JPH0218344B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hydrophilic polymer composition useful as fibers, films, and other molded articles.

Attempts have been made for a long time to impart hygroscopicity, sweat absorption, water absorption, water conductivity, antistatic properties, etc. by making synthetic polymers hydrophilic, and many proposals have been made. Among them, the method of blending an ionic or nonionic modifier (hydrophilic compound) into a synthetic polymer simplifies the process and improves performance 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 durability.

However, when conventionally known modifiers are blended into synthetic polymers, heat treatment, hot water treatment,
The modifier may fall off due to dyeing treatment, friction, long-term use, etc., resulting in poor durability of the hydrophilic effect, or conversely, the modifier may become trapped in the synthetic polymer, reducing its mobility and reducing the hydrophilic effect. In reality, the current situation is that it has not yet reached a satisfactory stage, as it has been pointed out that it is difficult to produce effects and is slow to produce results.

As a result of various studies on compounds having a zwitterion structure as substances that impart hydrophilicity to synthetic polymers, the present inventors found that conventionally known polyalkylene oxide compounds having a zwitterion structure (e.g., No. 44930) has the above-mentioned problems, but if a block copolymer type polymer with a fixed amount of polyalkylene oxide segments is used, a product with good hydrophilic effect and durability can be created. The present invention has been achieved based on the discovery that the present invention can be obtained.

That is, the present invention uses a polyalkylene oxide component of 10 to 80% by weight as a copolymerization component, and comprises a block copolyether ester, a block copolyether amide, or a block copolyether ester amide having a sulfo and/or carboxyammonium zwitterion structure. The gist is a polymer composition consisting of a selected block copolymer [A] and another synthetic polymer [B].

The block copolymer [A] in the present invention includes polyethylene oxide, polypropylene oxide,
Among copolymers having polyalkylene oxide segments, such as copolymers of ethylene oxide and propylene oxide, those having a sulfo and/or carboxyammonium zwitterion structure, and the following two types are preferably used: .

A compound having a zwitterionic structure and one or more (preferably two) ester- or amide-forming functional groups, i.e., hydroxyl group, carboxyl group, alkoxycarbonyl group, amino group, etc., such as N, A compound having an ester or amide forming functional group at the end of the polyalkylene oxide chain of N-bis(polyoxyalkylene)-N-alkyl (or aryl)-N-sulfo(or carboxy)alkyl(or aryl)ammonium betaine. A polymer obtained by copolycondensation by adding during the synthesis of polyester, polyamide, or polyesteramide.

A polyalkylene oxide having an ester- or amide-forming functional group and no zwitterion structure and a compound represented by the following general formula [R ₁ is a monovalent organic group, R ₂ to _{R 4} are divalent organic groups,
X and Y are ester- or amide-forming functional groups,
Z represents SO ₃ ^- or COO ^- . ] is added during the synthesis of polyester, polyamide, or polyesteramide, and a polymer obtained by copolycondensation.

In addition, the polyester or polyamide or polyester amide used in producing the polymers of and are adipic acid, sebacic acid, terephthalic acid,
Dicarboxylic acid components such as isophthalic acid, ethylene glycol, propylene glycol, 1,4-butadiol, 2,2-bis(p-hydroxyphenyl)propane, bis(p-hydroxyphenyl)
Diol components such as sulfone, ethylenediamine,
It is obtained by appropriately combining diamine components such as hexamethylene diamine, piperazine, phenylene diamine, and xylylene diamine, lactams such as caprolactam and laurin lactam, and aminocarboxylic acids such as aminocaproic acid and aminolauric acid.

It is necessary to adjust the amount of the polyalkylene oxide component in the polymer [A] to 10 to 80% by weight in order to give the polymer composition good hydrophilicity and durability. The oxide is
A suitable molecular weight is 800 to 20,000, preferably 1,000 to 10,000, and the amount of sulfo or/and carboxyammonium zwitterion structure in the polymer [A] is 200 equivalents/ton or more. is preferred.

The polymer composition of the present invention can be produced by a known compounding and molding method, that is, by adding and mixing the polymer [A] at any stage before molding the synthetic polymer [B] to form fibers, films,
Although it can be obtained by molding into sheets, strands, chips, and other molded products, the synthetic polymer [B] in the present invention refers to polyethylene terephthalate, polyethylene terephthalate,
Polybutylene terephthalate, poly-1,4-cyclohexylene dimethylene terephthalate, poly-p-ethyleneoxybenzoate, etc., and polyesters containing these as main components, nylon 6,
Nylon 12, nylon 66, nylon 610, poly
m-phenylene isophthalamide, poly-p-phenylene terephthalamide, etc., polyamides containing these as main components, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, etc. It refers to synthetic polymers that are generally poor in hydrophilicity, including vinyl polymers, polybutadiene, polyisoprene, etc., which have these as main components, and other thermosetting polymers, such as diene polymers, which have these as main components. In this case, it is preferable that the amount of polyalkylene oxide component in the polymer composition is 0.3 to 15% by weight, and the amount of zwitterion structure is 30 equivalents/ton or more.

In addition, the polymer composition of the present invention may be mixed or combined with other polymers to the extent that its hydrophilic effect is maintained, or may be used as a coloring agent, a heat resistant agent, a light resistant agent, a matting agent, a flame retardant, a foaming agent, etc. Of course, it is also possible to include a modifier such as:

The present invention will be explained in more detail with reference to Examples below. Hydrophilicity (water absorption) is determined to be good if it takes 3 seconds or less according to the JISL-1096 dropping method, and antistatic property is measured by The frictional charging voltage and the half-life of the charge were determined using the Kyoto University Institute of Chemical Research rotary static tester method in an atmosphere of 20°C and 40% RH using cotton cloth as a friction body. (Parts indicate parts by weight.) Example 1 Add sodium chlormethanesulfonate to N-butyldiethanolamine and desalt it to obtain N-butyl-N,N-bis(hydroxyethyl)-N-sulfomethylsulfoammonium. Obtained betaine.

