethane-4,4'-diyl group.

The main chain of the polyurethane elastic fiber of the present invention is
As described above, the polymer diol unit [a] and the structural units (IV) and (V) are contained as essential structural units, and the polymer diol unit [d] is contained in addition to these structural units. It may be.

The polymer diol unit [d] includes a polyester diol unit substantially consisting of a structural unit (I-3) and a structural unit (II-2) (hereinafter, such a polyester diol unit is referred to as a polymer diol unit [d]). -1]),
Substantially the structural units (I-2) and (I-3) and the structural unit (I
A polyester carbonate diol unit consisting of I-2) (hereinafter, such a polyester carbonate diol unit is referred to as a polymer diol unit [d-2]), substantially a structural unit (I-2) and a structural unit (II-2) (Hereinafter, such a polycarbonate diol unit is referred to as a polymer diol unit [d-3]) and the like. The number average molecular weight of the high molecular weight diol such as polyester diol, polyester carbonate diol and polycarbonate diol which gives the high molecular weight diol unit [d] is in the range of 500 to 10,000. When the number average molecular weight is less than 500, the cold resistance, low temperature properties and elongation of the polyurethane elastic fiber may be insufficient, and the number average molecular weight is 10,000.
When the ratio exceeds the above, the elongation recovery of the polyurethane elastic fiber may be insufficient. The content of the polymer diol unit [d] is desirably 60% by weight or less based on the polyurethane elastic fiber of the present invention.

General formula HAH giving structural unit (V) (where A is as defined above)

The compounds containing two active hydrogen atoms and having a molecular weight of 400 or less include those used as a chain extender in the production of ordinary polyurethane. Typical examples are ethylene glycol,
1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, xylylene glycol, 1,4-bis (β-hydroxyethoxy) benzene, bis (β-hydroxyethyl ) Diols such as terephthalate; 3,3′-dichloro-4,4′-diaminodiphenylmethane, isophoronediamine, 4,4 ′
Diamines such as diaminodiphenylmethane and ethylenediamine; hydrazine; heterocyclic compounds containing two imino groups such as piperazine in a cyclic structure; and low molecular compounds such as dihydrazide such as adipic dihydrazide and isophthalic dihydrazide. Particularly preferred is 1,4-butanediol. The content of the structural unit (V) is 20% by weight based on the polyurethane elastic fiber of the present invention.
For the purpose of obtaining a polyurethane having good melt spinnability, the content is preferably in the range of 2 to 15% by weight. In addition, in this specification, an active hydrogen atom means a hydrogen atom that can react with an isocyanate group.

The main chain of the polyurethane used for the elastic fiber of the present invention is mainly composed of the polymer diol unit [a], the structural unit (IV) and the structural unit (V), and the polymer diol unit [d] optionally contained. ] Form a urethane bond or a urea bond to form a bond. In the polyurethane of the present invention, the sum of the molar percentage of the high molecular diol unit [a], the molar percentage of the high molecular diol unit [d], and the molar percentage of the structural unit (V) is substantially equal to the molar percentage of the structural unit (IV). Equal. The content of silicon atoms in the polyurethane elastic fiber of the present invention is in the range of 0.01 to 20% by weight. When the content of silicon atoms is less than 0.01% by weight, the polyurethane elastic fiber cannot exhibit sufficient surface characteristics, and when the content of silicon atoms exceeds 20% by weight, the polyurethane elasticity fiber does not. The fiber strength, elongation and elongation recovery are insufficient.

The polyurethane used for the elastic fiber of the present invention comprises the above-mentioned polysiloxane side chain-containing polymer diol giving the above-mentioned polymer diol unit [a] and the organic diisocyanate giving the structural unit (IV), that is, the general formula O ＯC ＮNR ¹² -N ＝ C ＝ O (VI) wherein R ¹² is as defined above and an organic diisocyanate and a chain extender, to give a high molecular diol unit [d]. It is produced by polymerizing in the presence or absence of a molecular diol.

As the organic diisocyanate represented by the general formula (VI), for example, 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate,
Aromatic diisocyanates such as tolylene diisocyanate and 1,5-naphthylene diisocyanate; aliphatic diisocyanates such as xylylene diisocyanate and hexamethylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate. Can be Particularly preferred is 4,4'-diphenylmethane diisocyanate.

