JPH06116388A - Polyurethane elastic yarn - Google Patents

Abstract

PURPOSE:To obtain the subject yarn maintaining strength, elongation, etc., having improved lubricating properties, water repellency, etc., comprising a Si-containing polyurethane of a specific structure. CONSTITUTION:The objective yarn comprises a polyol containing (A) a diol unit made by removing each one H from hydroxyl groups at both ends of a polysiloxane side chain-containing polymer diol which contains OH groups at both ends and has a main chain consisting of a unit of formula I or formula II (R<1> is bifunctional hydrocarbon), a unit of the formula O-R<3>-O (R<3> is as shown for R<1>) and a unit of formula III or formula IV (R<5> is 3-6C alkanetriyl; R<6> is alkylene; R<7> to R<11> are 1-6C alkyl or aryl; (m) is 5-70), wherein these units form ester bond and/or carbonate bond and mutually bonded, content of Si derived from the unit III and the unit IV is 0.05-25wt.%, (B) a unit of formula V (R<12> is bifunctional organic group) and (C) a unit composed of a bifunctional organic group prepared by removing two active hydrogen atoms from a compound having two active hydrogen atoms and 400 or smaller molecular weight.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to polyurethane elastic fibers. More specifically, the present invention relates to a polyurethane elastic fiber having a good unwinding property, since the spinning spinneret is less contaminated during the production of the polyurethane elastic fiber by melt spinning.

The polyurethane elastic fiber provided by the present invention has abrasion resistance, lubricity, water repellency, etc. while retaining the original strength, elongation, elongation recovery and the like of polyester or polycarbonate polyurethane elastic fiber. The melt spinning property is excellent because it has improved surface characteristics.

[0003]

2. Description of the Related Art As means for permanently imparting unique surface properties such as water repellency and surface smoothness to polyurethane resins,
A polysiloxane chain produced by using a polysiloxane compound having one or two hydroxyl groups in the molecule in a urethane reaction of a polymer diol such as polyester diol and polycarbonate diol, an organic diisocyanate and a chain extender A modified polyurethane having is proposed. (JP-A-62-195389, JP-A-63-286466, JP-A-64-
43520, Japanese Patent Laid-Open No. 2-60935, etc.). Such a modified polyurethane has a polysiloxane chain as a kind of soft segment or a side chain branched from a hard segment.

[0004]

According to the studies made by the present inventors, a modified polyurethane having the above-mentioned known polysiloxane chain as a kind of soft segment and a modified polyurethane having a polysiloxane chain as a side chain branched from a hard segment. Then, if the proportion of polysiloxane chains is increased in order to improve the surface properties such as water repellency and surface smoothness, the strength, elongation and elongation recovery of the resulting polyurethane elastic fiber decrease. Was found to be significant.

Therefore, the object of the present invention is to improve the wear resistance, lubricity, water repellency, and other surface characteristics while maintaining strength, elongation, elongation recovery, etc. Therefore, it is to provide a polyurethane elastic fiber having excellent melt spinnability, such as less yarn breakage and good unwinding property.

[0006]

According to the present invention, the above-mentioned object is achieved by the main chain consisting mainly of (a) a structural unit (I-1) substantially represented by the following Chemical formula 7 and / or a structural unit The structural unit (I-2) shown below, the structural unit (II-1) shown below, and the structural unit (III-
1) or a structural unit (III-2) represented by Chemical formula 11, and structural units (I-1), (I-2), (II-1), (III-
1) and (III-2) are linked to each other by forming an ester bond and / or a carbonate bond,
The silicon atom derived from (III-1) and (III-2) is 0.
Of the polysiloxane side chain-containing high molecular weight diol, which contains 0 to 25% by weight, has hydroxyl groups at both ends of the main chain, and has a number average molecular weight of 500 to 10,000, located at both ends of the main chain. A polymer diol unit [a] in the form of removing one hydrogen atom respectively; (b) a structural unit (IV) represented by the following chemical formula 12; (c) a structural unit (V); d) A structural unit (I-2) substantially represented by the following chemical formula 8 and / or a structural unit (I-3) represented by the following chemical formula 9 and the following structural unit (II-2), I-2), (I
-3) and (II-2) are bound to each other by forming an ester bond and / or a carbonate bond, have hydroxyl groups at both ends of the main chain, and have a number average molecular weight of 50.
The polymer diol unit [a] is composed of a polymer diol unit [d] in the form of a polymer diol having a molecular weight of 0 to 10,000 and having one hydrogen atom in each of the hydroxyl groups located at both ends of its main chain. The sum of the mole percentage of the polymer diol unit [d] and the mole percentage of the structural unit (V) is substantially equal to the mole percentage of the structural unit (IV),
It is achieved by providing elastic fibers made from polyurethane having a weight percentage of (V) of not more than 30% by weight and containing 0.01 to 20% by weight of silicon atoms.

