JP2662971B2 - Fiber treatment composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a fiber treatment composition. More specifically, the present invention relates to a fiber treating agent composition which imparts a durable antistatic property, water absorption, and color fastness to fibers.

[Conventional technology]

In recent years, with the development of synthetic fibers, due to the hydrophobic nature of their chemical structure, static electricity has been generated in the production of the fibers, the processing process using them, and the stage of wearing after sewing. . In other words, shocks to the body due to electric shock, discomfort due to wrapping around the body, occurrence of disasters based on these, accidents such as reduced workability, etc. occur, and because it lacks moisture absorption, it absorbs dust in the air. There was a problem that it was easily stained.

Conventionally, in order to solve these problems, a fiber treatment agent containing a surfactant as a main component has been used.
Water absorption was given. However, the fiber treating agent containing a surfactant as a main component, when the treated fiber is washed, the treating agent is removed from the surface of the fiber and the performance is reduced,
The durability was poor. In recent years, as a highly durable fiber treatment method, a technique of adhering a resin having antistatic properties or water absorbency to the surface of the fiber has been developed, and 1) a method of treating with an aqueous solution of an amino compound and a crosslinking agent, and 2) a water solution. Methods for treating fibers with an aqueous solution of a water-soluble urethane compound have been reported. For example, 1) includes a treating agent containing a water-soluble polyglycidyl ether and a water-soluble polyamine (Japanese Patent Publication No. 37-3100), and an alkaline aqueous solution of a reaction product of a polyamine containing a polyalkylene oxide group, a halogen and drin (Japanese Patent Publication No. 37-3131), an alkaline aqueous solution of a mixture of a polyamine derivative or its hydrochloride and a bisepoxy compound (Japanese Patent Publication Nos. 3817898 and 38-21850), and a reaction product of polyethylene glycol bischlorohydrin and polyethylene polyamine. An acidic aqueous solution of a compound reacted with chlorhydrophosphorus (Japanese Patent Publication No. 43-280) is known.
As 2), a urethane composition which blocks a free isocyanate group of a urethane prepolymer with a bisulfite or the like, releases a blocking agent when used, and regenerates an isocyanate group, and the like are known.

[Problems of the prior art]

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

For example, in the method 1), the stability of the aqueous solution of the treating agent is low and the storage stability is poor, and even if the fiber is treated, the resinification reaction does not sufficiently proceed, so that the washing resistance and the durability are low, or the fiber amine is not used. However, the method 2) has a low antistatic effect, and the remaining isocyanate groups tend to cause yellowing of the fibers due to residual isocyanate groups, and also have disadvantages when the dyeing fastness is low. is there.

The present invention has been made in view of the above points, without deteriorating the quality of the treated fiber, while imparting excellent antistatic properties, water absorption, dyeing fastness to the fiber, these even after repeated washing It is an object of the present invention to provide a durable fiber treatment composition that does not lose its effect.

[Means for solving the problem]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a compound (A) obtained by blocking a reaction product of a polyether polyol compound and a polyvalent isocyanate compound with acidic sulfite, and a polyether polyol obtained by epihalohydrin By using the compound (C) obtained by crosslinking the compound with a polyalkylene polyamine and then reacting with the compound (B) obtained by reacting epihalohydrin, the resin is firmly resinized on the surface of the fiber and durable to the fiber The present invention has found a fiber treating agent composition which imparts a characteristic antistatic property, water absorption, and color fastness, and has little discoloration of the treated fiber because it has almost no free amine and isocyanate groups. .

That is, the present invention reacts a polyether polyol compound obtained by adding an alkylene oxide to a compound having two or more active hydrogens in the molecule with a polyvalent isocyanate compound to obtain a compound having an unreacted isocyanate group, Epihalohydrin is reacted with the compound (A) obtained by blocking the unreacted isocyanate group of the compound with an acidic sulfite and the same polyether polyol compound used in the production of the compound (A), and then reacted with a polyalkylene polyamine. Compound (A) of compound (B) obtained by reacting epihalohydrin with a reaction product having at least two active hydrogens bonded to an amino group in the molecule thereof in the presence of water And a compound (B) obtained by reacting the compound (B) with the compound (B).

The compound (A) used in the present invention is obtained by reacting a compound obtained by reacting a polyether polyol compound with a polyvalent isocyanate compound with an acidic sulfite to block unreacted isocyanate groups.

