JPH01239173A - Textile treating agent composition - Google Patents

Abstract

PURPOSE:To provide the title composition capable of imparting textiles with excellent persistent antistatic nature and water absorptivity, comprising a reaction product from a polyurethane derived from a polyether polyol and a compound prepared from said polyol and a specific compound. CONSTITUTION:The objective composition comprising a reaction product from (A) a compound prepared by reaction between (i) a polyether polyol compound formed by adding an alkylene oxide to a compound having in the molecule two or more active hydrogens (e.g., polyhydric alcohol) and (ii) a polyfunctional isocyanate followed by blocking the unreacted isocyanate group with an acid sulfite and (B) a compound prepared by reaction, in the presence of water, of an epihalohydrin with a reaction product having two active hydrogens bonded to the amino group in the molecule, derived from reaction of an epihalohydrin with the component (i) followed by reaction with an polyalkylene polyamine. A textile treated with this composition gives antistatic effect excellent in persistence in resistance to washing. Furthermore, freedom from unreacted amine, isocyanate groups etc. in this composition will protect the textile from discoloration.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a fiber treatment composition. More specifically, the present invention relates to a fiber treatment composition that imparts durable antistatic properties, water absorption properties, and color fastness to fibers.

[Conventional technology]

In recent years, with the development of synthetic fibers, due to their hydrophobic nature due to their chemical structure, static electricity damage has been occurring during the manufacturing process of the fibers, the processing process using them, and even during the wearing stage after sewing. . In other words, the shock to the body due to electric shock,
Accidents such as discomfort caused by clinging to the body, disasters caused by these, and decreased workability occur, and since it lacks hygroscopicity, it easily attracts dust in the air and becomes dirty.

Conventionally, in order to solve these problems, fiber treatment agents containing surfactants as a main component have been used to impart antistatic properties and water absorption properties to fibers. However, when fiber treatment agents containing surfactants as the main ingredient wash the treated fibers,
The treatment agent was removed from the surface of the fibers, resulting in decreased performance and poor durability. In recent years, as highly durable fiber treatment methods, techniques have been developed in which resins with antistatic or water-absorbing properties are attached to the fiber surface. A method of treating fibers with an aqueous solution of a polyurethane compound has been reported. For example, 1) includes a treatment agent containing a water-soluble polyglycidyl ether and a water-soluble polyamine (Japanese Patent Publication No. 37-3100), an alkaline aqueous solution of a reaction product of a polyamine containing a polyalkylene oxide group and a halogen hydrin (1. 37-3131), an alkaline aqueous solution of a mixture of a polyamine derivative or its hydrochloride and a bisepoxy compound (Japanese Patent Publication No. 38-17898, 38-
21850), an acidic aqueous solution of a compound obtained by further reacting epichlorohydrin with a reaction product of polyethylene glycol bischlorohydrin and polyethylene polyamine (Japanese Patent Publication No. 43-280), etc., and as 2), free isocyanate W of urethane prepolymer is known. Urethane compositions are known in which the isocyanate group is regenerated by blocking the isocyanate group with bisulfite or the like, and releasing the blocking agent during use.

[Problems with conventional technology]

However, these conventionally known fiber treatment compositions have various problems such as insufficient sustainability of antistatic effect, insufficient adhesion to fibers, and deterioration of the quality of treated fibers.

For example, in method 1), the stability of the aqueous solution of the treatment agent is low and storage stability is poor, the resinization reaction does not proceed sufficiently even after the fiber is treated, and therefore the washing resistance and durability are low, or free amines are produced. Since there are many isocyanate groups, there are drawbacks such as discoloration of the fibers, and method 2) has a low antistatic effect and the fibers tend to yellow due to the remaining isocyanate groups.
It has drawbacks such as low color fastness.

The present invention was developed with the above-mentioned points in mind, and it provides fibers with excellent antistatic properties, water absorption properties, and color fastness without degrading the quality of the treated fibers, and also provides these properties even after repeated washing. It is an object of the present invention to provide a fiber treatment agent composition that has durability and does not lose its effects.