[0007]

[Chemical 7] (In chemical formula 7, R ¹ represents a divalent hydrocarbon group)

[0008]

[Chemical 8]

[0009]

[Chemical 9] (In Chemical Formula 9, R ² represents a divalent hydrocarbon group)

—O—R ³ —O— (II-1) (In the formula, R ³ represents a divalent hydrocarbon group)

—O—R ⁴ —O— (II-2) (In the formula, R ⁴ represents a divalent hydrocarbon group)

[0012]

[Chemical 10] (In Chemical Formula 10, 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 and 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]

[Chemical 11] (In chemical formula 11, R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R
¹¹ and m are as defined above)

[0014]

[Chemical 12] (In chemical formula 12, R ¹² represents a divalent organic group)

-A- (V) (In the formula, A is a molecular weight of 400 containing two active hydrogen atoms.
2 in the form in which the two active hydrogen atoms have been removed from the following compounds
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. 2 to 1 carbon number
2 alkylene groups; 6-carbon atoms such as o-phenylene group, m-phenylene group, p-phenylene group, naphthylene group
Examples thereof include 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)
The divalent hydrocarbon group R ³ and the divalent hydrocarbon group R ^{4 in the} structural unit (II-2) are an ethylene group, a propylene group, a tetramethylene group, a 2-methyltrimethylene group and a pentamethylene group, respectively. , Hexamethylene group, 3-methylpentamethylene group, 2,2-dimethyltrimethylene group,
Examples thereof include alkylene groups having 2 to 14 carbon atoms such as nonamethylene group, 2-methyloctamethylene group and 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]

[Chemical 13] (In Chemical Formula 13, R ¹³ represents a hydrogen atom, a methyl group or an ethyl group) and the like.

Examples of the alkylene group R ⁶ in the structural units (III-1) and (III-2) include alkylene groups having 2 to 6 carbon atoms such as ethylene group and 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. Base,
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. Examples of the aryl group of 8 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. A typical example of the structural unit (III-1) is shown below.

[0021]

[Chemical 14] (In Chemical Formula 14, m is as defined above.) The structural unit (III-1 ′) shown below,

[Chemical 15] (In chemical formula 15, m is as defined above.)

Examples of the structural unit (III-1 ") include the structural unit (III-1").
16 below

[0023]

[Chemical 16] (In chemical formula 16, m is as defined above.)

The structural unit (III-2 ') represented by Instead of the structural unit (III-1) or the structural unit (III-2),

[0025]

[Chemical 17] (Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and m are as defined above) or the following chemical unit 18

[0026]

[Chemical 18] (In chemical formula 18, 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 contained, the contained C--O--Si portion is easily cleaved by a hydrolysis reaction, so that the surface properties such as abrasion resistance of the polyurethane elastic fiber are deteriorated, which is not preferable. .

The polymeric diol unit [a] which is one of the structural units constituting the polyurethane elastic fiber of the present invention is substantially the above structural unit (I-1) and / or (I-
2), the structural unit (II-1), and the structural unit (III-1) and / or (III-2). In the polymer diol unit [a], the molar amount of the structural unit (III-1) is The sum of the percentage and the molar percentage of the structural unit (III-2) is usually within the range of 0.4 to 10 mol%. From the viewpoint that the polyurethane elastic fiber has good surface properties such as abrasion resistance, lubricity and unwinding property and mechanical strength, the content of silicon atom in the polymer diol unit [a] is 0.05 to 25.
Must be in the range of wt%, 0.08-1
It is preferably within the range of 5% by weight.

The number average molecular weight of the polysiloxane side chain-containing polymer diol giving the polymer diol unit [a] is 50.
It is within the range of 0 to 10,000. Number average molecular weight is 50
When it is less than 0, the cold resistance, low temperature characteristics and elongation of the polyurethane elastic fiber are insufficient, and when the number average molecular weight exceeds 10,000, the elongation recovery of the polyurethane elastic fiber is insufficient. .

