JPS5818412A - Improved block copolymer fiber - Google Patents

Abstract

PURPOSE:The titled fiber that is made by subjecting a block copolymer obtained by copolymerizing an adduct of alkylene oxide to a bisphenol with a polyester, polyamide or polyester amide, to melt spinning, thus showing improved heat resistance. CONSTITUTION:A block copolymer that is obtained by copolymerizing (A) a polyester, preferably polyethylene terephthalate, polyamide, preferaly nylon 6 or polyeter amide with (B) a condensate of an alkylene oxide (preferably ethylene oxide and/or propylene oxide) addyct to a bisphenol [preferably 2, 2-bis (p-hydroxyphenyl) propane], is subjected to melt spinning to give the objective fiber. The component B is preferably 800-20,000 in molecular weight and contains 2-20 bisphenol units in one molecular chain. The amount of the polyalkylene oxide segments is preferably 3-60wt% in the block polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to block polymer fibers having improved heat resistance and having a special polyether as a copolymer component.

Fibers obtained from polyester and polyamide containing polyalkylene oxide as a copolymerization component can be produced by appropriately combining the types of copolymerization components, the amount ratio, etc., to improve dyeability, hygroscopicity, glossiness, mattness, elasticity, etc. Because it has unique properties such as elasticity, it has been studied for a long time as a means of modifying fibers, and some of it has already reached the stage of commercialization. However, because it is composed of aliphatic ether, it has poor heat resistance, and at high temperatures applied to melt polycondensation and melt spinning of polyesters and polyamides, it tends to cause decomposition of the polymer9 and coloration of the fibers. In many cases, the physical properties of For this reason, various solutions have been investigated, such as adding a heat resistant agent and chemically modifying boria-kylene oxide, but the reality is that they have not yet reached a satisfactory level.

In view of this situation, the present inventors developed polyester and polyamide containing polyethylene oxide.

As a result of various studies aimed at improving the heat resistance of polyesteramide, it was discovered that a block copolymer obtained by copolymerizing a combination of bispheno-ρ fullkylene oxide adducts exhibits extremely good heat resistance. Reached.

That is, the gist of the present invention is an improved block copolymer fiber obtained by melt-spinning a block copolymer obtained by copolymerizing a combination of alkylene oxide adducts of bisphenols with polyester p, polyamide, or polyesteramide, alone or together with other components. It is something.

It is well known that alkylene oxide adducts of bispheno-p exhibit good heat resistance, and that block copolymers obtained by copolymerizing this with polyester or polyamide also show good heat resistance.

The inventors have discovered that block copolymers from combinations of such adducts exhibit even better heat resistance.

The combination of alkylene oxide adducts of bispheno-μ in the present invention includes:

Two molecules of a compound obtained by adding a mixture of ethylene oxide V do, propylene oxide V do, and ethylene oxide V doderobylene oxide to a bispheno-μ compound represented by the general formula % formula %) -8ot- or -〇-) Preferably, the above condensed compounds are linked by ether bonds. Such compounds include, for example, the alkylene oxide adduct of bispheno-μ, hydroxy VIL/
It is synthesized by a deherogonization alkali reaction between a compound in which the group is halogenated and a compound in which the hydroxy Vμ group of another alkylene oxide adduct is converted into an alkaline fluoride with an alkali metal. It is used in the form of an ester ρ or amide-forming functional group such as a V~ group, a carboxy Vμ group, or an amino group.

The combination of alkylene oxide adducts of bispheno-p used in the present invention has an average molecular weight of 800 to
It is preferable that the molecular weight is 20,000, and the average number of bisphenol components in one molecular weight is preferably 2 to 20. The molecular weight and bisphenol component content are appropriately selected depending on the use and purpose, but when particularly high heat resistance is required, it is preferable to increase the bisphenol-p component content.

Next, the polyester, polyamide, or polyester amide in the present invention refers to polycarboxylic acids such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalic acid, and esters thereof.

Ethylene glycol-p, diethylene glycol, propylene glycol, trimethylene glycol.

Tetofumethylene glycol μ, 1,4-cyclohexane V
Hydroxycarboxylic acid compounds such as glyco-j'sP-β-hydroxyV-ethoxybenzoic acid and its ester μ, such as methanol, cabroctam.

fuctams such as lauri μ fuctam, aminocaproic acid,
Aminocarboxylic acids such as aminofuric acid.

Ethylene diamine, hexyl methylene diamine, bis(p
-AminoVClohexV~) It means a thermoplastic polycondensate obtained by appropriately combining diamines such as methane, pipefudine, phenylenediamine, and xylylenediamine, and particularly preferred polycondensates include polyethylene terephthalate, Polybutylene tele 7 sauce, -t,
Poly 1.4-V Chloheki V Dimethylene Tereph Grate.

Polyethylene-2,6-naphthalate, poly p-ethylene oxybenzoate, etc., and lrieste containing these as main components, nylon 6, nylon 66, nylon 6
10 and polyamides containing these as main components.