[Means for solving problems]

As a result of intensive research to solve the above problems, the present inventors found that a compound (A) obtained by blocking a reaction product of a polyether polyol compound and a polyvalent isocyanate compound with an acidic sulfite, and a polyether polyol with epihalohydrin. By using the compound (C) obtained by crosslinking the compound with a polyalkylene polyamine and then reacting the compound (B) obtained by reacting with epihalohydrin, it becomes a strong resin on the surface of the fiber, giving the fiber durability. It provides excellent antistatic properties, water absorption, and color fastness,
Furthermore, since there are almost no free amines, isocyanate groups, etc., a fiber treatment agent composition that causes less discoloration of treated fibers was discovered and the present invention was achieved.

That is, in the present invention, a polyether polyol compound obtained by adding alkylene oxide to a compound having two or more active hydrogens in the molecule is reacted with a polyvalent isocyanate compound to obtain a compound having unreacted isocyanate groups, and then A compound (A) obtained by blocking unreacted isocyanate i of the compound with an acidic sulfite, and a compound (
A reaction product obtained by reacting the same polyether polyol compound used in the production of A) with epihalohydrin and then reacting with a polyalkylene polyamine, and having a small number (both 2 active hydrogens) bonded to the amino groups in the molecule. A fiber treatment agent composition using a compound (B) obtained by reacting a compound (B) with an epihalohydrin in the presence of water, and a compound (C) obtained by reacting a compound (A) with a compound (B). be.

The compound (A) used in the present invention can be obtained by reacting a polyether polyol compound with a polyvalent isocyanate compound, reacting the compound with an acidic sulfite, and blocking unreacted isocyanate groups.

That is, when compound (A) reacts a polyether polyol compound and a polyvalent isocyanate compound, at least one isocyanate group on one side of the polyvalent isocyanate compound is reacted with the polyether polyol compound, and It is obtained by reacting an acidic sulfite with a compound having a chemical structure in which at least one isocyanate group remains unreacted.

Blocking here refers to reacting unreacted isocyanate groups with acidic sulfite to temporarily block the isocyanate groups from reacting with active hydrogen.
In the reaction between compound (A) and compound (B), the blocking acidic sulfite is removed and the reaction proceeds, yielding compound (C).

The compound having an unreacted isocyanate group is a polyether polyol compound and a polyvalent isocyanate compound in the presence or absence of a solvent at 80 to 130°C, preferably i.
It is obtained by reacting at oo~110°C for 1~5 hours and removing the solvent if necessary. The reaction between a polyether polyol compound and a polyvalent isocyanate compound is performed by adding 1 polyvalent isocyanate group compound to 1 mol of the polyether polyol compound.
．． It is preferable to carry out the reaction by 5 to 6 moles. If the number of reacted moles of the polyvalent isocyanate compound is 1.5 moles or less, the viscosity of the product increases and it becomes difficult to handle. If the amount is 6 moles or more, a large amount of the polyvalent isocyanate compound remains unreacted, which discolors the fibers and reduces color fastness. The blocking reaction of a compound having an unreacted isocyanate group is carried out by adding 1 to 1.5 molar amount of acidic sulfite per 1 molar equivalent of the remaining unreacted isocyanate group, and heating at 30 to 50°C for 1 to 3 hours. Let's do it. In blocking, it is preferable to use the acidic sulfite as a 20 to 50% by weight aqueous solution, so that compound (A)
can be obtained as an aqueous solution.

The polyether polyol compound used for compound (A) is a compound having two or more active hydrogens such as polyhydric alcohol, bisphenol, polyalkylene polyamine, sorbitan alkyl monoester, sorbitan alkyl diester, castor oil, hydrogenated castor oil, etc. These compounds include oxide-added compounds, and these compounds can be prepared by adding ethylene oxide, propylene oxide, It can be obtained by addition polymerizing an alkylene oxide selected from butylene oxide or the like, or by addition polymerizing two or more alkylene oxides in random or block form. The number of moles of alkylene oxide added is preferably 20 to 200 moles. Among compounds that add alkylene oxide, polyhydric alcohols include ethylene glycol, polyethylene glycol, butanediol, propylene glycol, polypropylene glycol, glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, and bisphenol. Examples of the polyalkylene polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and polyethyleneimine. Sorbitan alkyl esters include monoesters or diesters of sorbitan and fatty acids, and fatty acids constituting the esters include lauric acid, oleic acid, stearic acid, valmitic acid, myristic acid, coconut oil fatty acid, beef tallow fatty acid, etc. Can be mentioned.

