JPS5884849A - Hydrophilic polymer composition - Google Patents

Abstract

PURPOSE:To obtain titled composition of improved hydrophilic nature and durability, comprising a thermoplatic polymer and a second polymer selected from polyester, polyamide, and polyesteramide, each containing, as a copolymerizable component, a specific polyalkylene oxide compound. CONSTITUTION:The objective composition comprising (A) a polyester, polyamide, or polyesteramide, each containing, as a copolymerizable component, an alkylene oxide adduct of, or its condensate with a sulfonated bisphenol (bisphenol A, sulfonated bisphenol S, etc.) (pref. with the numbers of alkylene oxide and bisphenol units being 5-400 (esp. 10-300) and 1-20, respectively) and (B) a second thermoplastic polymer. The contents of the in the component (A) polyalkylene oxide segment and the sulfonate group in the component (A) are preferably 10- 60wt% and 100-800 equivalents/ton, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymer composition with improved hydrophilic properties useful as fibers, films and oil moldings.

Hygroscopicity achieved by making the synthetic polymer hydrophilic.

Attempts have been made for a long time to impart sweat-absorbing properties, water-conducting properties, antistatic properties, etc., and numerous proposals have been made. Even in a strong force field, the method of blending an ionic or nonionic hydrophilic compound (modifier) into a synthetic polymer simplifies the process compared to the method of treating the surface of the synthetic polymer with a modifier. It is said to be advantageous in terms of improved performance and durability. however.

When a conventionally known modifier is blended into a synthetic polymer, the modifier falls off due to heat treatment, hot water treatment, dyeing treatment, friction, long-term use, etc. There are disadvantages in that the durability of the hydration effect is poor, or conversely, the modifier is bound in the synthetic polymer, reducing its mobility and making it difficult to develop the hydrophilic effect.

As a result of intensive studies to obtain a polymer product with good hydrophilic effect and durability, the present inventor has developed polyester, polyamide, or polyester containing a l-realkylene oxide compound having a specific structure as a copolymerization component. The inventors have discovered that by blending an amide into a synthetic polymer, a polymer composition free from the above-mentioned drawbacks can be obtained, and the present invention has been achieved.

That is, 9 the present invention provides sulfonated bispheno-A'l
A polyester containing an alkylene oxide adduct and/or a condensate thereof as a copolymer component, TI! The gist is a polymer composition consisting of a yamide or polyesteramide CA) and another thermoplastic polymer CB).

In the present invention, sulfonated bisphenols refer to compounds in which an alkali metal sulfonate base (sulfonate group) is introduced into the benzene nucleus of bispheno-A/II, and specifically, compounds represented by the following general formula: can be mentioned.

(501M)m (SOaM)n(1::
, -CHa, C(CHs)z, S
Og, O.

M: Na, m: 1-2. neo ~2) Sulfonated bisphenols are obtained by sulfonating bisphene/-~ with a sulfonating reagent such as **acid; ``fuming sulfuric acid, chlorosulfonic acid, etc.'' to form NaCl JPKC.
The sulfonate group obtained by treatment with I is introduced at the ortho position to the hydroxyl group of bispheno-/I/, but the number of sulfonate groups depends on the amount of reagent during sulfonation, temperature at 0 hours, etc. be able to.

The alkylene oxide adduct in the present invention is a compound having hydroxyl Vlv groups at both ends obtained by adding a mixture of ethylene oxide, propylene oxide, and ethylene oxide to the sulfonated bisphenols, or Examples include compounds in which part or all of the terminal end is modified with an ester or amide-forming functional group such as a carboxy VA/group, a boa-coxyl group, an amino group, etc., and these can be produced by a conventional method.

In addition, the condensate of an alkylene oxide adduct of sulfonated bisphenols means a compound in which the ends of the above-mentioned γρ etc. alkylene oxide adduct are linked together in the form of an ether bond, an ester bond, or an amide bond. Of these, the ester bond and the amide bond can be easily produced by utilizing the condensation reaction between the hydroxyl group, the .mu.boxy group, and the amino group of the alkylene oxide adduct. Ether bonds are formed, for example, by a dehalogenating alkali reaction between a compound in which the terminal hydroxy V~ group of an alkylene oxide adduct is substituted with a halogen and a compound in which the hydroxy VA/ group of another alkylene oxide adduct is substituted with an alkotute. However, the ether bond is a preferable bond in that there is no exchange reaction with the ester bond or amide bond in polyester, laryamide, polyester, or amide.

