JPH06184943A - Antistatic sizing agent for fiber - Google Patents

Abstract

PURPOSE:To obtain an antistatic sizing agent for fiber, comprising a cationized pullulan, excellent in antistatic effects at a low humidity without discoloring fiber, good in hand and capable of manifesting excellent sizing effects without causing the deterioration in color fastness. CONSTITUTION:A raw material pullulan is made to react with a cationizing agent selected from formulas I and II (R1 to R3 are hydrocarbon; X and Y are halogen) to provide a cationized pullulan, expressed by formula III [R4 is H or substituent group expressed by formula IV; n is 20-20000; (R1 to R3 are hydrocarbon, R1 and R2 are preferably 1-3C alkyl; R3 is 1-18C alkyl; X is halogen, especially chlorine)] and having preferably a substituent group, expressed by formula IV and present in an amount of >=0.01 expressed in terms of the degree of substitution based on the anhydroglucose unit. The resultant cationized pullulan is then used as a substrate and a cationic surfactant, as necessary, is added thereto. A textile material such as natural or synthetic fiber is subsequently immersed and treated with the prepared treating solution to afford the objective antistatic sizing agent capable of assuming excellent sizing effects. Trimethylammonium chloride, dimethyloctylammonium chloride, etc., can be exemplified as a common part of NR1R2R3X expressed by formulas I and II.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic sizing agent for fibers. More specifically, it has an excellent sizing effect and an antistatic property at low humidity, and is excellent without discoloring the fibers. The present invention relates to an antistatic sizing agent for fibers that gives a texture.

[0002]

BACKGROUND OF THE INVENTION As conventional antistatic agents for fibers, novel quaternary compounds disclosed in JP-A-51-63104 and cationized cellulose and cationized compounds disclosed in JP-A-57-82576. An antistatic agent for synthetic fibers using starch or chitosan is known. Further, as a softening agent, a fiber softening agent composition of JP-A-52-132193 containing a cationic activator and a cation-modified cellulose as main components, and as a sizing agent, JP-A-53-94688.
No. 10 household paste composition is known.

[0003]

However, according to these conventional techniques, the fibers are yellowed and grayed by the repeated softening treatment of the product, and the dyeing fastness is lowered. Further, there are problems in that the adhesive strength of gluing and the antistatic effect at low temperatures are insufficient, and the texture is not good, and these problems have been desired to be solved.

Therefore, an object of the present invention is to provide a more effective antistatic sizing agent, that is, to a synthetic fiber having almost no hygroscopic property and having a high electrostatic property, that is, a dye which does not discolor the fiber and is dyed. An object of the present invention is to provide an antistatic sizing agent that maintains fastness, has excellent antistatic properties at low humidity, and exhibits an excellent sizing effect without impairing good texture.

[0005]

[Means for Solving the Problems] The present inventors have made repeated studies especially on the physical properties of the film of the pullulan derivative. As a result, it was found that the above-mentioned function can be sufficiently obtained by using cationized pullulan as a base or by using a cationic surfactant together.

To achieve the above object, the antistatic sizing agent for fibers according to claim 1 is characterized by containing cationized pullulan.

To achieve the above object, the antistatic sizing agent for fibers according to claim 2 contains 0.005 to 5 parts of cationized pullulan.
It is characterized by containing 5% by weight and 2 to 12% by weight of a cationic surfactant.

In order to achieve the above object, the invention of claim 3 is
The antistatic sizing agent for fibers according to claim 1 or 2, wherein
A compound of pullulan represented by the general formula (I) (Chemical formula 3) and a compound represented by the general formula (II) (Chemical formula 4) [in the above general formulas (I) and (II), R ₁ , R ₂ , R ₃ Is a hydrocarbon group and X and Y are halogen atoms], and contains cationized pullulan obtained by reacting with at least one cationizing agent selected from the group consisting of:

[0009]

[Chemical 3]

[Chemical 4]

The antistatic sizing agent for fibers according to the present invention is characterized by containing a cationized pullulan represented by the following general formula (III) as a base.

[0011]

[Chemical 5]

However, in the above formula, R ₄ is a hydrogen atom or
A substituent represented by the following general formula (IV), wherein the substituent is R depending on the degree of substitution of the cationized pullulan obtained.
Replaces the hydrogen atom in ₄ .

[0013]

[Chemical 6]

The above-mentioned substituents are derived from a cationizing agent, and R ₁ , R ₂ and R ₃ represent a hydrocarbon group, and R ₁ and R ₂ have carbon atoms, as described later for the cationizing agent. An alkyl group having 1 to ₃ is preferable, and R ₃ has 1 to 1 carbon atoms.
An alkyl group of 8 is preferred.