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

The blocking herein refers to reacting an unreacted isocyanate group with an acidic sulfite to temporarily block the isocyanate group from reacting with active hydrogen. In the reaction between the compound (A) and the compound (B), , The blocking acid sulfite is removed and the reaction proceeds,
Compound (C) is obtained.

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 at 100 to 130 ° C.
It is obtained by reacting at 110 ° C. for 1 to 5 hours and, if necessary, removing the solvent. In the reaction between the polyether polyol compound and the polyvalent isocyanate compound, it is preferable to react 1.5 to 6 mol of the polyvalent isocyanate compound with respect to 1 mol of the polyether polyol compound. The viscosity of the product increases, making it difficult to handle. If it is 6 mol or more, a large amount of the polyvalent isocyanate compound remains unreacted, which causes discoloration of the fiber and lowers the color fastness. The blocking reaction of the compound having an unreacted isocyanate group is
1 to 1 mole equivalent of remaining unreacted isocyanate groups
Add 1.5 mole times the amount of acidic sulfite, and add 1 to 30 to 50 ° C.
Perform by heating for 3 hours. In the blocking, the acidic sulfite is preferably used as an aqueous solution of 20 to 50% by weight, whereby the compound (A) can be obtained as an aqueous solution.

Examples of the polyether polyol compound used for the compound (A) include polyhydric alcohol, bisphenol, polyalkylene polyamine, sorbitan alkyl monoester,
Compounds obtained by adding an alkylene oxide to a compound having two or more active hydrogens such as sorbitan alkyl diester, castor oil, and hydrogenated castor oil. These compounds are compounds having two or more active hydrogens according to a conventional method. In addition, in the presence or absence of a catalyst, at 150 to 190 ° C., ethylene oxide, propylene oxide, addition polymerization of alkylene oiside selected from butylene oxide,
Alternatively, it can be obtained by random or block addition polymerization of two or more alkylene oxides. The addition mole number of the alkylene oxide is preferably from 20 to 200 moles. Among the 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. And polyalkylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine. Examples of the sorbitan alkyl ester include a monoester or diester of sorbitan and a fatty acid, and the fatty acids constituting the ester include lauric acid, oleic acid, stearic acid, barmitic acid, myristic acid, coconut oil fatty acid, tallow fatty acid, and the like. No.

Examples of the polyvalent isocyanate compound used in the production of compound (A) include methylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate,
4'-dicyclohexylmethane diisocyanate, xylylene diisocyanate, nitrodiphenyl diisocyanate, diphenylmethanesulfone diisocyanate, nitrodiphenylmethane diisocyanate, diphenylsulfone diisocyanate, naphthalene diisocyanate, full orange isocyanate, chrysene diisocyanate, methoxy phenylene diisocyanate,
Biphenyl diisocyanate, dimethoxybiphenyl diisocyanate, triphenylmethane triisocyanate and the like can be mentioned.

As the acidic sulfite used for the production of the compound (A),
Sodium acid sulfite or potassium acid sulfite is mentioned.

The compound (B) used in the present invention is obtained by reacting a polyether polyol compound with epihalohydrin and then reacting with a polyalkylene polyamine (hereinafter referred to as “reaction product (b)”). It is obtained by reacting epihalohydrin in the presence, and the reaction product (b) obtained here as an intermediate material is a reaction product having a chemical structure in the form of a polyether polyol compound and a polyalkylene polyamine crosslinked with epihalohydrin. is there. That is, the reaction product (b) is added to one or more hydroxyl groups (hereinafter referred to as “OH groups”) of one molecule of the polyether polyol compound by adding 1 mol of epihalohydrin to each of the OH groups. Then, one mole of each of the halohydrin groups formed in the addition reaction product molecule is reacted with a polyalkylene polyamine, and then the reaction product (b) is reacted with active hydrogen bonded to nitrogen in the molecule. The appropriate moles of epihalohydrin are added and reacted to obtain compound (b).

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

First, 2 to 7 mol of epihalohydrin is added to 1 mol of the polyether polyol compound, and a reaction is performed at 60 to 80 ° C. for 1 to 2 hours to obtain an epihalohydrin adduct of the polyether polyol compound. In addition, by reacting at 120 to 130 ° C. for 3 to 5 hours, a compound in which a polyether polyol compound and a polyalkylene polyamine are crosslinked with epihalohydrin is obtained. The reaction amount of the polyalkylene polyamine is preferably from 2 to 7 mol, and if it is less than 2 mol, the viscosity of the reaction product (b) increases, making it difficult to handle. If it is more than 7 mol, the polyalkylene polyamine becomes excessive and unreacted. It remains as it is and causes coloring.

