JPS5953396B2 - Antistatic agent for synthetic fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antistatic agent for synthetic fibers, and more specifically,
The present invention relates to an antistatic agent for synthetic fibers that has excellent antistatic properties at low humidity, can be used in combination with various finishing agents, and has excellent fastness properties.

In general, synthetic fibers, unlike natural fibers, have almost no hygroscopicity and are known to be easily charged with electricity. In particular, the three major synthetic fibers, polyester fibers, nylon fibers, and acrylic fibers, are highly electrostatically charged. It causes various obstacles.

Conventionally, as a method for preventing static electricity on synthetic fibers, there has been known a method of treating fibers using a cationic activator, a cationic polymer surfactant, highly hygroscopic guanidine hydrochloride, lithium chloride, etc., either alone or in combination.

For example, Japanese Patent Publication No. 54-8800 discloses a polymer of guanidine hydrochloride and dimethyl diallylammonium chloride, a quaternized product of dialkylamine ethyl methacrylate polymer with dimethyl sulfuric acid or hydrochloric acid, or an aminomethylated product of polyacrylamide with dimethyl sulfuric acid or hydrochloric acid. Disclosed is an antistatic agent comprising at least one cationic polymeric surfactant selected from quaternized products according to the present invention.

Furthermore, JP-A-53-130400 discloses an antistatic agent consisting of a phosphoric acid compound and a cationic polymeric surfactant. Quaternized product with hydrochloric acid, quaternized product of diethylaminoethyl acrylamide polymer with dimethyl sulfuric acid, quaternized product of diethylaminopropyl methacrylate polymer with methyl iodide
List of graded products, etc.

However, systems using cationic surfactants have the drawbacks of decreased color fastness and discoloration, and systems using cationic polymeric surfactants have insufficient antistatic effect at low humidity and are not sufficient. If a large amount is used to achieve an effect, the texture becomes hard, and the result is not always completely satisfactory.

Therefore, the present inventors conducted intensive research to find an antistatic agent that solved the above drawbacks, and as a result, they found an antistatic agent that has excellent antistatic properties at low humidity, does not reduce color fastness, and does not change texture. The present invention has been completed.

That is, the present invention contains at least one selected from cationized cellulose, cationized starch, or mineral acid salts of chitosan, and at least one selected from the group consisting of the compounds shown in (a) to (b) below. An antistatic agent for synthetic fibers is provided.

(a) Deliquescent or hygroscopic amine salts or inorganic salts.

(b) General formula M1M2M3PO4 (M19M2 in the formula
9M3 means hydrogen, ammonium or alkali metal).

The cationized cellulose and cationized starch used in the present invention are used as conditioning shampoos and fiber sizing agents.

For example, JP-A-53-140305 and JP-A-54
-101996 can be mentioned.

However, although cationized cellulose and cationized starch contain quaternary nitrogen, their content is low (
(It is difficult to obtain a high quaternary nitrogen content from a manufacturing standpoint), it has not been used as an antistatic agent for highly charged synthetic fibers, and no such proposal has been made.

However, according to the experiments of the present inventors, these cationized cellulose and cationized starch can be treated with (a) deliquescent or hygroscopic amine salts or inorganic salts, or (b) with the general formula M1M2M3PO4 (in the formula Ml, When used in combination with a phosphate represented by M2゜M3 means hydrogen, ammonium or an alkali metal, it surprisingly becomes possible to use a cationic polymer with a high content of quaternary nitrogen, which is conventionally used as an antistatic agent. It has been revealed that it has even better antistatic properties than surfactants (cationic polymers), especially antistatic properties at low humidity.

The cationized cellulose and cationized starch of the present invention are
deliquescent or hygroscopic amine salts or inorganic salts,
It is not clear how the antistatic effect is achieved at low humidity when used in combination with phosphate, but it is probably due to the synergistic effect of the salt used in combination with the special structure of cellulose and starch. However, it is not known for sure.

Therefore, when chitosan hydrochloride, which has a similar structure to cellulose and starch, was also investigated, similar effects were obtained.

The cationized cellulose or cationized starch used in the present invention refers to cellulose or starch that has been processed to have quaternary nitrogen, and includes, for example, those represented by the following formula (I).

1 (wherein A: cellulose residue or starch residue R: alkylene group or hydroxyalkylene group R': H or methyl group R, R2, R3: the same or different, alkyl group, aryl, aralkyl group , or a nitrogen atom in the formula may be included to form a heterocycle.

One may be H. X: Anion (chlorine, bromine, iodine,
sulfuric acid, sulfonic acid, methyl sulfuric acid, phosphoric acid, nitric acid, etc.) l: Positive integer m: 0 to 10 on average) The degree of cation substitution of cationized cellulose or cationized starch is 0.01 to 1, that is, per anhydrous glycose unit. 0.
It is preferable that 0.01 to 1, preferably 0.02 to 0.5, cationic groups are introduced.

A degree of substitution of 0.01 or less is not sufficient, and a degree of substitution of 1 or more is acceptable, but from the viewpoint of reaction yield, 1 or less is preferable.

Although cationized cellulose or cationized starch synthesized by any method can be used, the following method can be mentioned as a typical synthesis method.