As described above, the polymer diol that gives the polymer diol unit [d] includes the polymer diol unit [d]
-1], a polyester carbonate diol that provides a polymer diol unit [d-2], a polycarbonate diol that provides a polymer diol unit [d-3], and the like. Examples of the polyester diol include polytetramethylene adipate diol, polyethylene adipate diol, polyhexamethylene adipate diol, poly-3-methylpentamethylene adipate diol, polyalkylene adipate diol containing ethylene glycol and propylene glycol as alkylene glycol components, And known polyester diols such as polyalkylene adipate diol, poly-3-methylpentamethylene azelate diol, and polycaprolactone diol having an alkylene glycol component of 2,9-nonanediol and 2-methyl-1,8-octanediol. Is exemplified. Examples of the polycarbonate diol include known polycarbonate diols such as polyhexamethylene carbonate diol and polyalkylene carbonate diol having 1,9-nonanediol and 2-methyl-1,8-octanediol as alkylene glycol components. Is done.

Polysiloxane side chain-containing high molecular weight diols include polyester diols substantially consisting of structural units (I-1), (II-1) and (III-1) (hereinafter, such polyester diols). Is referred to as a polymer diol [A-1]), substantially the structural unit (I-1),
(I-2), structural unit (II-1) and structural unit (III-1)
A polyester carbonate diol (hereinafter, such a polyester carbonate diol is referred to as a polymer diol [A-2]) consisting essentially of a structural unit (I-2),
A polycarbonate diol composed of the structural unit (II-1) and the structural unit (III-1) (hereinafter, such a polycarbonate diol is referred to as a polymer diol [A-3]), substantially the structural unit (I-2), and the structure Polycarbonate diols comprising units (II-1) and structural units (III-2) (hereinafter, such polycarbonate diols are referred to as polymer diols [A-4]) and the like are included. The polymer diol (A-1), the polymer diol (A-2), the polymer diol (A-3) and the polymer diol (A-4) are each contained in the polyurethane elastic fiber of the present invention. Polymer diol unit (a-1), polymer diol unit (a
-2), a polysiloxane side chain-containing polymer diol which provides a polymer diol unit (a-3) and a polymer diol unit (a-4).

The polymer diol (A-1) is, for example, a monomer which gives a desired structural unit (I-1), that is, a general formula HOOC-R ¹ -COOH (VII) (wherein R ¹ is as defined above) And a monomer that gives a desired structural unit (II-1), that is, a general formula HO—R ³ —OH (VIII) (wherein R ³ is A monomer which gives a desired structural unit (III-1), that is, a diol represented by the following formula:

[0042]

Embedded image (Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and m are as defined above) or a diol (IX-1) containing a side chain of a polysiloxane, Below 20

[0043]

Embedded image (In the formula, R ¹³ represents an alkylene group having 1 to 4 carbon atoms, and R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and m are as defined above.)

The polysiloxane chain-containing alkylene oxide (IX-2) is used at a predetermined ratio, and these are subjected to an esterification reaction or a transesterification reaction at 150 to 250 ° C. to obtain a low polymer. From 180 to 25
It is produced by subjecting to a polycondensation reaction at 0 ° C. Such a polycondensation reaction is usually performed under reduced pressure in the presence of a polycondensation catalyst. As the polycondensation catalyst, polycondensation catalysts used in the production of ordinary polyesters can be employed, and titanium compounds such as tetraisopropoxytitanium and tetra-n-butoxytitanium; di-n-butyltin dilaurate, di- Examples include tin compounds such as n-butyltin oxide and dibutyltin diacetate; combinations of metal salts of acetic acid such as magnesium acetate, calcium acetate and zinc acetate with antimony oxide or the above titanium compounds. These polycondensation catalysts are
It is preferable to use it within the range of 500 ppm.

The polymer diol (A-2) is, for example, a monomer which gives the structural unit (I-1), that is, a monomer represented by the general formula (VII):
And a monomer giving the desired structural unit (I-2), that is, a carbonate ester such as dialkyl carbonate, diaryl carbonate, or alkylene carbonate; and the desired structural unit (II-1) A diol represented by the general formula (VIII); and the desired structural unit (III-
The monomer giving 1), that is, a polysiloxane side chain-containing diol (IX-1) or a polysiloxane chain-containing alkylene oxide (IX-2) is used at a predetermined ratio, and these are subjected to an esterification reaction at 100 to 230 ° C. After subjecting to a transesterification reaction, the obtained low polymer was further converted to 180 to 23.
It is produced by subjecting to a polycondensation reaction at 0 ° C. Such a polycondensation reaction is usually performed under reduced pressure in the presence of a polycondensation catalyst. As the polycondensation catalyst, catalysts used in the production of ordinary polyesters and polycarbonates can be employed, and titanium compounds such as tetraisopropoxytitanium and tetra-n-butoxytitanium; di-n-
Tin compounds such as butyltin dilaurate, di-n-butyltin oxide and dibutyltin diacetate; combinations of metal salts of acetic acid such as magnesium acetate, calcium acetate and zinc acetate with antimony oxide or the above-mentioned titanium compounds can be exemplified. . These catalysts are preferably used in an amount of 1 to 500 ppm based on the product.