The relationship between the reaction molar ratio of epihalohydrin and polyalkylene polyamine to the polyether polyol compound changes 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 2 to 2.5 moles of polyalkylene polyamine with respect to 1 mole of the polyether polyol compound. Also OH
When there are three groups, the polyether polyol compound, epihalohydrin, and polyalkylene polyamine are each 1: 3
The reaction is preferably performed at a molar ratio of ~ 35: 3 to 3.5, and similarly, when there are four OH groups, each is 1: 4 to 4.5: 4 to 4: 5, and when there are five OH groups, each is 1: 5. When the number of OH groups is 5.5, the reaction is preferably performed at a molar ratio of 1: 6 to 6.5: 6 to 6.5, respectively.

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

Since the above reaction is rapid and easily gelled, it is preferable to carry out the reaction in the presence of water.
An amount that results in a concentration of 20 to 50% by weight is preferred.

As the polyether polyol compound and the polyalkylene polyamine used in the production of the compound (B), the same polyether polyol compound and polyalkylene polyamine used in the production of the compound (A) described above can be used, and epichlorohydrin is used as the epihalohydrin. , Epibromohydrin and the like.

The compound (A) and the compound (B) obtained as described above are added to an aqueous solution containing 1 mol of the compound (A), and an aqueous solution containing 1 to 4 mol of the compound (B) is added thereto. The reaction is carried out for up to 10 hours to obtain an aqueous solution of the compound (C) of the present invention. The aqueous solution of the compound (C) thus obtained is used as a fiber treating agent by adding water, a pH adjuster, a soft finish, a water repellent, a hard finish, a smoothing agent, or the like as it is or as necessary. .

The fiber treating agent of the present invention can be applied to general synthetic fiber knitted fabrics, and is particularly effective for polyester, polyamide and acrylic fiber knitted fabrics. In use, the amount of the fiber treating agent is 0.1 to 5.0 (wt)% as an active ingredient, or a mixed aqueous solution with other processing aids, an emulsified dispersion, or an organic solvent. As a solution, the fiber is attached to the fiber by dipping, spraying, or the like, and then dried or, preferably, subjected to heat treatment to simultaneously impart excellent durable antistatic properties, water absorption, and color fastness. I can do it.

 Hereinafter, the present invention will be described with reference to examples.

〔Example〕

Example 1 To 200 parts of a polyether polyol compound having an average molecular weight of 3000 obtained by adding ethylene oxide to polypropylene glycol having an average molecular weight of 2,000, 23 parts of hexamethylene diisocyanate was added.
For 1 hour to remove free isocyanate groups from 2.
A product containing 3% was obtained. 65 parts of a 20% aqueous sodium bisulfite solution was added to the total amount of the product, reacted at room temperature for 1 hour, and further added with 944 parts of water to give a clear aqueous solution of compound (A) (hereinafter abbreviated as "A-1"). I got

Then the same polyether polyol compound used above
Add 0.4 parts of boron trifluoride etherate to 200 parts, and add 70 parts
While maintaining the temperature at ~ 80 ° C, 12.3 parts of epichlorohydrin is gradually added, and after the addition, the reaction is carried out at 90 to 100 ° C for 1 hour. Further, 13.9 parts of diethylenetriamine is added, and the reaction is carried out at 120 to 130 ° C for 3 hours. (B) was obtained. 30 parts of water and epichlorohydrin 1 were added to the total amount of the obtained reaction product (b).
2.3 parts were added and reacted at 50-60 ° C. for 3 hours. Further, 954 parts of water was added, and a reddish brown transparent aqueous solution of compound (B) (hereinafter referred to as “B-
1 ").

50 parts of A-1 and 50 parts of B-1 obtained above are mixed and reacted at 50 to 60 ° C. for 5 hours to give an aqueous solution of the urethane compound of the present invention (concentration: 20%, viscosity at 25 ° C .: 330 centipoise, PH
6.3) was obtained.

Examples 2 to 10 Production of Compound (A) Using a polyether polyol compound, a polyvalent isocyanate compound and an acidic sulfite shown in Table 1, an example was prepared.
A polyisocyanate compound was reacted with the polyether polyol compound in the same manner as in 1, and then free isocyanate groups were blocked with sulfite to obtain aqueous solutions A-2 to A-10 of the compound (A).