Cationized cellulose is produced by reacting hydroxyethylcellulose obtained by adding ethylene oxide to cellulose with a quaternizing agent such as 3-chloro-2-hydroxypropyltrimethylammonium chloride or glycidyltrimethylammonium chloride in the presence of an alkali catalyst. Cationized starch is obtained by reacting the starch with the above-mentioned quaternizing agent.

The mineral acid salt of chitosan used in the present invention refers to a deacetylated product of chitin that is made water-soluble by reacting with a mineral acid such as hydrochloric acid.

Deliquescent or hygroscopic amine salts or inorganic salts include, for example, methylamine hydrochloride, guanidine hydrochloride, lithium chloride, luciram chloride, lithium nitrate, calcium nitrate 1, potassium hydrogen sulfate, sodium amate, etc. As a phosphate, (NH4)
3PO4゜(NH4)2HPO4, NH4H2PO4,
Na3PO4゜Na2HPO4, NaH2PO4, ni3
PO4, 2HPO4゜KH2PO4, Li3PO4,
Examples include Li2HPO4 and LiH2PO4.

The above amine salts, inorganic salts, or phosphates may be used alone or in combination, and in particular, amine salts or inorganic salts and phosphates may be mixed to form mineral salts of cationized cellulose, cationized starch, or chitosan. A system that is used in combination with this product exhibits even more effective results.

The antistatic agent comprising the composition of the present invention is usually used as an aqueous solution of 0.01 to 1% by weight.

(a) at least one selected from mineral salts of cationized cellulose, cationized starch, or chitosan; and (b) at least one selected from deliquescent or hygroscopic amine salts or inorganic salts, or phosphates. The blending ratio of both is a/b
~0.01-5 (weight ratio), preferably 0.05
~1.

By using the antistatic agent of the present invention, it is possible to effectively prevent static electricity from synthetic fibers, especially polyester fibers and acrylic fibers, without changing their texture, and also to impart excellent color fastness. .

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

All parts and percentages in the examples are parts and percentages by weight.
shows.

Example 1 A polyester georgette weight loss product (0.75 denier) was immersed in the formulation solution shown in Table 1, squeezed to a squeezing rate of 90%, dried at 105°C for 5 minutes, and further heated with a pin tenter at 108°C. Heat set for a minute.

The obtained test cloth was subjected to antistatic properties, dry and wet dyeing fastness to rub, dyeing sweat fastness and rust tests.

The results are shown in Table 2. Antistatic property> Using a rotary static tester at Kyoto University Kaken 2, the friction cloth used was Clamping Cloth No. 3, and the charging voltage after 1 minute was measured.

Here, in order to investigate the effect under low humidity conditions, the machine was covered with a PVC box that can control humidity, and measurements were taken inside the box.

Humidity is measured using a desensitized hygrometer (Ace Research Institute, Tokyo, error ±2%)
was used.

<Dyeing fastness to rubbing> Measured using a JIS-L-0849 Gakushin type rubbing fastness machine, and staining gray scale (JIS-L-080
5) was evaluated.

<Dyeing fastness to rubbing> Measured according to JIS-L-0848, Method A, and evaluated using a gray scale for staining (JIS-L-0805).

<Rust Test> Commercially available insect pins (thoroughly washed with acetone to remove oil) were immersed in the treatment solution, and the occurrence of rust was observed after 24 hours.

On a 5-level scale, the higher the number, the less rust will occur.

Example 2 The same measurements as in Example 1 were carried out using the formulation liquid shown in Table 3.

The results are shown in Table 4. Example 3 Nylon tack was immersed in the distribution prescription solution shown in Table 5, squeezed to a squeezing rate of 30%, dried at 105°C for 5 minutes, and further heat set at 150°C for 1 minute using a pin tenter. A test similar to 1 was conducted.

Fastness test fabric is Kayalon Milling Red R5-12
5 (manufactured by Nippon Kayaku Gyokugyo ■) at 5% 0. Those stained with W and F were used.

The results are shown in Table 6. Example 4 An acrylic jersey was immersed in the formulation shown in Table 7, and after reaching a squeezing rate of 100%, it was dried at 80° C. for 30 minutes and tested in the same manner as in Example 1.

The fastness test fabric was Kayacrylic film (Kayacr).
yl Blue) GRL stained with 5% o, w, f, was used.

The results are shown in Table 8.

Claims (1)

[Scope of Claims] 1 At least one selected from cationized cellulose, cationized starch, or mineral acid salts of chitosan, and the following (a) to
An antistatic agent for synthetic fibers, characterized in that it contains at least one selected from the group consisting of the compounds represented by (b). (a) Deliquescent or hygroscopic amine salts or inorganic salts. (b) General formula M1M2M3PO4 (M19M2 in the formula
5M3 means hydrogen, ammonium or alkali metal). 2. Claim 1 in which the deliquescent or hygroscopic amine salt or inorganic salt is methylamine hydrochloride, guanidine hydrochloride, lithium chloride, calcium chloride, lithium nitrate, potassium hydrogen sulfate, and sodium aluminate.
An antistatic agent for synthetic fibers as described in .