Sulfonated bisphenol used in the present invention
The pv-inclined alkylene oxide adduct or condensate thereof has 5 to 400, preferably 10 to 500, ap-kylene oxide units in one molecular chain. Those containing 1 to 20 bisphenol units are preferred.

In the present invention, the polyester, polyamide or polyester amide (A) refers to dicarboxylic acids such as adipic acid, sepacic acid, azefinic acid, terephthalic acid, isofI/I/acid, naphthalene dicarboxylic acid, and esters thereof, p-β -Hydroxycarboxylic acid compounds such as hydroxy-V, ethoxy-V, monocarboxylic acid and its esters, ethylene glycol, diethylene glycol, propylene glyco-A
/, 1.4-diol, neopentyl glycol, 1.4-V chlorhexanedimethanol-fi/, xylylene glyco-, 2.2-bis(p-β-hydroxyethoxyVpheni/I/ ) Glyco-/I/ such as propane, bis(p-β-hydroxyVethoxypheni/L/)sulfone
.

Diamines such as ethylenediamine, hexamethylenediamine, phenylenediamine, chlorodiamine, and bis(p-aminocyclohexyμ)methane.

Copolycondensation by adding the above-mentioned polyalkylene oxide compound during the synthesis of polyester, polyamide, or polyesteramide obtained by appropriately combining aminocaproic acid, aminotucric acid, etc., amizuka μ-bonic acid, cabroctam, lauryllactam, etc. means a polymer obtained by

These polymers can be obtained by known methods, but the contents of boriakylene oxide V-dosegment and sulfonate group are 10 to 60% by weight and 100 to 80% by weight, respectively.
It is preferable to adjust the amount to 0 equivalent/ton.

Next, 9 thermoplastic polymer CB used in the present invention #C
) is ethylene terephthalate F.

Polybutylene terephthalate, Kelly 1. A-V Chloheki V Dimethylene Terephthalate, Polyethylene-2
, 6-naphthalate, poly p-ethylene oxybenzoate, and poly/lyesters containing these as main components, nylon 6, nylon 12. Nylon 66, nylon 610
Polyamides containing these as main components, polyethylene, polypropylene, etc., and polyolefins containing these as main components and polymers with good melt moldability are preferred.

The polymer composition of the present invention can be obtained by a known melt-mixing method, that is, by melt-mixing [A] and CB) at any stage before molding, and [A] is the final kylene of the polymer composition. 1c is added so that the amount of oxide segment is 0,stt* or more, preferably 1 part by weight or more. The polymer composition obtained in this manner exhibits significantly better hydrophilicity than the case where a block copolymer containing ordinary polyalkylene oxide as a copolymerization component is added. It has the advantage of providing products that are stable against high temperatures and are easily dyed with disperse dyes or basic dyes.

It goes without saying that the polymer composition of the present invention may also contain additives such as a matting agent, a light stabilizer, and a flame retardant.

The polymer composition of the present invention provides fibers, films, and other molded products having good properties and good properties.

In addition, its hydrophilic properties are determined by heat treatment during secondary processing, hot water treatment,
Even after dyeing, rubbing, washing, dry-cleaning, and long-term use, it remains almost permanent with almost no change.

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

As an evaluation of hydrophilic performance, the electrostatic property was measured using a rotary stack tester method at 20°C and 40'
The frictional charging voltage and the half-life of the charge were determined in an atmosphere of 1°''RFI using cotton cloth as a friction body. (Parts indicate parts by weight.) Example 1 2.2-bis(p-hydroxyphenylene/ I/) Addition of 80 times the mole of ethylene oxide to 2,2-bis (p- to droxy-〇-natritum)propane C synthesized by sulfonating propane (bisphenol A) with concentrated sulfuric acid and treating it with a chlorinated meter. Compound (al) was obtained.

