JPH0342354B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a water absorbency imparting agent for synthetic fibers and a method thereof. [Prior Art] Conventionally, as a method for imparting water absorbency to synthetic fibers, a fiber structure made of synthetic fibers is mainly composed of a dicarboxylic acid component consisting of terephthalic acid and/or isophthalic acid and a glycol component consisting of alkylene glycol and polyalkylene glycol. A method for attaching polyether ester is known (for example, Japanese Patent Publication No. 43238/1983). [Problems to be Solved by the Invention] However, there are problems in that the water absorbency of these materials is not durable and the water absorbency decreases with washing. [Means for Solving the Problems] The present inventor has arrived at the present invention as a result of extensive studies on durable water absorbency imparting agents and methods of imparting them. A polyurethane resin made of an organic diisocyanate (A), a polymeric diol (B) consisting of an oxyethylene group-containing polyether diol (b ₁ ), and a chain extender (C), the oxyethylene content of the resin being but
20-80% by weight, the chain extender content in the resin is 2-30%
A water absorbency imparting agent for synthetic fibers consisting of % by weight. Or organic diisocyanate (A), oxyethylene group-containing polyether diol (b ₁ ) and other polymeric diol (b ₂ ) (hereinafter, for the purpose of simplifying the description, (b ₂ ) is used) A polyurethane resin made of a polymeric diol (B) consisting of a polymeric diol (described as "other polymeric diol (b ₂ ) if necessary") and a chain extender (C), wherein the oxyethylene content in the resin is A water absorbency imparting agent for synthetic fibers, comprising 20 to 80% by weight of other polymeric diols, up to 50% by weight of other polymeric diols, and a chain extender content of 2 to 30% by weight in the resin; , an organic diisocyanate (A), a polymer diol (B) consisting of an oxyethylene group-containing polyether diol (b ₁ ) and, if necessary, another polymer diol (b ₂ ), and a chain extender (C). A polyurethane resin in which the oxyethylene content in the resin is 20 to 80% by weight, and the content of other polymeric diols in the polymeric diol (B) is 0%.
A method for imparting water absorbency to synthetic fibers, which comprises immersing synthetic fibers in a polyurethane resin solution containing 50% by weight and a chain extender content of 2% to 30% by weight, and subjecting the synthetic fibers to wet treatment. be. The oxyethylene group-containing polyether diol (b ₁ ) in the present invention includes polyethylene oxide polymer (polyethylene ether glycol),
Among block and/or random copolymers of ethylene oxide and propylene oxide or tetrahydrofuran, ethylene oxide is usually
Examples include those containing more than % by weight and mixtures of two or more of these. Preferred is polyethylene ether glycol (hereinafter abbreviated as PEG).
The average molecular weight of (b ₁ ) is usually 500 to 5000, preferably
It is 1000-3000. Other polymeric diols (b ₂ ) that may be used as necessary in the present invention include polyether diols other than the oxyethylene group-containing polyether diol (b ₁ ), polyester diols, and mixtures thereof. Polyether diols other than oxyethylene group-containing polyether diol (b ₁ ) include polypropylene ether glycol, polytetramethylene ether glycol, polytetramethylene-
Examples include propylene (block and/or random) ether glycol, block and/or random copolymers of ethylene oxide and propylene oxide or tetrahydrofuran containing less than 50% by weight of ethylene oxide, and mixtures of two or more thereof. Examples of polyester diols include condensed polyester diols obtained by reacting low-molecular diols and/or polyether diols with a molecular weight of 1000 or less with dicarboxylic acids, and polylactone diols obtained by ring-opening polymerization of lactones. The low molecular weight diols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-,1,3
-butanediol, neopentyl glycol,
1,6-hexanediol, 1,8-octamethylenediol, alkyl dialkanolamine,
Low-molecular-weight diols having a cyclic group [e.g.