The polymeric diol unit [a] substantially includes the structural unit (I-1), the structural unit (II-1) and the structural unit (I
II-1) consisting of a polyester diol unit (hereinafter, the polyester diol unit is referred to as a polymer diol unit [a-1]), and substantially structural units (I-1) and (I
-2), a polyester carbonate diol unit composed of the structural unit (II-1) and the structural unit (III-1) (hereinafter, the polyester carbonate diol unit is referred to as a polymer diol unit [a-2]), Structural unit (I
-2), a structural unit (II-1) and a structural unit (III-1). A polycarbonate diol unit (hereinafter, such a polycarbonate diol unit is referred to as a polymer diol unit [a-
3]), substantially structural unit (I-2), structural unit
Polycarbonate diol unit consisting of (II-1) and structural unit (III-2) (hereinafter, this polycarbonate diol unit is referred to as polymer diol unit [a-4])
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 and dicyclohexylmethane- group.
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 preferable. Particularly preferred is the dicyclohexylmethane-4,4'-diyl group.

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

The polymeric diol unit [d] is a polyester diol unit consisting essentially of the structural unit (I-3) and the structural unit (II-2). -1]),
Substantially the structural units (I-2), (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]), a structural unit (I-2) and a structural unit (II-2) And a polycarbonate diol unit (hereinafter, such a polycarbonate diol unit is referred to as a polymer diol unit [d-3]). The number average molecular weight of the polymer diol such as polyester diol, polyester carbonate diol, and polycarbonate diol that gives the polymer 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 characteristics and elongation of the polyurethane elastic fiber may be insufficient, and the number average molecular weight is 10,000.
If it exceeds, the elongation recovery of the polyurethane elastic fiber may be insufficient. The content of the polymer diol unit [d] is preferably 60% by weight or less based on the polyurethane elastic fiber of the present invention.

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

The compounds having two or less active hydrogen atoms and having a molecular weight of 400 or less include those used as a chain extender in ordinary polyurethane production. As a typical example, 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 in a cyclic structure such as piperazine; and low molecular compounds such as dihydrazides such as adipic acid dihydrazide and isophthalic acid 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.
It is below, and for the purpose of obtaining a polyurethane having good melt spinnability, it is preferably in the range of 2 to 15% by weight. In addition, in this specification, an active hydrogen atom means the hydrogen atom which 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 above-mentioned polymer diol unit [a], structural unit (IV) and structural unit (V), and optionally a polymer diol unit [d]. ] Is formed by forming a urethane bond or a urea bond and bonding. In the polyurethane of the present invention, the sum of the mole percentage of the polymer diol unit [a], the mole percentage of the polymer diol unit [d] and the mole percentage of the structural unit (V) is substantially the same as the mole percentage of the structural unit (IV). Equal to each other 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 properties, and when the content of silicon atoms exceeds 20% by weight, the polyurethane elastic fiber is not elastic. The strength, elongation and elongation recovery of the fiber are insufficient.

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

Examples of the organic diisocyanate represented by the general formula (VI) include 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; or alicyclic diisocyanates such as isophorone diisocyanate and 4,4′-dicyclohexylmethane diisocyanate. To be Particularly preferred is 4,4'-diphenylmethane diisocyanate.

As described above, the polymer diol giving the polymer diol unit [d] is a polymer diol unit [d].
-1], a polyester diol giving a polymer diol unit [d-2], a polycarbonate diol giving 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 1 Known polyester diols such as polyalkylene adipate diols containing 2,9-nonanediol and 2-methyl-1,8-octane diol as alkylene glycol components, poly-3-methylpentamethylene azelate diols, polycaprolactone diols, and the like are available. It is illustrated. Examples of the polycarbonate diol include polyhexamethylene carbonate diol, and known polycarbonate diols such as polyalkylene carbonate diol containing 1,9-nonanediol and 2-methyl-1,8-octanediol as alkylene glycol components. To be done.