Polyvalent isocyanate compounds used in the production of compound (A) include methylene diisocyanate, hexamethylene diisocyanate, 2,2.4-)limethylhexamethylene diisocyanate, isophorone diisocyanate, 4
．． 4'-dicyclohexylmethane diisocyanate, xylylene diisocyanate, nitrodiphenyl diisocyanate, diphenylmethane sulfone diisocyanate, di-l-rodiphenylmethane diisocyanate, diphenyl sulfone diisocyanate, naphthalene diisocyanate, fluorene diisocyanate, chrysene diisocyanate, methoxyphenylene diisocyanate, biphenyl diisocyanate, diphenyl diisocyanate Toxibiphenyl diisocyanate, Examples include triphenylmethane triisocyanate.

Examples of the acidic sulfite used in the production of compound (A) include acidic sodium sulfite and acidic potassium sulfite.

The compound (B) used in the present invention is a reaction product obtained by reacting a polyether polyol compound with epihalohydrin and then a polyalkylene polyamine (hereinafter referred to as "reaction product (b)"), and adding water to the reaction product (hereinafter referred to as "reaction product (b)"). The reaction product (b) obtained as an intermediate raw material is a reaction product having a chemical structure in which a polyether polyol compound and a polyalkylene polyamine are crosslinked with epihalohydrin. be. In other words, the reaction product (b) is obtained by adding 1 mole of epihalohydrin to each OH5 of two or more hydroxyl groups (hereinafter referred to as "rOH group") possessed by one molecule of a polyether polyol compound, and then It is obtained by reacting 1 mole of each of the halohydrin groups generated in the addition reaction product molecule with a polyalkylene polyamine, and then the reaction product (b) is added with a mole corresponding to the active hydrogen bonded to the nitrogen in the molecule. A number of epihalohydrins are added and reacted to obtain compound (b).

Compound (B) can be produced, for example, as follows.

First, 2 to 7 moles of epichlordrin are added to 1 mole of a polyether polyol compound, and the reaction is carried out at 60 to 80°C for 1 to 2 hours to obtain an epihalohydrin adduct of a polyether polyol compound, and then a polyalkylene polyamine 2 to 7 mol is added and reacted at 120 to 130°C for 3 to 5 hours to obtain a compound in which a polyether polyol compound and a polyalkylene polyamine are crosslinked with epihalohydrin. The reaction amount of polyalkylene polyamine is 2
~7 mol is preferable, and 2 mol or less is the reaction product (b)
The viscosity of the polyalkylene polyamine increases, making it difficult to handle, and if the polyalkylene polyamine exceeds 7 moles, the polyalkylene polyamine becomes excessive and remains unreacted, causing coloration.

The relationship between the reaction molar ratio of epihalohydrin and polyalkylene polyamine to polyether polyol compound is as follows:
It varies depending on the number of OH groups in the polyether polyol compound molecule. That is, when there are two OH groups, it is preferable to react 2 to 2.5 moles of epichlorohydrin and then react 2 to 2.5 moles of polyalkylene polyamine with respect to 1 mole of the polyether polyol compound. Mata.

When there are 3 H groups, 1 polyether polyol compound, 1 epihalohydrin, and 1 polyalkylene polyamine each.
:3 to 3.5: It is preferable to react at a molar ratio of 3 to 3.5;
4-4.5: 4-4.5, 1:5-5.5: 5-5.5 when there are 5 OI-1 groups, 1:6-6. when there are 6 OH groups. Preferably, the reaction is carried out in a molar ratio of 5:6 to 6.5.

Next, epihalohydrin is added to the reaction product (b) obtained above in the presence of water, and the reaction is carried out at 50 to 60"C for 5 to 10 hours to obtain an aqueous solution of compound (B). The amount of epihalohydrin added to b) is preferably 2 to 20 mol per 1 mol of reaction product (b).

Since the above reaction is fast and easy to gel, it is preferable to conduct it in the presence of water, and the amount of water added is such that compound (B) is
The amount giving a concentration of 0 to 50% by weight is preferred.