45-1474: Bis(hydroxymethyl)cyclohexane, m- and p-xylylene glycol, bis(hydroxyethylbenzene,
1,4-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)-
diphenylpropane (ethylene oxide adduct of bisphenol A)], and mixtures of two or more thereof. Examples of polyether diols having a molecular weight of 1000 or less include the aforementioned polyether diols such as polyethylene glycol, polytetramethylene ether glycol, polypropylene glycol, triethylene glycol; and mixtures of two or more thereof. In addition, dicarboxylic acids include aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.),
Examples include aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.) and mixtures of two or more thereof. Examples of lactones include ε-caprolactone. Polyester diols can be prepared by conventional methods, such as adding low-molecular diols and/or polyether diols with a molecular weight of 1000 or less to dicarboxylic acids or their ester-forming derivatives [such as anhydrides (maleic anhydride, phthalic anhydride, etc.), lower esters (terephthalic anhydride, etc.)]. dimethyl acids, etc.), halides, etc.] or their anhydrides and alkylene oxides (e.g. ethylene oxide and/or propylene oxide)
It can be produced by reacting (condensing) with or by adding lactone to an initiator (low molecular diol and/or polyether diol with a molecular weight of 1000 or less). Specific examples of these polyester diols include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene propylene adipate, polyethylene butylene adipate,
Polybutylene hexamethylene adipate, polydiethylene adipate, poly(polytetramethylene ether) adipate, polyethylene azelate, polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polycaprolactone diol; and a mixture of two or more thereof Can be mentioned. Polycarbonate diols can also be used. The average molecular weight (by hydroxyl value measurement) of these other polymeric diols (b ₂ ) is usually 500 to 5000, preferably 700 to 4000. The weight ratio of (b ₁ ) and (b ₂ ) in the polymer diol (B) is usually 100:0 to 50:50, preferably 100:0.
~70:30. If (b ₁ ) is smaller than the above range, the water absorbency of the polyurethane resin will be reduced. In addition, the oxyethylene content is usually 20 to 80% by weight, preferably 30 to 70% by weight in the polyurethane resin.
It is. If the oxyethylene group content is less than 20%, the water absorbency of the polyurethane resin will be low, and if it is more than 80%, the hydrophilicity of the polyurethane resin will be large, making it easy to fall off during washing, resulting in poor durability. The organic diisocyanate (A) in the present invention includes aromatic diisocyanates (4,4'-diphenylmethane diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, etc.), Examples include aromatic aliphatic diisocyanates (such as xylylene diisocyanate), aliphatic diisocyanates (such as hexamethylene diisocyanate and lysine diisocyanate), and alicyclic diisocyanates (such as isophorone diisocyanate and hydrogenated 4,4'-diphenylmethane diisocyanate). .
Details are described in Japanese Patent Application Laid-Open No. 53-42294.
Among these, in consideration of film-forming properties, aromatic diisocyanates are preferred, and 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) is particularly preferred. As the chain extender (C) in the present invention, JP-A No. 53
-42294, such as low-molecular diols [ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, bis(hydroxymethyl)cyclohexane, 1,4-bis(2-hydroxy ethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)diphenylpropane, etc.], aliphatic diamines (ethylenediamine, etc.), alicyclic diamines (isophorone diamine, 4,4'-diaminodicyclohexylmethane, etc.), aromatic Group diamines (4,
(4'-diaminodiphenylmethane, etc.), aromatic aliphatic diamines (xylylene diamine, etc.), alkanolamines (ethanolamine, etc.), hydrazine, dihydrazides (adipate dihydrazide, etc.), and mixtures of two or more of these. . Among these, preferred are low molecular weight diols, and particularly preferred are ethylene glycol (hereinafter abbreviated as EG), 1,4-butanediol,
1,6-hexanediol and a mixture of two or more thereof. The chain extender (C) in the present invention is usually 2 to 30% by weight, preferably 4 to 25% by weight in the polyurethane resin.
It is. If the content of the chain extender (C) is larger than the above range, the water absorbency will be low, and if it is smaller than the above range, the hydrophilicity of the polyurethane resin will become large, making it easy to fall off during washing, resulting in poor durability. In polyurethane resin, the ratio (equivalent ratio) of organic diisocyanate (A) to polymeric diol (B) and chain extender (C) is usually
Isocyanate group from (A): active hydrogen-containing group from polymeric diol (B) and chain extender (C) = 0.9~
1:1, 1:1, preferably substantially 1.
When the ratio is outside the above-mentioned normal range, it is difficult to produce a polyurethane resin having practically useful physical properties. Polyurethane resin can be manufactured using normal methods.
For example, organic diisocyanate (A) and polymeric diol
One shot method in which (B) and chain extender (C) are reacted simultaneously, or organic diisocyanate (A) and polymeric diol (B) are reacted first, and then chain extender (C) is reacted. One example is the prepolymer method. The preparation can be carried out in the presence or absence of a solvent inert towards isocyanate groups. When carrying out the reaction in the presence of a solvent, suitable solvents include amide solvents [dimethylformamide (hereinafter referred to as DMF)]
water-soluble solvents such as sulfoxide solvents (dimethyl sulfoxide, etc.) and sulfoxide solvents (dimethyl sulfoxide, etc.). DMF is practically preferred. The reaction temperature may be the same as the temperature normally employed when carrying out the urethanization reaction in the relevant industry, and when a solvent is used, it is usually 20 to 100°C, preferably 50 to 100°C.
