JPS6233879A - Hydrophilicity imparting agent of synthetic fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a hydrophilic treatment agent for synthetic fibers.

[Prior Art] Di(meth)acrylate, which is an algylene oxide adduct of bisphenol A, is used as a hydrophilic treatment agent for synthetic fibers (Japanese Patent Publication No. 34818/1981).

[Problems to be Solved by the Invention] However, when this material is used, it has a low adhesion rate to synthetic fibers, so a large amount must be used, and its durability is also insufficient.

[Means for Solving the Problems] The present inventors have conducted intensive studies to develop a hydrophilic treatment agent for synthetic fibers that improves the adhesion rate and durability, and as a result, they have arrived at the present invention.

The present invention is based on the general formula % (1) (where 8 is a residue of an active hydrogen-containing unsaturated monomer, Y is a residue of a hydrophilic polyoxyalkylene chain-containing NCO urethane prepolymer, and n is 1 or more This is a synthetic wc miscellaneous hydrophilic treatment agent consisting of a hydrophilic compound represented by (an integer).

In the general formula (1), the active hydrogen-containing unsaturated polymer of A is
The unsaturated monomers forming the residue are listed below.

(1) Unsaturated upper hydroxyalkyl containing a hydroxyl group (alkyl group usually has 2 to 4 carbon atoms) (meth)acrylate (represents acrylate and/or methacrylate).

The following is also shown in the same manner. ) [hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc.], N-hydroxyalkyl acrylamide [N-methylol (meth)acrylamide, N-ethylol (meth)acrylamide, etc.], (meth)allyl alcohol etc.

(2) Amino group-containing unsaturated monomers (meth)allylamine, (meth)acrylamide of alkylene polyamine [ethylenediamine 7) (meth)acrylamide, diethylenetriamine 7-(meth)acrylamide, etc.;

Among these anti-af [monomers, preferred are 1
-roxyalkyl (meth)acrylate, particularly preferred is 2-hydroxyethyl (meth)acrylate.

The prepolymers forming the residue of the hydrophilic polyoxyalgylene chain-containing \CO urethane prepolymer of Y include:
A \CO urethane prepolymer of an organic polyisocyanate and a polyol (at least a part of which contains a hydrophilic polyoxyalkylene chain; the same applies hereinafter) can be used.

The above-mentioned organic polyisocyanates include aliphatic and aromatic isocyanates, such as fatty IIJ group polyisocyanates 1 (tetramethylene diisocyanate, hexamethylene diisocyanate, etc.), alicyclic polyisocyanates (isoborone diisocyanate, etc.), to l(IPDI>
, 4,4°-dicyclohexylmethane diisocyanate, etc.), araliphatic polyisocyanates (xylylene diisocyanate, etc.), aromatic polyisocyanates (
[・Lylene diisocyanate is DI), 4,4'-diphenylmethane diisocyanate (MDI), crude MDI, modified MDI, etc.), multimers of the above polyisocyanates [TDI multimers (e.g., diadem, trimam), etc.] etc. are set back.

Among these, preferred are aliphatic polyisocyanates, and particularly preferred are IPDI, hexamethylene diisocyanate, and 4,4-dicyclohexylmethane diisocyanate.

Examples of the polyols include high molecular polyols (such as polyether polyols and polyester polyols), low molecular polyols, and alkanolamines.

As polyether polyols, low molecular polyols (
Ethylene glycol, propylene glycol, 1,4-
butanediol, glycerin, trimethylolpropane, hexanetriol, sorbitol, sucrose, etc.), or alkylene oxides (with 2 to 4 carbon atoms) of amines (alkanolamines, aliphatic polyamines, etc.)
Fullylene oxides such as ethylene oxide, propylene oxide, butylene oxide> adducts and ring-opening polymers of alkylene oxides are required, and specifically include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Polyester polyols include polycarboxylic acids (aliphatic polycarphonic acids such as adipic acid, maleic acid, trimerized linoleic acid; aromatic polycarphonic acids such as phthalic acid) and low molecular weight polyols or polyether polyols containing terminal human xyl groups. Noester polyol, polycaprolactone polyol For example, initiator [glycol (ethylene glycol, etc.), triol, etc.]
Based on this (substituted) caprolactone (ε-caprolactone, α~methyl-ε-caprolactone, ε-
Examples include polyols obtained by addition-polymerizing medyl (ε-caprolactone, etc.) in the presence of a catalyst (organometallic compound, metal chelate compound, fatty acid metal acylated product, etc.).

The equivalent weight of the polymer polyol is usually 100 to 4,000, preferably 500 to 3,000.

As the low-molecular-weight polyol, the same low-molecular-weight polyols as explained in the polyether polyol can be used.

Examples of alkanolamines include N,N-dialkylmonoalkanolamine, N,N-dimethylethanolamine, etc.)
, N-alkyl dialkanolamine (N-methylgetanolamine, N-butylgetanolamine, etc.)
, trialkanolamines (triethanolamine, tripropaturamine, etc.), and their nitrogen atom quaternized products using a quaternizing agent such as dimethyl 5AW or pencil chloride.