The polysiloxane side chain-containing polymer diol includes a polyester diol substantially composed of the structural unit (I-1), the structural unit (II-1) and the structural unit (III-1). Is referred to as polymeric 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, this polyester carbonate diol is referred to as a polymer diol [A-2]), and a structural unit (I-2),
Polycarbonate diol comprising structural unit (II-1) and structural unit (III-1) (hereinafter, such polycarbonate diol is referred to as polymer diol [A-3]), substantially structural unit (I-2), structure A polycarbonate diol composed of the unit (II-1) and the structural unit (III-2) (hereinafter, the polycarbonate diol is referred to as a polymer diol [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 the same as those in the polyurethane elastic fiber of the present invention. Polymer diol unit (a-1), polymer diol unit (a
-2), a polymeric diol unit (a-3) and a polymeric diol unit (a-4) which provides a polymeric diol unit (a-4).

The polymeric 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). A dicarboxylic acid represented by the formula) or an ester-forming derivative thereof; a monomer giving the desired structural unit (II-1), that is, a general formula HO—R ³ —OH (VIII), wherein R ³ is A diol represented by the following); a monomer giving the desired structural unit (III-1),

[0042]

[Chemical 19] (Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and m are as defined above) or a polysiloxane side chain-containing diol (IX-1) or Below

[0043]

[Chemical 20] (In Chemical Formula 20, 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) represented by is used in 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. 180 to 25
It is produced by subjecting it to a polycondensation reaction at 0 ° C. Such polycondensation reaction is usually carried out under reduced pressure in the presence of a polycondensation catalyst. As the polycondensation catalyst, a polycondensation catalyst used in the production of ordinary polyesters can be adopted, and titanium compounds such as tetraisopropoxy titanium and tetra-n-butoxy titanium; di-n-butyltin dilaurate, di- Examples thereof include tin compounds such as n-butyltin oxide and dibutyltin diacetate; combinations of acetic acid metal salts such as magnesium acetate, calcium acetate and zinc acetate with antimony oxide or the above titanium compounds. These polycondensation catalysts are 1 to the product.
It is preferable to use it in the range of 500 ppm.

The polymeric diol (A-2) is, for example, a monomer giving the structural unit (I-1), that is, the general formula (VII).
A dicarboxylic acid or an ester-forming derivative thereof; a monomer giving the desired structural unit (I-2), that is, a carbonic acid ester such as dialkyl carbonate, diaryl carbonate or alkylene carbonate; desired structural unit (II-1) With a diol represented by the general formula (VIII); a desired structural unit (III-
1) is used, that is, a polysiloxane side chain-containing diol (IX-1) or a polysiloxane chain-containing alkylene oxide (IX-2) is used in a predetermined ratio, and these are subjected to an esterification reaction at 100 to 230 ° C. or The resulting low polymer was subjected to a transesterification reaction and further added to 180 to 23
It is produced by subjecting it to a polycondensation reaction at 0 ° C. Such polycondensation reaction is usually carried out under reduced pressure in the presence of a polycondensation catalyst. As the polycondensation catalyst, a catalyst used in the production of ordinary polyesters and polycarbonates can be adopted, and titanium compounds such as tetraisopropoxytitanium and tetra-n-butoxytitanium; di-n-
Examples thereof include tin compounds such as butyltin dilaurate, di-n-butyltin oxide, and dibutyltin diacetate; combinations of acetic acid metal salts such as magnesium acetate, calcium acetate, and zinc acetate with antimony oxide or the above titanium compound. . These catalysts are preferably used so as to be in the range of 1 to 500 ppm with respect to the product.

The polymeric diol (A-3) is, for example, a monomer which gives the structural unit (I-2), ie, a carbonic acid ester such as dialkyl carbonate, diaryl carbonate or alkylene carbonate; desired structural unit (II-1) A monomer that gives the general formula (VIII)
And a monomer giving the desired structural unit (III-1), that is, a polysiloxane side chain-containing diol (IX-1), are used in a predetermined ratio, and these are used.
It is produced by subjecting to a transesterification reaction at 0 to 230 ° C. Such transesterification reaction can be carried out 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 it is desired to accelerate the reaction. As such a catalyst, a transesterification catalyst used in the production of ordinary polycarbonate can be adopted, and a titanium compound such as tetraisopropoxytitanium or tetra-n-butoxytitanium; di-n-
Examples thereof include tin compounds such as butyltin dilaurate, di-n-butyltin oxide, and dibutyltin diacetate; combinations of acetic acid metal salts such as magnesium acetate, calcium acetate, and zinc acetate with antimony oxide or the above titanium compound. . These catalysts are preferably used so as to be in the range of 1 to 500 ppm with respect to the product.