The block copolymer in the present invention is produced by a known method by adding a condensate of bispheno-μ aquinone oxide adduct during the synthesis of polyester, polyamide, or polyesteramide. At this time, although it differs depending on the use and purpose, polyalkylene oxide V in the block copolymer
The amount of dosegment is preferably 5 to 60% by weight 9 For example, 5 to 20% by weight when the purpose is easy dyeability and antistatic properties, and 60 to 60% when the purpose is to make stretchable fibers (elastic fibers).
It is adjusted as appropriate, such as the electric power percentage.

The Glock copolymer of the present invention exhibits much better heat resistance than a block copolymer made from ordinary polyalkylene oxide, but if further heat resistance is required, a heat resistant agent may be used. 6-(3', da$F-t-]flL'-
4'-”Hydroki V7x-:=p) Propionate tumethane, o, o'-diethyl/k-6,5-dit, butyA/-4-hydroxybenzylphosphonate, hexamethylene-bis[s- <xs'.

Hindered phenol-based blood-heating agents (antioxidants) such as 5'-Gt, 4'-4'-and drochydiphenylglobamide] are preferably used. Also.

Needless to say, a matting agent, a light-fastening agent, an antistatic agent, a flame retardant, etc. may be added.

The fibers of the present invention can be obtained by melt-spinning the above block copolymers alone or in a mixed or composite form with other components to the extent that their properties are not lost by a conventional method.

The present invention will be explained in more detail below with reference to Examples.

(Parts indicate parts by weight.) Example 1 5 to 292-bis(p-hydroxyphenylene)propane
A compound obtained by adding twice the molar amount of ethylene oxide (a compound obtained by adding ethylene oxide at both ends by boiling it with hydrogen seeding gas in the presence of zinc chloride) was synthesized. Separately, Compound (I) was expanded with metallic sodium to form an alcohoot-type compound (Wl
) obtained 6 Next, (7) and (4) were reacted with sodium dehydration at a molar ratio of 2:5 and neutralized to obtain an average of 5 bisphenol-j% in one molecular chain. A condensate (g) containing component ' and having an average molecular weight of about 2,000 was obtained.

Then, 7 parts of the condensate (bis(β-hydroxy Vethyl
/) Telefta t/-) 95 parts and = antimony oxide 0.
03 parts were placed in a polymerization pot equipped with a stirrer, and the pressure was gradually reduced while maintaining the temperature at 275 t to reach 0.1) A/ in 1 hour, and the polycondensation reaction was further carried out for 3 hours.

A white block copolymer having an intrinsic viscosity of 0.82 was obtained with a melting point of 254 T: t pheno-A//tetofucloμethane 1 mixed*in.

This block copolymer was spun using an Exto μm Goo type melt spinning machine at a melting temperature of 2 aoc! Spun for 8 minutes and then spun to obtain 75d/36f, strength 4.5Mc
A white fiber with an elongation of 52g6 was obtained. Operability during spinning was good, and no acetaldehyde gas was detected directly under the spinneret. This situation did not change even when the melting temperature was increased to 285r.

The obtained fibers were heated at 100C in a dyeing machine containing disperse dyes.
When dyed under normal pressure, it showed good stainability.

Comparative Example 1 A compound obtained by adding 40 times the mole of ethylene oxide to 2.2-bis<p-hydroxyVphenyfi/)furopane was directly added to bis(β-hydroxyethy A/) terephthalate in the same manner as in Example 1. Polycondensation was performed to form a block copolymer.

When this block copolymer was melt-spun in the same manner as in Example 1, it was in good condition at 280U, but
At 285'C, acetaldahyde gas was detected just below the spinneret, and the yarn turned slightly yellow.

Example 2 A compound obtained by adding 10 times 7 ρ of ethylene oxide to bis(p-phenylene A/) sulfone was treated in the same manner as in Example 1 to obtain a condensate of 9-molecular weight of about 3,500. ), and then reacted with acrylonitrile to form V-anoethylated 1
Next, by hydrogenation, a compound having amino groups at both ends (
4).

Then 40 parts of compound Cv0, ! -Kabloc Tom 55
Set 5 parts of t-aminocaproic acid and 1 part of adipic acid
5 parts were placed in a polymerization vessel and reacted for 5 hours at 25°C in a nitrogen stream to obtain a white block copolymer having a melting point of 212c and an intrinsic viscosity of 1.2 at 25'c in 98% sulfuric acid.

This block copolymer is demonomer-free.

After drying, it was spun at a melting temperature of 270E and a melting time of 10 minutes, and then stretched to obtain a 150 (1/2
A white drawn yarn of SOf was obtained. The spinning drawability was extremely good.

Patent applicant: Unitika Co., Ltd. Procedural amendment @ (spontaneous) September 25, 1980 Commissioner of the Japan Patent Office 1, Indication of the case Patent application No. 116589/1989 2, Name of the invention Improved block copolymer fiber 3, Amendment Relationship with the case of a person who does
Unitika Co., Ltd. Patent Department Telephone: 06-252-6111 (Representative) Years of age Financial condition of amendment
(Contents of column amendments to the statement at the beginning of the specification, “Claims” and “Detailed Description of the Invention” (1) As shown in the attached appendix to the scope of claims (2) Line 1 of page 1 of the specification “ Correct "detailed schedule" to "detailed statement."