The molar value for the hydroxyl group of the isocyanate group is usually 1.0.
5 to 3.01, preferably 1.3 to 2.2.

\Preferred among CO urethane prepolymers are urethane prepolymers made from polyether polyols and aliphatic polyisocyanates, and particularly preferred are polyethylene glycols (average molecular weight 1000-60).
00) and IPDI and/or hexamethylene diisocyanate and/or 4,4-dicyclohexylmethane diisocyanate.

Preferably n in general formula (1) is 2.

When organic polyisocyanate is represented by the formula It has a group represented by the formula % at the end, and the prepolymer and the active hydrogen-containing unsaturated polymer are represented by the formula A-H (where A is an active hydrogen-containing unsaturated group). The compound of general formula (1) formed from saturated heptamer residue has a group represented by the formula at its terminal.

Diisocyanate [X
(The compound of general formula (1) when NCO>2i is used has a group represented by the formula at the terminal.

Examples of the compound represented by the general formula (1) include hydroxydiyl methacrylate and a 2:2:1 molar urethane of IPDI and polyethylene glycol (average molecular weight 4000).

The compound of general formula (1) can be obtained by a conventional urethanization reaction method. For example, (1) a method of reacting polyols with an organic boronisocyanate with an excess of isocyanate groups to produce an NCO urethane prepolymer, and (2) reacting this with an unsaturated polymer containing active hydrogen; A method of reacting a monomer and an organic polyisocyanate with an excess of isocyanate groups to produce an NCO urethane prepolymer containing unsaturated double bonds, and reacting this with polyols, and A method of reacting polyisocyanates can be used.

(However, at least a part of the polyols contains a hydrophilic polyoxyalkylene chain.) The reaction temperature is usually 40°C.
-140'C, preferably 60-100'C. In order to accelerate the reaction, known catalysts for urethanization reactions are used, such as organometallic compounds such as dibutyltin dilaurate and stannous octoate, triethylenediamine, triethylamine, and 1,8-diazabicyclo[5.4.0]. It is also possible to use tertiary amine compounds such as endecene-7.

Synthetic fibers to which the treatment agent of the present invention is applied include polyester, polyamide, polyacrylonitrile, polyolefin, polyurethane, modified raw materials thereof, and blends of these synthetic fibers with other natural, recycled, and semi-synthetic fibers. Its forms include cotton, thread, tow, top, skein, striped fabric, and non-woven fabric5.

When using the embedding agent of the present invention, the amount applied to the fiber material is usually 0.1 to 30%, preferably 0.1 to 30%, preferably 0.1 to 30%, based on the fiber nail.
Adjustment is made so that the adhesion is 5 to 5%. If the amount of adhesion is too low, the performance will be insufficient, and if it is too high, it will cause the object to be treated to stagnate and the quality of the material to be deteriorated.

The processing agent of the present invention can be used by the following method. For example, ■ synthetic fibers are immersed in an aqueous solution or aqueous dispersion containing the treatment agent and hand initiator of the present invention,
40'(:, method of carrying out the treatment, ■ immersing the synthetic fiber in an aqueous solution or aqueous dispersion containing the treatment agent and polymerization initiator of the present invention, or (or spraying these solutions onto the synthetic fiber) 80~200 after squeezing and squeezing.
A method of performing moist heat treatment at 'C', after attaching the treatment agent of the present invention to synthetic fibers in the same manner as in ■■, 120 to 200
An example is a method of dry heat treatment at 'C.

The above polymerization initiators include common radical polymerization catalysts, such as peroxides such as benzoyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide; inorganic peroxides such as perammonium peroxide,
Sodium persulfate, potassium persulfate, etc.), azo compounds (azobisisobutyronitrile, azobisisovaleryl acid, etc.), redox compounds (hydrogen peroxide, persulfate, diacyl peroxide, etc.) Examples include metal ions, diluted sulfates, mercaptans, amines, and other reducing agents). Preferably, it is a peroxide, particularly preferably a persulfate. The amount of polymerization initiator used is usually 0.1 to 50%, preferably 1 to 10%, based on the weight of the treatment agent.
It is necessary.

The above-mentioned dispersion in water is a liquid in which a processing agent is finely dispersed in water. In this case, water-soluble solvents (methanol, isopropanol, avitone, dimethylformamide, etc.), water-insoluble solvents (toluene, xylene, benzyl alcohol, etc., and chlorobenzene, methylnaphthalene, etc. with carrier effect), as necessary, Common surfactants used as emulsifiers and dispersants and unsaturated monomers having a hydrophilic group may be used. Examples of unsaturated monomers containing the above-mentioned hydrophilic groups include acidic unsaturated monomers such as (meth)acrylic acid, maleic acid, styrenesulfonic acid, vinylsulfonic acid, and 2-hydroxy-3-(meth)acryloxypropylsulfonic acid. ], basic unsaturated meth)acrylamide, N,N-dihydroxyethyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylate, morpholinoethyl(meth)acrylate, 4-vinylpyridine, 2-Vinylpyridine, etc. 1, Other unsaturated polymers [(meth)allyl alcohol, hydroxypropyl (meth)acrylate, polyoxyethylene oxypropylene (random or block) glycol mono(meth)allyl ether, N,N , N-trimethyl-
N-(meth)acryloxyethylammonium chloride, etc.] are essential.