As the polyether polyol compound and polyalkylene polyamine used in the production of compound (B), the same polyether polyol compound and polyalkylene polyamine as used in the production of compound (A) described above can be used, and as the epihalohydrin, epichlorohydrin can be used. ,
Examples include shrimp bromohydrin.

Compound (A) and compound (B) obtained as above
and to an aqueous solution containing 1 mol of compound (A).
B) Add an aqueous solution containing 1 to 4 mol and heat at 50 to 60°C for 5
The reaction is carried out for ~10 hours to obtain an aqueous solution of the compound (C) of the present invention. The aqueous solution of compound (C) thus obtained can be used as it is or, if necessary, mixed with water and P H
It is used as a fiber treatment agent by adding conditioning agents, softening agents, water repellents, hard finishing agents, smoothing agents, etc.

The fiber treatment agent of the present invention can be applied to general synthetic fiber knitted fabrics, but is particularly effective for polyester, polyamide, and acrylic fiber knitted fabrics. When used, a fiber treatment agent in an amount of 0.1 to 5.0 (wt)% as an active ingredient is added to the knitted fabric alone, or in a mixed aqueous solution or emulsified dispersion with other processing aids. Alternatively, it can be applied to fibers as a solution of an organic solvent by dipping, spraying, etc., and then dried or preferably heat-treated to simultaneously provide excellent and durable antistatic properties, water absorption, and color fastness. Can be granted.

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

〔Example〕

Example 1 Polypropylene glycol with an average molecular weight of 1i2000,
The average molecular weight obtained by adding ethylene oxide is 30
23 parts of hexamethylene diisocyanate was added to 200 parts of the polyether polyol compound No. 00, and the reaction was carried out at 100 to 110°C for 1 hour under a nitrogen stream to obtain a product containing 2.3% of free isocyanate groups. . 65 parts of a 20% sodium bisulfite aqueous solution was added to the total amount of this product, and the reaction was carried out for 1 hour at room temperature. Further, 944 parts of water was added to obtain a transparent aqueous solution of compound (A) (hereinafter abbreviated as rA-IJ). Ta.

Next, the same polyether polyol compound 2 used above
To 00 parts, 0.4 part of boron trifluoride etherate was added, and 12.3 parts of epichlorohydrin was gradually added while keeping the temperature at 70 to 80°C. After the addition, the reaction was carried out at 90 to 100°C for 1 hour, and diethylenetriamine 13 .9 parts were added thereto, and the reaction was carried out at 120 to 130°C for 3 hours to obtain a reaction product (b). Add 3 parts of water to the entire amount of the reaction product (b) obtained.
Add 0 parts and 12.3 parts of epichlorohydrin, and make 50~
The reaction was carried out at 60° C. for 3 hours, and 954 parts of water was further added to obtain a reddish-brown transparent aqueous solution of compound (B) (hereinafter abbreviated as rB-IJ).

Mix 150 parts of A-1 and 150 parts of B-obtained above,
The reaction was carried out at 50 to 60°C for 5 hours to obtain an aqueous solution of the urethane compound of the present invention (concentration 20%, viscosity at 25°C 330 centiboise, pH 6.3).

Example 2 - Production of Compound (A) Using the polyether polyol compound, polyvalent isocyanate compound and acidic sulfite shown in Table 1, Example 1
Similarly, a polyether polyol compound is reacted with a polyvalent isocyanate compound, and then free isocyanate groups are blown with sulfite to prepare an aqueous solution A of compound (A).
-2 to A-10 were obtained.

Production of Compound (B) Using the polyether polyol compound, epihalohydrin-1,2, and polyalkylene polyamine shown in Table-2,
Similarly to Example 1, with a polyether polyol compound
- 1 〇' - Reaction product (b) obtained by reacting epihalohydrin (this will be referred to as "epihalohydrin-1") and then reacting with a polyalkylene polyamine, and epihalohydrin (this will be referred to as "epihalohydrin-2"). were reacted to obtain aqueous solutions B-2 to B-7 of compound (B).

Table 3 Production of urethane compound Compound (A) in Table 1 and compound (B) in Table 2 were mixed in the ratio shown in Table 3, and reacted in the same manner as in Example 1 to produce urethane compound. Aqueous solutions of compounds (Examples 2 to 10) were obtained.