(3) Insert the following sentence between page 11, line 18 and line 19.

"Example 3 Addition of 44 ethylene oxides to 2.2-bis(P-hydroquinophenyl)propane by 20 times 4Jll/
A condensate was obtained in the same manner as in Example 1 except for the following.

Next, 100 parts of this condensate was added to the esterification product of terephthalic acid and ~65 parts of ethylene glycol, and polycondensation was carried out in a conventional manner to obtain a white boottaco damer with a viscosity of 0.91. Ta.

10 parts of the 19 mer chips of Boots wolfberry and 90 parts of polyethylene terephthalate chips were mixed, melt-spun and drawn by a conventional method to obtain 75 (1156 f, strength 4).
．． A drawn yarn having an elongation of 2 f/d and an elongation of over 28 was obtained. The operability during spinning and drawing was good.

The resulting fibers are dyed in a dyebath containing disperse dyes.

When high-pressure dyeing was carried out at a temperature of 125 C for 1 hour, good dyeability was exhibited, and the dyed fiber (fabric) had good antistatic properties and durability.

Example 4 From a compound obtained by adding 15 times more ethylene oxide to bis(p-hydroxyphenylated A/) sulfone, 1
A compound containing an average of 6 bisphenol components in the side molecular chain and having amino groups at both ends was obtained.

Then, 100 parts of this compound, 10 parts of -carbroxtam
0 parts, 10 parts of t-aminocaproic acid, and 3 parts of adipic acid were polymerized in a conventional manner.

A block copolymer with an intrinsic viscosity of 0.95 was obtained.

This block copolymer was added in an amount of (1) 100% by weight based on polyethylene terephthalate and (2) 8% by weight based on Nacilin 6C, and then melt-spun and stretched by a conventional method.
A drawn yarn of 5d/24f was obtained.

The antistatic properties of the obtained fibers aI were measured after dyeing 11 Esthep fiber in a disperse dye solution at 125°C for 1 hour, and nylon 6mIm in an acid dye solution for 1 hour at 125°C. It demonstrated antistatic properties and durability.

”Claim (1) Ho9Este/&/, polyamide or polyesteramide with bispheno-A/Jig alkylene oxide V
An improved gwack cobolymer fiber made by melt-spinning a block copolymer obtained by copolymerizing a condensate of an adduct alone or together with other components.

(2) The block copolymer me according to claim 1, wherein the polyester is polyethylene terephthalate or a polymer whose main component is polyethylene terephthalate, and the polyamide is nylon 6, nylon 66, or a polymer whose main component is these.

(3) Hisphenols are 2.2-bis(p-hydroxyphe=A/)propane, bis(p-hydroxyphe=A/), bis(p-hydroxyphe=A/)
A/) sulfone, p,p'-dihydroxybiphenyl, bis(P-hydroxyVphenyS/)methane, bis(
1 selected from the group of p-t-droxyphenyl)ether
The block copolymer fiber according to claim 1, which is a species or a compound of two or more species.

(4) The average molecular weight of the condensate of the alkylene oxide adduct of bisphenols is 80
2. The bootsquek copolymer fiber according to claim 1, wherein the average number of bisphenol components per molecular chain is 2 to 20.

(.) The block crucible 9-mer fiber according to claim 1, wherein the amount of I9 alkylene oxide V-dosegment in the block copolymer is 3 to 60% by weight.

Claims (1)

[Scope of Claims] (1) /Reeste~, an improved product obtained by melt-spinning Blitzko dalimer, which is a copolymerization product of alkylene oxide adducts of bisphenols and polyamide or polyesteramide, alone or together with other components. Rock comelymer fiber. 2. The Glock copolymer fiber according to claim 1, wherein the polyester is d-lyethylene deV phthalate or a polymer having this as its main component, and the posiamide is nylon 6, nylon 66, or a polymer having these as its main component. (1) Bispheno-μ is 2.2-bis(P-hydroxyVpheniμ)propane, bis(p-w ylokivphenyA/)sulfone, p,p'-dihydrokiVbiphenyp
, bis(p-hydroxy Vfe=A/)methane, bis(p
- 11 selected from the group of human pki V phenymu) ethers
The Glock copolymer fiber according to claim 1, which is one or more compounds. (4) The block copolymer fiber according to claim 1, wherein the alkylene oxide is ethylene oxide and/or propylene oxide. (5) The average molecular weight of the condensate of the alkylene oxide adduct of bispheno-μ is 800 to 20,000, and the average number of bisphenol components in one 9-molecular chain is 2 to 20.
The block copolymer fiber according to claim 1, which is ilI. (6) The Pudatsuku copolymer fiber according to claim 1, wherein the amount of realkylene oxide segment in the block colimer is 5 to 60 wt*.