[Examples] The present invention will be further described below with reference to Examples and Test Examples, but the present invention is not limited thereto. The performance evaluation method in the test example is as follows.

(a) Adhesion rate: Determined from the change in weight of the test fabric before and after treatment.

The same electric training property: The temperature of the treated fabric was controlled in an atmosphere of 20°C, 140% RH for 6 hours, and the frictional charging voltage was measured using a rotary static tester at Kyoto University Kakenji under conditions of 20°C and 40% RH. It was measured.

(c) Water absorption: One drop of water (10 μm) was dropped on the test cloth, and the time required for it to be completely absorbed was measured.

Example 1 Polyethylene glycol 40 with average molecular weight ff 14000
0 parts of isophorone diisocyanate and 44.4 parts of isophorone diisocyanate were reacted for 4 hours at 120 to 125 °C under a nitrogen atmosphere, and then 26 parts of hydroxyethyl methacrylate, 0.02 parts of dibutyltin dilaurate, and 0.5 parts of monomethylhydroquinone were added to give 75 parts of isophorone diisocyanate. After reacting at ~80''C for 200 hours, the processing agent (a) of the present invention was obtained as a white solid.

Polyester Amundsen fabric 59 was immersed in a treatment bath of 1 q of 0.4 y of this treatment agent (A) and 0.019 of potassium persulfate dissolved in 100 9 of water, and these were placed in a stainless steel sealed container and kept in a sealed state. 120'Cx while rotating with
Heat treatment was performed for 30 minutes. After the heat treatment, the polyester Amundsen was taken out, washed with water, dried, and used as a finished cloth for performance evaluation. In addition, a part of the finished cloth was soaked in a 2 g/l neutral detergent (ZABU: manufactured by Kao Soap) aqueous solution at 40'C for 1 hour.
Washed for 0 minutes, then rinsed for 10 minutes. This process 5
After washing for 5 times (washing) was repeated 5 times, the treatment was treated as 5 and subjected to performance evaluation.

Example 2 A polyester suede fabric was immersed in an alpha bath containing 2% of the treatment agent (a) of the present invention obtained in Example 1 and 0.29% of sodium persulfate, and squeezed with a mangle to an impregnation rate of 80%.

The fabric was then treated in saturated steam at 110'C for 5 minutes, washed with water and dried to obtain a finished fabric. Washing was carried out in the same manner as in Example 1, and a finished cloth, Treatment 15 after 85 washes, was prepared and subjected to performance evaluation.

Comparative Example 1 Polyesteramundzen, Sashimono 53, was immersed in a treatment bath obtained by dissolving 0.43 of diacrylate, which is an adduct of 40 moles of ethylene oxide to bisphenol, and 0.019 of potassium persulfate in 100% of water. A specimen No. 5 was prepared by heat treatment in the same manner as in Example 1, and after 5 times of washing and finishing, No. 5 was prepared, and subjected to a 1-viability evaluation.

Test Example 1 The adhesion rate was measured and the performance evaluation (electrification property and water absorption property) was performed on Finish 15 obtained in Examples 1 to 2 and Comparative Example 1 and Ifi washed 5 times, and the results are shown in Table 1. Ta.

Table-1 [Effects of the invention 1 The processing agent of the present invention has the following effects.

(1) To give synthetic fibers durable and excellent electrostatic properties and water absorption properties.

(2) Since it has better adhesion to fibers than conventional hydrophilic treatment agents, sufficient effects can be obtained with a small amount of use.

Claims (1)

[Claims] 1. General formula Y-(NHCOA)_n(1) (wherein A is the residue of an active hydrogen-containing unsaturated monomer, Y is the residue of a hydrophilic polyoxyalkylene chain-containing NCO urethane prepolymer) A hydrophilic treatment agent for synthetic fibers comprising a hydrophilic compound represented by the following formula (n is an integer of 1 or more). 2. The processing agent according to claim 1, wherein the prepolymer is an NCO urethane prepolymer of an organic polyisocyanate and a polyol (at least a part of which contains a hydrophilic polyoxyalkylene chain). 3. The compound has the general formula -CONHX-(NHCOA)_m_-_1 (in the formula, A
is a residue of an active hydrogen-containing unsaturated monomer, X is a residue of an organic polyisocyanate that constitutes the end of the NCO urethane prepolymer containing a hydrophilic polyoxyalkylene chain, and m is the valence of the polyisocyanate, which is an integer of 2 or more. be. ) The processing agent according to claim 2, which has a group represented by the following. 4. The processing agent according to any one of claims 1 to 3, wherein n is 2.