80°C, typically 20-22°C if no solvent is used
℃, preferably 150-200℃. To accelerate the reaction, amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.) and tin catalysts (trimethyltin laurate,
dibutyltin dilaurate, etc.) may also be used. Furthermore, if necessary, a polymerization terminator such as a monohydric alcohol (methanol, butanol, cyclohexanol, etc.), a monohydric amine (methylamine, dimethylamine, dibutylamine, cyclohexylamine, etc.), etc. can also be used. The production of polyurethane resin can be carried out using production equipment commonly employed in the industry.
Moreover, when a solvent is not used, manufacturing equipment such as a kneader or an extruder can be used. The solution viscosity of the polyurethane resin produced in this way, measured as a 30% by weight (solid content) DMF solution, is usually 1,000 to 1,000,000 CPS/20°C, and practically preferred is 10,000 to 200,000 CPS/20.
It is ℃. The polyurethane resin obtained according to the present invention can be used as a durable water absorbency imparting agent for synthetic fibers.
Examples of synthetic fibers include polyester (hereinafter abbreviated as PET), nylon, and acrylic. Examples of its form include thread, nonwoven fabric, woven fabric, knitted fabric, and raised fabric (hereinafter abbreviated as substrate). Examples of the water absorption imparting method of the present invention include PET,
This can be carried out by immersing threads of nylon, acrylic, etc. and substrates mainly processed from these threads in a solution of polyurethane obtained according to the present invention, and subjecting them to wet treatment. The concentration of the polyurethane solution in which the substrate is immersed is usually 1 to 20% by weight, preferably 5 to 15% by weight, and the viscosity at that time is usually 1 to 10,000 CPS/
It is 20℃. Preferably it is 10-2000 CPS/20°C. Further, the amount of polyurethane resin (solid content) to be adhered to the substrate is preferably smaller than that of artificial leather or synthetic leather, and is usually 1 to 20% by weight, preferably 5 to 10% by weight, based on the substrate. If it is less than 1%, water absorption will be insufficient, and if it exceeds 20%, the texture will be hard and difficult to post-process. Water, ethylene glycol, glycerin, ethylene glycol monoethyl ether, hydroxyethyl acetate, and mixtures of two or more thereof can be used as the coagulation bath (nonsolvent) used in the wet treatment. Moreover, a mixture (mixing ratio: usually 90:10 to 30:70) of the above-mentioned non-solvent and the above-mentioned solvent can also be used.
Preferred among these are a mixture of water and a solvent (preferably DMF) and water. Wet processing methods include conventional methods, such as immersing a substrate in a polyurethane solution in a coagulation bath, coagulation with steam, partial coagulation with steam and then immersion in a coagulation bath, There is a method in which the substrate is immersed in a colloidal dispersion liquid by adding a solvent, and then immersed in a coagulation bath. The usual wet processing method is (a) described in columns 10 to 11 of U.S. Patent No. 3,284,274.
It is also described as methods (b), (c), and (d). After wet treatment, apply a defoliant and wash (water,
dried with methanol, etc.). Anionic, nonionic, cationic or amphoteric surfactants can also be used to promote solvent removal. Also British patent no.
Crosslinking treatment can also be carried out by the method described in No. 1168872. [Examples] The present invention will be further described below with reference to Examples, but the present invention is not limited thereto. Example 1 A polyurethane resin with a molecular weight of 2000 and consisting of PEG, EG, and MDI, and the oxyethylene content in the resin is
The imparting agent A of the present invention was obtained, which consisted of a DMF solution of a polyurethane resin having a chain extender content of 44% and a chain extender content of 10%. Example 2 A polyurethane resin consisting of PEG and EG with a molecular weight of 600, isophorone diisocyanate, and 4,4'-diaminodicyclohexylamine, with an oxyethylene content of 31% and a chain extender content of 25%.
An imparting agent B of the present invention consisting of a DMF solution of a polyurethane resin was obtained. Example 3 Polymer diol consisting of PEG with a molecular weight of 2000 and ethylene adipate with a molecular weight of 2000, and EG
A polyurethane resin consisting of MDI, the oxyethylene content in the resin is 23%, the chain extender is 9%,
An imparting agent C of the present invention was obtained which consisted of a DMF solution of a polyurethane resin in which the ethylene adipate content was 50% in the polymer diol. Comparative Example 1 A polyurethane resin consisting of PEG and MDI with a molecular weight of 2000, and the oxyethylene content in the resin is 89.
% of a polyurethane resin in DMF solution was obtained. Comparative Example 2 Polymer diol consisting of PEG with a molecular weight of 2000 and ethylene adipate with a molecular weight of 2000, and EG.
A polyurethane resin consisting of MDI, with an oxyethylene content of 19% and a chain extender content of 8%.