The polymer diol (A-3) is, for example, a monomer giving the structural unit (I-2), that is, a carbonate such as dialkyl carbonate, diaryl carbonate, or alkylene carbonate; and the desired structural unit (II-1) Monomer, ie, the general formula (VIII)
And a monomer giving a desired structural unit (III-1), that is, a polysiloxane side chain-containing diol (IX-1) is used at a predetermined ratio, and these are used in an amount of 10%.
It is produced by subjecting it to a transesterification reaction at 0 to 230 ° C. Such a transesterification reaction can be performed under any pressure of normal pressure or reduced pressure depending on the progress of the reaction. In the transesterification reaction, a catalyst is not always necessary, but it is desirable to use a catalyst when the reaction is desired to be accelerated. As such a catalyst, transesterification catalysts used in the production of ordinary polycarbonates can be used, and titanium compounds such as tetraisopropoxytitanium and tetra-n-butoxytitanium; di-n-
Tin compounds such as butyltin dilaurate, di-n-butyltin oxide and dibutyltin diacetate; combinations of metal salts of acetic acid such as magnesium acetate, calcium acetate and zinc acetate with antimony oxide or the above-mentioned titanium compounds can be exemplified. . These catalysts are preferably used in an amount of 1 to 500 ppm based on the product.

The polymer diol (A-4) is, for example, a monomer giving the structural unit (I-2), that is, a carbonate such as dialkyl carbonate, diaryl carbonate, or alkylene carbonate; and the desired structural unit (II-1) and the general formula ^{-O-R 3 -O- (III-} 2a) ( wherein, R ³ is as defined above) in a desired structural unit (III-2) monomers giving fragments represented by, i.e. A diol represented by the general formula (VIII): embedded image in the desired structural unit (III-2)

[0048]

Embedded image (Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and m are as defined above)

A monomer giving the fragment (III-2b) represented by the formula, ie, a polysiloxane chain-containing alkylene oxide (IX-2) is used at a predetermined ratio, and
It is produced by subjecting to a transesterification reaction accompanied by a fragmentation addition reaction at 0 to 230 ° C. Such a transesterification reaction can be performed under any pressure of normal pressure or reduced pressure depending on the progress of the reaction. In the transesterification reaction, a catalyst is not always necessary, but it is desirable to use a catalyst when the reaction is desired to be accelerated. As such a catalyst, transesterification catalysts used in the production of ordinary polycarbonates can be employed, and titanium compounds such as tetraisopropoxytitanium and tetra-n-butoxytitanium; di-n-butyltin dilaurate, di-n −
Examples include tin compounds such as butyltin oxide and dibutyltin diacetate; combinations of metal salts of acetic acid such as magnesium acetate, calcium acetate and zinc acetate with antimony oxide or the above titanium compounds. These catalysts are preferably used in an amount of 1 to 500 ppm based on the product.

Representative examples of the dicarboxylic acids represented by the general formula (VII) include saturated aliphatic dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; isophthalic acid, terephthalic acid, phthalic acid; 6-
Aromatic dicarboxylic acids such as hydroxy-2-naphthoic acid; and saturated alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid. Representative examples of the ester-forming derivative of the dicarboxylic acid include di-lower alkyl esters such as dimethyl ester and diethyl ester of the above-described dicarboxylic acid.

Examples of the carbonic ester giving the structural unit (I-2) include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; diaryl carbonates such as diphenyl carbonate; and alkylene carbonates such as ethylene carbonate and propylene carbonate. .

Representative examples of the diol represented by the general formula (VIII) include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 3-methyl-1 , 5-
Pentanediol, neopentyl glycol, 1,9-
Examples include nonanediol, 2-methyl-1,8-octanediol, and 1,10-decanediol.

Polysiloxane side chain-containing diol (IX-
A typical example of 1) is shown below.

Embedded image (Wherein m is as defined above), a compound represented by the following formula:

[0054]

Embedded image (Wherein, m is as defined above).

Representative examples of the polysiloxane chain-containing alkylene oxide (IX-2) are shown below.

Embedded image Wherein m is as defined above, and the like.