The polymeric diol (A-4) is, for example, a monomer giving the structural unit (I-2), that is, a carbonic acid ester such as dialkyl carbonate, diaryl carbonate or alkylene carbonate; desired structural unit (II-1) And a monomer giving a fragment of the general formula —O—R ³ —O— (III-2a) in the desired structural unit (III-2), where R ³ is as defined above, ie A diol represented by the general formula (VIII);

[0048]

[Chemical 21] (In Chemical Formula 21, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and m are as defined above.)

Monomers giving the fragment (III-2b) represented by ## STR3 ## ie, polysiloxane chain-containing alkylene oxide (IX-2), were used at a predetermined ratio, and these were used in an amount of 10
It is prepared by subjecting it to a transesterification reaction involving a oxidative addition reaction at 0 to 230 ° C. Such transesterification reaction can be carried out 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 it is desired to accelerate the reaction. As such a catalyst, a transesterification catalyst used in the usual production of polycarbonate can be adopted, and titanium compounds such as tetraisopropoxy titanium and tetra-n-butoxy titanium; di-n-butyltin dilaurate and di-n. −
Examples thereof include tin compounds such as butyltin oxide and dibutyltin diacetate; combinations of acetic acid metal salts such as magnesium acetate, calcium acetate and zinc acetate with antimony oxide or the above titanium compounds. These catalysts are preferably used so as to be in the range of 1 to 500 ppm with respect to the product.

Typical examples of the dicarboxylic acid 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; 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-exemplified dicarboxylic acid.

Examples of the carbonic acid 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. .

Typical 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-
Nonanediol, 2-methyl-1,8-octanediol, 1,10-decanediol and the like can be mentioned.

Polysiloxane side chain-containing diol (IX-
As a typical example of 1),

[Chemical formula 22] (Wherein, m is as defined above),

[0054]

[Chemical formula 23] (In Chemical Formula 23, m is as defined above) and the like.

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

[Chemical formula 24] (Wherein, m is as defined above) and the like.

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

The polyurethane thus obtained is
It is possible to adopt a method in which the pellets are once pelletized and then melt-spun, or the polyurethane obtained by melt polymerization is directly spun in a molten state through a spinneret. From the viewpoint of spinning stability, polymerization direct binding spinning is preferable. 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. At this time, since the spinneret is less dirty,
It has excellent features such as less yarn breakage and good unwinding property.

[0059]

EXAMPLES The present invention will be described in more detail 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 shown by abbreviations. Tables 1 and 2 show the relationship between abbreviations and compounds.

[0061]

[Table 1]

[0062]

[Table 2]

The silicon atom content in the polymeric diol and the polyurethane elastic fiber was measured by the atomic absorption method.

The strength and elongation of the polyurethane elastic fiber was measured according to JIS L-1013. For the instantaneous elastic recovery rate, JIS L-1096 was applied, and after 200% elongation, it was held for 2 minutes, and the returning property immediately after the stress was removed was determined according to the following formula. Instantaneous elastic recovery rate = 100 × [nl− (l′−l)] / n
l (n: elongation ratio, l: initial length, l ': length after stress relief)

Further, the soiling of the spinneret and the unwinding property of the wound elastic yarn after 24 hours from the continuous spinning were evaluated in four levels.

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. Tetraisopropoxy titanium 0.03 g at the time when almost no water was distilled off
Was added and the degree of vacuum was gradually raised to complete the reaction under a vacuum of 3 mmHg. The obtained polymeric diol 1 has a hydroxyl value of 5
It had a pH of 5.5 and an acid value of 0.15 and its silicon atom content was 0.14% by weight.

Reference Examples 2-5 Reference Example 1 except that the predetermined amounts of the monomers shown in Table 3 were used.
Polymer diols 2 to 5 were obtained in the same manner as in.

[0068]

[Table 3]

Reference Example 6 (Polymer diol [A-2]) 3-methyl-1,5-pentanediol 640 g, 1,
6-hexanediol 640 g, azelaic acid 855
g, 480 g of ethylene carbonate and 20 g of XA were charged into a reactor, and esterification and carbonate reaction were carried out under a nitrogen stream while distilling out water and ethylene glycol produced at 200 ° C. to the outside of the system. Tetraisopropoxy titanium 0.03 when almost no distillate
g was added and the degree of vacuum was gradually raised to complete the reaction under a vacuum of 3 mmHg. The obtained polymeric diol 6 has a hydroxyl value of 5
It had a pH of 5.5 and an acid value of 0.10, a number average molecular weight of 2020 and a silicon atom content of 0.35% by weight.