Thus, an imparting agent B consisting of a DMF solution of a polyurethane resin having an ethylene adipate content of 70% in the polymer diol was obtained. Comparative example 3 Ethylene adipate with a molecular weight of 2000 and EG
A polyurethane resin consisting of MDI, with a chain extender content of 6% in the resin.
An imparting agent C consisting of a DMF solution was obtained. Comparative example 4 85 mol% terephthalic acid and 15 mol% isophthalic acid
An imparting agent D was obtained which was an aqueous solution containing 20% by weight of a polyether ester containing 30% by weight of polyethylene glycol units based on the ester unit consisting of ethylene glycol and ethylene glycol. Examples 4 to 6, Comparative Examples 7 to 11 (Water absorption processing) The imparting agent consisting of the resin solution obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was diluted with DMF to form a solution with a resin solid content of 10%. It was created. A PET nonwoven fabric (200 g/m ₂ , approximately 1 denier) was soaked in this, and after squeezing it at a squeezing rate of 100%,
After being immersed in a 10% DMF aqueous solution at ℃ for 5 minutes to solidify, and then immersed in warm water at 50 to 60℃ for 20 minutes,
It was dried at 120°C for 10 minutes. On the other hand, the imparting agent made of the resin solution obtained in Comparative Example 4 was diluted with water to prepare a solution with a resin solid content of 10%. The same PET nonwoven fabric as above was dipped in this, and 100%
After squeezing at a squeezing rate of , it was dried at 120°C for 10°C. One drop of water was dropped with a dropper onto the dip-processed PET nonwoven fabric obtained above, and the time required for the water droplet to be completely absorbed into the nonwoven fabric was measured. Furthermore, the above-mentioned soaked PET nonwoven fabric was washed in a household washing machine filled with 40℃ water containing 1 g of neutral detergent.
After washing for 300 minutes, after washing with water at about 20℃ for 10 minutes,
It was dried at 100°C for 10 minutes. The water absorption rate test results are shown in Table 1.

[Table] Comparative Example 11 is a non-soaked PET nonwoven fabric without any imparting agent. [Effect of the invention] The polyurethane resin in the imparting agent of the present invention is
It has the advantage of superior water absorption compared to polyether-based or polyester-based polyurethane resins conventionally used for coating synthetic leather, artificial leather, and textiles. In addition, as a water absorption finishing agent for synthetic fibers, it has excellent durability compared to polyether ester, which is mainly composed of a dicarboxylic acid component consisting of known terephthalic acid and/or isophthalic acid, and a glycol component consisting of alkylene glycol and polyalkylene glycol components. It has the advantage of being Because of the above-mentioned effects, the synthetic fibers processed with the imparting agent of the present invention are useful as industrial materials such as filters, canvases, and dew condensation preventive agents for tents, wall coverings, etc. that require water absorption.

Claims (1)

[Scope of Claims] 1. A polyurethane resin comprising an organic diisocyanate (A), a polymeric diol (B) consisting of an oxyethylene group-containing polyether diol (b ₁ ), and a chain extender (C), The oxyethylene content in the resin is 20 to 80% by weight, and the chain extender content in the resin is 2 to 80% by weight.
A water absorption agent for synthetic fibers consisting of 30% by weight. 2. Polymer diol (B) consisting of organic diisocyanate (A), oxyethylene group-containing polyether diol (b ₁ ) and other polymer diol (b ₂ )
and a chain extender (C), wherein the oxyethylene content in the resin is 20 to 80% by weight, and the content of other polymeric diols is up to 50% by weight in the polymeric diol. The chain extender content in the
A water absorption agent for synthetic fibers consisting of 30% by weight. 3 A polyurethane resin made of an organic diisocyanate (A), a polymeric diol (B) consisting of an oxyethylene group-containing polyether diol (b ₁ ), and a chain extender (C), wherein oxyethylene in the resin The content is 20-80% by weight, and the chain extender content in the resin is 2-80% by weight.
A method for imparting water absorbency to synthetic fibers, which comprises soaking the synthetic fibers in a polyurethane resin solution containing 30% by weight and subjecting the synthetic fibers to wet treatment. 4 Polymer diol (B) consisting of organic diisocyanate A, oxyethylene group-containing polyether diol (b ₁ ) and other polymer diol (b ₂ )
and a chain extender (C), wherein the oxyethylene content in the resin is 20 to 80% by weight, and the content of other polymeric diols is up to 50% by weight in the polymeric diol. The chain extender content in the
A method for imparting water absorbency to synthetic fibers, which comprises soaking the synthetic fibers in a polyurethane resin solution containing 30% by weight and subjecting the synthetic fibers to wet treatment. 5 Polyurethane resin 1 to 20 to synthetic fiber
5. The method according to claim 3 or 4, wherein % by weight is applied.