In producing the polyurethane used for the elastic fiber of the present invention, various known methods and apparatuses of a batch type or a continuous type can be employed. In particular, it is preferable to carry out the polymerization of the polyurethane in a molten state substantially in the absence of a solvent, and it is more preferable to carry out the continuous melt polymerization using an extruder such as a multi-screw type. Although the temperature at this time is not particularly limited, it is usually preferably in the range of about 200 to 260 ° C. By maintaining the temperature at the time of polymerization at 260 ° C or lower, the heat resistance and mechanical properties of the polyurethane are improved. By maintaining the temperature at 200 ° C. or higher, a polyurethane having excellent melt spinnability can be produced. At this time, it is preferable that the ratio (R value) between the isocyanate group and the active hydrogen atom in the raw material is in the range of 1.0 to 1.1.

The polyurethane thus obtained is
Once pelletized and then melt-spun, or a method in which polyurethane obtained by melt polymerization is directly spun through a spinneret in a molten state can be adopted. From the viewpoint of spinning stability, a directly-polymerized spinning yarn is preferred. When the polyurethane elastic fiber of the present invention is obtained by melt spinning, the spinning temperature is 250 ° C or lower, more preferably 200 ° C or higher and 235 ° C.
It is practical to spin below.

The polyurethane elastic fiber of the present invention has improved surface properties such as abrasion resistance, lubricity, and water repellency while maintaining excellent strength, elongation, elongation recovery, and the like. When the spinneret is less stained,
It has excellent features such as low thread breakage and good unwinding properties.

[0059]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

The compounds used in Examples, Comparative Examples and Reference Examples are indicated by abbreviations. Tables 1 and 2 show the relationship between the abbreviations and the compounds.

[0061]

[Table 1]

[0062]

[Table 2]

The content of silicon atoms in the polymer diol and the polyurethane elastic fiber was measured by an atomic absorption method.

The measurement of the strength and elongation of the polyurethane elastic fiber was performed according to JIS L-1013. The instantaneous elastic recovery rate was obtained by applying JIS L-1096, holding for 2 minutes after elongating at 200%, and determining the resilience immediately after removing the stress according to the following equation. Instantaneous elastic recovery rate = 100 × [nl− (l′−l)] / n
l (n: elongation ratio, l: initial length, l ': length after stress relief)

The stain on the spinneret after 24 hours of continuous spinning and the unwinding property of the wound elastic yarn were evaluated on a four-point scale.

Reference Example 1 (Polymer diol [A-1]) 1000 g of 3-methyl-1,5-pentanediol, 1310 g of azelaic acid and 8 g of XA were charged into a reactor, and water produced at 200 ° C. under a nitrogen stream was added. The esterification reaction was carried out while distilling out of the system. 0.03 g of tetraisopropoxy titanium at the time when distilling of water is almost gone
And the degree of vacuum was gradually increased to complete the reaction under a vacuum of 3 mmHg. The resulting polymer diol 1 has a hydroxyl value of 5
It had 5.5 and an acid value of 0.15, and its silicon atom content was 0.14% by weight.

[0067] except for using a predetermined amount of monomer in Reference Example 2-4 in Table 3 in the same manner as in Reference Example 1 to obtain a polymer diol 2-4.

[0068]

[Table 3]

Reference Example 5 (Polymer diol [A-2]) 640 g of 3-methyl-1,5-pentanediol,
6-hexanediol 640 g, azelaic acid 855
g, 480 g of ethylene carbonate and 20 g of XA were charged into a reactor, and an esterification and a carbonate reaction were carried out under a nitrogen stream while distilling off water and ethylene glycol produced at 200 ° C. out of the system. When the distillation almost disappeared, tetraisopropoxy titanium 0.03
g was added, and the degree of vacuum was gradually increased to complete the reaction under a vacuum of 3 mmHg. The resulting polymer diol 5 has a hydroxyl value of 5
It had 5.5 and an acid value of 0.10, its number average molecular weight was 2020, and its silicon atom content was 0.35% by weight.

Reference Example 6 (Polymer diol [A-3]) 475 g of 3-methyl-1,5-pentanediol,
475 g of 6-hexanediol, 853 g of 1,9-nonanediol, 1130 g of ethylene carbonate and X
10 g of A was charged into a reactor, and a condensation reaction was carried out while distilling off ethylene glycol produced at 200 ° C. out of the system.
The degree of vacuum was gradually increased from the point when almost no distilling occurred, and ethylene glycol was completely distilled off under a vacuum of 5 to 10 mmHg. The resulting polymer diol 6 had a hydroxyl value of 55.
8 and an acid value of 0.06, and its number average molecular weight is 20.
10, and the silicon atom content was 0.18% by weight.