Reference Example 7 (Polymer diol [A-3]) 3-methyl-1,5-pentanediol 475 g, 1,
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 performed while distilling out ethylene glycol produced at 200 ° C. to the outside of the system.
From the time when the distillation was almost stopped, the degree of vacuum was gradually increased and ethylene glycol was completely distilled off under a vacuum of 5 to 10 mmHg. The polymer diol 7 thus obtained 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 Polymeric diols 1 and 1, respectively 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, continuous melt polymerization was performed, and the produced polyurethane was formed into a strand. Extruded into water and cut into pellets. The pellets were vacuum dried at 80 ° C. for 20 hours, and a 40 denier elastic yarn was obtained at a spinning temperature of 215 ° C. and a spinning speed of 500 m / min by 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 a humidity of 60% to measure various physical properties. In addition, Table 4 shows the results of evaluation of stains on the spinneret and unwinding properties of the wound elastic yarn in four stages after 24 hours of continuous spinning.

[0072]

[Table 4]

Examples 2 to 6 and Comparative Examples 1 to 4 In the same manner as in Example 1, polyurethane was synthesized so as to have the composition shown in Table 4, pelletized and then spun to give 40.
An elastic thread of denier was obtained. These are aged under the same conditions as in Example 1 and the elastic fibers obtained are evaluated and the results are shown in Table 4.
Shown in. As is clear from the above examples, the elastic fiber provided by the present invention has a high strength and elongation, has less stain on the spinneret during spinning, and is excellent in unwinding property.

[0074]

The polyurethane elastic fiber of the present invention has strength,
It has improved surface properties such as abrasion resistance, lubricity, and water repellency while maintaining elongation and elongation recovery properties. It is possible to provide a polyurethane elastic fiber having a small amount and excellent melt spinnability such as unwinding property.

Claims (1)

[Claims] 1. A main chain mainly comprises (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) below.
-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) is bound to each other by forming an ester bond and / or a carbonate bond, and the silicon atoms derived from the structural units (III-1) and (III-2) are contained in an amount of 0.05 to 25
1% of hydroxyl groups located at both ends of the main chain from a polysiloxane side chain-containing polymer diol having a weight average content of 500 to 10,000 and having hydroxyl groups at both ends of the main chain. Polymer diol unit [a] in the form of removing one hydrogen atom; (b) structural unit (IV) represented by the following chemical formula 6; (c) structural unit (V); and, if desired, (d) substance Structural unit (I-2) represented by the following chemical formula 2 and / or structural unit (I-3) represented by the following chemical formula 3 and the following structural unit (II-2). ), (I
-3) and (II-2) are bound to each other by forming an ester bond and / or a carbonate bond, have hydroxyl groups at both ends of the main chain, and have a number average molecular weight of 50.
A polymer diol unit [a], which is composed of a polymer diol unit [d] in the form of a polymer diol having a molecular weight of 0 to 10,000 and having one hydrogen atom in each of the hydroxyl groups located at both ends of its main chain is removed. And the sum of the mole percentage of the polymeric diol unit [d] and the mole percentage of the structural unit (V) is substantially equal to the mole percentage of the structural unit (IV).
An elastic fiber produced from polyurethane having a weight percentage of (V) of 30% by weight or less and containing 0.01 to 20% by weight of silicon atoms. [Chemical 1] (In Chemical Formula 1, R ¹ represents a divalent hydrocarbon group.) [Chemical 3] (In Chemical Formula 3, R ² represents a divalent hydrocarbon group) —OR ³ —O— (II-1) (In the formula, R ³ represents a divalent hydrocarbon group) —O—R ^4- O- (II-2) (In the formula, R ⁴ represents a divalent hydrocarbon group) (In Chemical Formula 4, 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 represent an alkyl group or an aryl group having 1 to 6 carbon atoms, and m represents a number of 5 to 70). (In Chemical formula 5, R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹
And m are as defined above) (In Chemical Formula 6, R ¹² represents a divalent organic group) -A- (V) (In the formula, A is a molecular weight of 40 containing two active hydrogen atoms.
It represents a divalent organic group in a form in which the two active hydrogen atoms are removed from a compound of 0 or less)