Comparative Examples 1 to 5 As a comparative example, aqueous solution A- of compound (A) shown in Table-1
1 (Comparative Example 1), A-9 (Comparative Example-2), and Table-2
Aqueous solution B-1 of compound (B) shown in (Comparative Example-3),
B-6 (Comparative Example-4) and a commercially available cationic antistatic agent (Comparative Example-5) were used.

[Test example]

Polyester dyed fabric (dark blue) and acrylic knit dyed fabric (skin tone) were treated using the aqueous solutions obtained in Examples 1 to 10 and Comparative Examples 1 to 5, and the charge amount, half-life, and water absorption were determined by the methods described below. The properties and abrasion fastness were measured.

Charge amount, half-life, water absorption for polyester dyed cloth,
Table 4 shows the measurement results for rubbing fastness, and Table 5 shows the measurement results for the amount of charge, half-life, and water absorption of dyed acrylic knit fabric.
Shown below.

○Processing conditions for polyester dyed cloth Padding: 1 dip-1ni+).

Aperture rate: 85% Pre-drying: 110℃ x 10 minutes Heat set: 170℃ x 1 minute Resin concentration: 3% as active ingredient ○Processing conditions for acrylic knit dyed fabric Banding: 1 dip - 1 nip.

Squeezing rate: 40% Pre-drying: 80°C x 30 minutes Heat setting: 120°C x 30 seconds Resin concentration: 3% as active ingredient ○Measurement methods for charge amount, half-life, fastness to rubbing, and water absorption (1) Charge amount (Fj friction charge voltage) Using a Kyoto University Kaken 2 rotary static tester (Koa Shokai type), a test cloth that had been conditioned at 20°C and 40% R11 for 48 hours was tested in the same atmosphere under a load of 500 g and at a rotation speed. The sample was brought into contact with Kanakin No. 3 cotton cloth for 60 seconds at 400 rpm and a voltage of 100 cm, and the charged voltage at that time was measured.

(2) Using a half-relative osteotomer (manufactured by Otsuki Shokai), 20°C14
A test cloth that had been conditioned with 0% R1+ for 48 hours was charged in the same atmosphere with an applied voltage of 10 KV and an application time of 4 seconds, and the time until the charged voltage was halved was measured.

(3) Water absorption Measured by method A of JIS L-1096.

(41FJ Rubbing Fastness Measured according to the method of JIS L-0849 using a friction test! S! machine type ■.

(5) Washing test The washing test was carried out using a reversible electric washing machine, using Millon New Jump as the detergent at a ratio of 2 g/β.
0°C for 5 minutes) - Spin drying, rinsing (2 minutes at room temperature) - Spin drying, rinsing (2 minutes at room temperature) - Spin dry] as one wash.
Repeated 0 times.

Table 4 Table 5 [Effects of the Invention] As explained above, the present invention uses a urethane compound derived from a polyether polyol compound and a crosslinked product of a polyether polyol and a polyalkylene polyamine as a fiber treatment composition. It uses a compound obtained by reacting with a compound obtained by adding shrimp halohydrin to
According to the fiber treatment composition of the present invention, it imparts excellent antistatic properties, water absorption properties, and color fastness to fibers, and
Because the treatment agent firmly forms a resin on the surface of the fiber, it provides good, durable performance with little deterioration due to washing, and since it does not contain unreacted amines or isocyanate groups, it does not cause discoloration of the fiber. It has the effect of less.

Patent applicant Miyoshi Yushi Co., Ltd.

Claims (1)

[Claims] A polyether polyol compound obtained by adding an alkylene oxide to a compound having two or more active hydrogens in the molecule is reacted with a polyvalent isocyanate compound to obtain a compound having unreacted isocyanate groups, and then the unreacted portion of the compound is reacted with a polyvalent isocyanate compound. A compound (A) obtained by blocking the isocyanate groups of with an acidic sulfite is reacted with the same polyether polyol compound used to produce compound (A) with epihalohydrin, and then with a polyalkylene polyamine. and compound (B) obtained by reacting a reaction product having at least two active hydrogens bonded to amino groups in the molecule with epihalohydrin in the presence of water. ) A fiber treatment agent composition characterized in that it uses a compound (C) obtained by reacting with the compound (C).