Next, 100 parts of bis(β-human p-xyethyl A/) terephthalate, 80 parts of compound (&I), and 0.03 parts of antimony trioxide were placed in a stirring choreographed polymerization vessel, and the temperature was raised to 270°C.
The temperature was kept at ℃ and the pressure was gradually reduced to reach 100 °C in 1 hour. During the plot,
The intrinsic viscosity at 25°C is 1. A white block copolymer [A1] of o2 was obtained.

Compared to normal polyethylene terephthalate CB+)
A1] was added in an amount of 10% by weight, and melt IM! The yarn was spun at 280 c and then drawn to obtain a white drawn yarn having a density of 75 d/24 f, a strength of 4.19/d, and an elongation of 28%.

One set of tubes was refined from this drawn yarn at a density of 509/d.

Dyeing was carried out at 120'C for 1 hour in a bath containing a blue fractional dye. Dyed cloth has a frictional charging voltage of 1500 V and a half-life of 1.
It showed a good anti-trapping property of 2 seconds, and this performance hardly deteriorated even after washing with a normal Hof Fundro 1-50.

Comparative Example 1 The same operation as in Example 1 was carried out except that ordinary polyethylene oxide (average degree of polymerization 80) was used instead of compound (al), but the 4-voltage voltage of the dyed cloth and its half-life were Each exhibited a voltage of 3000 V for 50 seconds, and no sufficient antistatic effect was observed.

*Example 2 Compound (as) After V anoethylation by adding c acrylonitrile, hydrogenation was performed to obtain a compound (al) having amino groups at both ends.

Next, 100 parts of cabrotam, compound (am) 9
0 parts of adipic acid, 3 parts of adipic acid, and 20 parts of water were placed in a polymerization container and polycondensed at 250°C under the conditions of a pressure period of 4 #/d x 5 hours, a pressure release period of 1 hour, and a normal pressure period of 2 hours. Glocopolymer with an intrinsic viscosity of 1.1 at 25″C in 96% sulfuric acid (
At) was obtained.

This block copolymer (0 part of AILll) was mixed and spun with 90 parts of regular nylon 6 (Ba) at a melting temperature of 260°C, and stretched in the usual manner to give a strength of 4.29/d and an elongation of 30 g6. It was made into a drawn thread.

After knitting this honed yarn, it is refined and placed in an acid dye bath.

The cloth obtained by dyeing at 100°C for 1 hour shows good antistatic properties, with a charging voltage of 1300 V per ml and a half-life of 1.
0 seconds), and the washing resistance was also good.

Example 3 Disulfonated sodium salt I of bis(p-hydroquine A/)sulfone obtained by sulfonating bis(p-hydroquine A/)sulfone (bispheno-1vS)
The compound (
I). A compound (K'') obtained by treating compound (I) with hydrogen chloride gas to monomerize both ends, and a separate compound (I)
By reacting Alcolade type compound (1) obtained by reacting with metallic sodium with dechlorinated sodium at a 9 molar ratio of 2:5, a compound containing an average of 5 bisphenol S components in one molecular chain. A compound (a=) was obtained.

Compound (a-) was used in place of (a) in the same manner as in Example 1 to obtain a 9wI triboelectric voltage of 12.00V and a half-life of 10.
I was able to get the cloth in seconds.

Patent applicant: Unitika Co., Ltd.

Claims (1)

[Scope of Claims] (1) Polyester, polyamide, or polyesteramide [mu] containing a kylene oxide V-do adduct of sulfonated bisphenol/I/IN and/or its condensate as a copolymerization component, and other thermal A polymer composition comprising a plastic polymer CB). (2) View of the composition of the aggregate according to claim 1, wherein the sulfonated bispheno-A/M is a sulfonated product of bispheno-A/A or bispheno-A/S. (3) The alkylene oxide V is ethylene oxide. The polymer composition according to claim 1, which is propylene oxide and/or propylene oxide. (4) Akylene oxide V-do adduct of sulfonated bisphenol and/or its condensate is Cη in the molecular chain 1 side.
Claim III containing 5 to 4001 alkylene oxide units and 1 to 20 bisphenol units
2. Polymer composition according to item 1. (&) (The polymer composition according to claim 1, wherein the content of polyalkylene oxide segments and sulfonate groups in the muco is 10 to 601 equivalents/ton and 100 to 800 equivalents/ton, respectively.