Production of Compound (B) Using a polyether polyol compound, epihalohydrin-1,2, and a polyalkylene polyamine shown in Table 2,
A reaction product (b) obtained by reacting a polyether polyol compound with epihalohydrin (hereinafter referred to as “epihalohydrin-1”) and then reacting with a polyalkylene polyamine in the same manner as in Example 1 is added to epihalohydrin (which is referred to as “ephalohydrin”). Epihalohydrin-2 ") to give aqueous solutions B-2 to B-7 of compound (B).

Production of urethane compound The compound (A) in Table 1 and the compound (B) in Table 2 were
The mixture was mixed at the ratio shown in Table 3 and reacted in the same manner as in Example 1 to obtain an aqueous solution of a urethane compound (Examples 2 to 10).

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

(Test example)

Using the aqueous solutions obtained in Examples 1 to 10 and Comparative Examples 1 to 5, a polyester dyed cloth (dark blue) and an acryl knit dyed cloth (skin color) were treated, and the charge amount, half life, Water absorption and rub fastness were measured.

Table 4 shows the measurement results of the charge amount, half-life, water absorption and friction fastness of the polyester dyed fabric, and Table 5 shows the measurement results of the charge amount, half-life and water absorption of the acryl knit dyed fabric.

○ Processing conditions for polyester dyed cloth Padding: 1 dip-1 nip.

Drawing ratio: 85% Predrying: 110 ° C × 10 minutes Heat setting: 170 ° C × 1 minute Resin concentration: 3% as active ingredient ○ Processing conditions for acrylic knit dyed cloth Padding: 1 dip-1 nip.

Squeezing ratio: 40% Predrying: 80 ° C x 30 minutes Heat setting: 120 ° C x 30 seconds Resin concentration: 3% as active ingredient ○ Measurement method of charge amount, half-life, friction fastness, water absorption (1) Charge amount (Friction band voltage) Using a Kyoto University Chemical Research-type rotary static tester (manufactured by Koa Shokai Co., Ltd.), a test cloth conditioned for 48 hours at 20 ° C. and 40% RH was loaded in the same atmosphere at a load of 500 g, a rotation speed of 400 rpm,
It was brought into contact with Kanakin No. 3 cotton cloth for 60 seconds at a voltage of 100 V, and the charged voltage at that time was measured.

(2) Half-life 20 ° C, 40% using Honest meter (made by Shishido Shokai)
A test cloth conditioned for 48 hours at RH was charged in the same atmosphere at an applied voltage of 10 KV and an applied time of 4 seconds, and the time until the charged voltage was reduced to half was measured.

(3) Water absorption Measured according to the method A of JIS L-1096.

(4) Friction fastness Measured by the method of JIS L-0849 using a friction tester type II.

(5) Washing test In the washing test, an inverted electric washing machine was used, and Miyoshi New Jump was used as a detergent at a rate of 2 g /.
Dehydration → Rinse (2 minutes at room temperature) → Dehydration →
Rinsing (at room temperature for 2 minutes) → dehydration] was repeated 10 times as one washing.

[Effects of the Invention] As described above, the present invention provides, as a fiber treatment composition, a urethane compound derived from a polyether polyol compound, and a compound obtained by adding epihalohydrin to a crosslinked product of a polyether polyol and a polyalkylene polyamine. According to the fiber treating agent composition of the present invention, the fiber has excellent antistatic properties, water absorption, and color fastness, and is treated on the surface of the fiber. Because the agent is strongly resinified,
Gives a good durable performance with little decrease due to washing,
Further, since it does not contain an unreacted amine, isocyanate group, or the like, it has the effect of little discoloration of the fiber.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shoji Ogihara 1366 Nishiide, Noyoro-cho, Iwakura-shi, Aichi Pref. JP-A-61-70076 (JP, A)

Claims (1)

(57) [Claims] 1. A polyether polyol compound obtained by adding an alkylene oxide to a compound having two or more active hydrogens in a molecule and a polyvalent isocyanate compound to obtain a compound having an unreacted isocyanate group. Epihalohydrin is reacted with the compound (A) obtained by blocking the unreacted isocyanate group of the compound with an acid sulfite and the same polyether polyol compound used for producing the compound (A), and then the polyalkylene polyamine is converted to a polyalkylene polyamine. A compound (A) obtained by reacting an epihalohydrin with a reaction product obtained by reaction and having at least two active hydrogens bonded to an amino group in the molecule thereof in the presence of water; ) And a compound (B) obtained by reacting the compound (B). Composition.