Next, 40 parts of bis(β-hydroxyethyl) terephthalate, 40 parts of bis(β-hydroxyethyl) isophthalate, 20 parts of compound [], and 0.02 part of zinc acetate were charged into a reaction vessel equipped with a stirrer, and the temperature was lowered.
The reaction mixture was maintained at 210° C. and reacted at normal pressure for 1 hour, then the pressure was gradually reduced to reach 0.1 Torr in 30 minutes, and the polycondensation reaction was further carried out for 3 hours to obtain a polymer [A ₁ ].

20 parts of this polymer [A ₁ ] and 80 parts of ordinary polyethylene terephthalate [B ₁ ] were mixed and spun using an extruder-type melt spinning machine at a melt temperature of 280°C and a residence time of 5 minutes, and then spun using a conventional method. A drawn yarn having a width of 75 d/16 f, a strength of 3.8 g/d, and an elongation of 30% was obtained by thorough drawing. The operability during spinning and drawing was good.

Using this drawn yarn, warp 110/2.54cm, weft 100
Book/After weaving into taffeta with a weave density of 2.54cm, it is refined,
Dyeing was carried out at 120°C for 1 hour in a bath containing a blue disperse dye. The obtained dyed fabric exhibited good hydrophilicity, and this performance did not change even after 50 repetitions of home laundry in which the fabric was treated in a washing solution containing 1 g of neutral detergent for 10 minutes at room temperature.

Examples 2 and 3 Reacting pivalolactone with N-lauryl-N,N-bis(p-carboxypropyl)amine,
Desalting gave a compound [ ] having a carboxyammonium zwitterion structure.

Next, 80 parts of caprolactam, 20 parts of compound []
1, 4.5 parts of hexamethylene diamine, and 5 parts of water were placed in a polymerization vessel equipped with a stirrer, and the temperature was maintained at 230°C, and polycondensation was carried out under the conditions of a pressure period of 3 kg/cm ² × 3 hours and a pressure release period of 1 hour. Thus, a polymer [A ₂ ] was obtained.

This polymer [A ₂ ] was combined with nylon 6 [B ₂ ] (Example 2) and polyethylene terephthalate [B ₁ ].
Added 20% by weight to (Example 3),
It was melt-spun in a conventional manner and drawn to obtain a drawn yarn of 75d/16f.

After weaving these drawn yarns in the same manner as in Example 1, the nylon fibers (Example 2) were woven at 100°C in an acid dye bath.
The polyester fibers (Example 3) were dyed in a disperse dye bath at 120° C. for 1 hour. The hydrophilicity of the dyed fabric and its home laundry after 50 washes was good.

Example 4 A compound obtained by adding 50 times the mole of ethylene oxide to stearylamine was reacted with sodium monochloromethanesulfonate, and then desalted to form N,
N-bis(polyoxyethylene)-N-stearyl-sulfomethylammonium betaine [] was obtained.

Next, 80 parts of terephthalic acid, 20 parts of adipic acid, and 65 parts of ethylene glycol were charged into a reaction vessel equipped with a stirrer, and an esterification reaction was carried out at 4 kg/cm ² and 240°C for 4 hours. 1 part and 0.03 part of antimony trioxide were added, the temperature was maintained at 240°C and the pressure was gradually reduced to reach 0.1 torr in 1 hour, and the polycondensation reaction was further carried out for 3 hours to obtain block copolymer chips [A ₃ ]. .

10 parts of this block copolymer chip [A ₃ ] and ordinary polyethylene terephthalate chip [B ₁ ]
Using an extruder-type melt spinning machine, the mixture was mixed with 90 parts and spun at a melting temperature of 280°C and a residence time of 10 minutes, and then stretched in a conventional manner to obtain a strength of 75d/24f.
A drawn yarn having an elongation of 4.3 g/d and an elongation of 30% was obtained. The operability during spinning and drawing was good.

This drawn yarn was tube-knitted at a density of 60 g/ ^m2 , then scoured and dyed under high pressure at 125°C for 1 hour in a bath containing a blue disperse dye.The frictional charging voltage and half-life of the cloth obtained were 1200V for 15 seconds, demonstrating good antistatic properties.

The antistatic property remained good even after washing 50 times at home laundry.

Example 5 Compound [] 2 parts and polyethylene oxide with hydroxyl groups at both ends (average molecular weight 4000) 60
A block copolymer [A ₄ ] was obtained by polycondensation in the same manner as in Example 4 using the above compound instead of the compound [].

This block copolymer [A ₄ ] was added in an amount of 10% by weight to polyethylene terephthalate [B ₁ ], and yarn spinning, knitting, scouring, and dyeing were performed according to Example 4, and the result was a frictional charging voltage of 1200 V and a half-life of 16 seconds. A fabric was obtained that exhibited this property, and this performance hardly deteriorated even after 50 home laundry washes.

Claims (1)

[Scope of Claims] 1. Blocked copolyether ester, blocked copolyether amide, or blocked copolyether ester amide, which contains 10 to 80% by weight of a polyalkylene oxide component as a copolymerization component and has a sulfo and/or carboxyammonium zwitterion structure. A polymer composition comprising a block copolymer [A] selected from the following and another synthetic polymer [B].