Example 1 Polymer diols 1 and 1, each heated to 80 ° C.
4-Butanediol and MDI heated and melted at 50 ° C. were continuously supplied to a twin-screw extruder by a metering pump so that the composition shown in Table 4 was obtained, and continuous melt polymerization was performed. It was extruded into water and cut into pellets. The pellets were vacuum-dried at 80 ° C. for 20 hours, and a 40-denyl elastic yarn was obtained at a spinning temperature of 215 ° C. and a spinning speed of 500 m / min using a conventional spinning machine equipped with a single screw extruder. The wound elastic yarn was aged at 80 ° C. for 20 hours under low humidity, and further aged for 3 days at room temperature and 60% humidity to measure various physical properties. In addition, Table 4 shows the results of evaluating dirt on the spinneret after 24 hours of continuous spinning and the unwinding property of the wound elastic yarn in four stages.

[0072]

[Table 4]

Examples 2 to 6, Comparative Examples 1 and 2 In the same manner as in Example 1, a polyurethane was synthesized so as to have the composition shown in Table 4, and after pelletizing, spinning was performed.
A denenyl elastic yarn was obtained. These were aged under the same conditions as in Example 1 and the obtained elastic fibers were evaluated.
Shown in The elastic fiber provided by the present invention has high strength and elongation as well as little stain on the spinneret at the time of spinning, and is excellent in unwinding property, as is clear from the above examples.

[0074]

The polyurethane elastic fiber of the present invention has strength,
It has improved surface properties such as abrasion resistance, lubricity, water repellency, etc., while maintaining elongation, elongation recovery, etc. It is possible to provide a polyurethane elastic fiber which is low in melt spinnability such as good unwinding property.

Claims (1)

(57) [Claims] The main chain is mainly composed of (a) a structural unit (I-1) substantially represented by the following chemical formula 1 or a structural unit (I-2) represented by the chemical formula 2 and a structural unit (II)
-1) and a structural unit (III-1) represented by the following chemical formula 4 or a structural unit (III-2) represented by the following chemical formula 5,
(I-1), (I-2), (II-1), (III-1) and (III
-2) form an ester bond and / or a carbonate bond and are mutually bonded, and a silicon atom derived from the structural units (III-1) and (III-2) is added in an amount of 0.05 to 25.
% Of a polysiloxane having a hydroxyl group at both ends of the main chain and having a number average molecular weight of 500 to 10,000. (B) a structural unit (IV) represented by the following formula (6); (c) a structural unit (V) shown below; and, if desired, (d) a substantial unit. Specifically, the structural unit (I-2) comprises a structural unit (I-2) represented by the following chemical formula 2 and / or a structural unit (I-3) represented by the following chemical formula 3 and the following structural unit (II-2). ), (I
-3) and (II-2) form an ester bond and / or a carbonate bond and are mutually bonded, have hydroxyl groups at both ends of the main chain, and have a number average molecular weight of 50
A polymer diol unit [a] comprising a polymer diol unit [a] obtained by removing one hydrogen atom in each of hydroxyl groups located at both ends of the main chain from a polymer diol having a molecular weight of 0 to 10,000. And the sum of the molar percentage of the high molecular weight diol unit [d] and the molar percentage of the structural unit (V) is substantially equal to the molar percentage of the structural unit (IV).
An elastic fiber produced from a polyurethane having a weight percentage of (V) of 30% by weight or less and containing 0.01 to 20% by weight of silicon atoms. Embedded image (In the formula ¹ , R ¹ represents a divalent hydrocarbon group.) Embedded image (Wherein R ² represents a divalent hydrocarbon group) —OR ³ —O— (II-1) (wherein, R ³ represents a divalent hydrocarbon group). ⁴ -O- (II-2) (wherein, R ⁴ represents a divalent hydrocarbon group) embedded image (Wherein, R ⁵ represents an alkanetriyl group having 3 to 6 carbon atoms, R ⁶ represents an alkylene group, and R ⁷ , R ⁸ , R ⁹ , R ¹⁰
And R ¹¹ each represents an alkyl group or an aryl group having 1 to 6 carbon atoms, and m represents a number of 5 to 70. (Wherein R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹
And m are as defined above. (Wherein R ¹² represents a divalent organic group) -A- (V) (where A is a molecular weight of 40 containing two active hydrogen atoms)
A divalent organic group in which the two active hydrogen atoms are removed from a compound having 0 or less)