X is a halogen atom such as chlorine, iodine and iodine, preferably chlorine. Further, in the general formula (III), n is usually 20 to 20,000.

The substituent represented by the general formula (IV) is preferably present in an average degree of substitution of 0.01 or more per anhydroglucose unit, more preferably 0.1 or more per unit thereof. When the degree of substitution is less than 0.01, when used as a base of an antistatic sizing agent, it imparts characteristics such as dispersion uniformity when the product is used for softening treatment, and moisturizing properties necessary for sufficiently functioning antistatic properties. It may not be possible, which is not preferable.

In the present invention, the cationized pullulan used as the base for the antistatic sizing agent for fibers is the general formula (I) as the raw material pullulan in the presence of water and an alkaline substance.
A compound represented by the chemical formula 7 and a compound represented by the general formula (II) (chemical formula 8) [in the general formulas (I) and (II), R is
₁ , R ₂ and R ₃ are hydrocarbon groups, and X and Y are halogen atoms]
It can be obtained by reacting with at least one cationizing agent selected from the group consisting of

[0018]

[Chemical 7]

[Chemical 8]

The above-mentioned raw material pullulan has the general formula (V)
As described above, the unit of maltotriose, which is a trimer of glucose, is α-, which is a bond different from that of the trimer.
It is a linear polymer that is repeatedly linked by 1,6 bonds. The molecular weight of pullulan is preferably 10,000 to 10,000,000, and more preferably 100,000 to 10,000,000. Therefore, n in the general formula (V) is usually 20 to 20,000.
It is 0.

[0020]

[Chemical 9]

The raw material pullulan is not particularly limited in its production method. For example, Aureobasidium pullulul, a kind of black yeast
ans) can be obtained as a viscous polysaccharide produced in the culture solution by culturing under an appropriate condition using sucrose or a decomposed product of starch as a carbon source. The physical properties of pullulan produced differ slightly depending on the type of strain used,
Any of these can be used in the present invention.

The reaction between the raw material pullulan and the cationizing agent is
It is carried out in the presence of a predetermined amount of water and an alkaline substance.

The amount of water added in the reaction is preferably a molar ratio of 2 per unit of anhydrous glucose of pullulan as a raw material.
~ 80 times. When the amount is less than this, the alkaline substance functioning as a catalyst is not uniformly involved in the reaction, and the contact efficiency between the cationizing agent and the pullulan as a raw material is lowered, so that the reaction may not proceed sufficiently, which is not preferable. On the other hand, if the addition amount is the above or more, the reaction between water and the cationizing agent, which is a side reaction, may proceed,
It is not preferable because the effective amount of the cationizing agent decreases. The amount of water added is more preferably 5 to 40 times the molar ratio per anhydroglucose unit.

In order to exemplify the cationizing agent which can be used in the present invention, a specific example of the -NR ₁ R ₂ R ₃ X moiety (trialkylammonium base) common to the above general formulas (I) and (II) is given. Examples include trimethylammonium chloride, triethylammonium chloride, tripropylammonium chloride, etc., and higher fatty acids such as dimethyloctylammonium chloride, dimethyldecylammonium chloride, dimethyllaurylammonium chloride, dimethylmyristylammonium chloride, dimethylpalmitylammonium chloride. Examples thereof include those containing a group alkyl group.

The amount of the cationizing agent added is arbitrarily selected according to the desired degree of cation modification, but is preferably 0.01 times or more the molar ratio of the raw material pullulan per anhydroglucose unit. If it is 0.01 times or less, the average substitution degree of the cationized pullulan per anhydroglucose unit by the cation group (β-hydroxypropyltrialkylammonium base) derived from the cationizing agent becomes 0.01 or less, I can't get a pullulan to do. More preferably, the molar ratio per anhydroglucose unit is 0.1 or more.

The reaction temperature is preferably 40 to 80 ° C. The addition order of the alkaline substance and the cationizing agent is not particularly limited.

After completion of the cationization reaction, the alkaline substance which is the catalyst is neutralized with a mineral acid or an organic acid, and then acetone, methanol, propanol, butanol, tetrahydrofuran, which is a non-solvent of the cationized pullulan,
Crystallization and recovery are performed by mixing with dioxane or the like or a mixed solvent thereof. After that, by re-dissolving in water, repeating the steps of recrystallization, and then drying, a purified cationized pullulan can be obtained. This is used as a base for an antistatic sizing agent for fibers.

The antistatic sizing agent provided by the present invention contains 0.005 to 0.005 parts of cationized pullulan as a main component.
Even when used as a 5.0% by weight aqueous solution, a sufficient effect for sizing can be obtained, but a cationic surfactant can be added for the purpose of imparting a more effective antistatic effect. The content of the cationic surfactant at that time is 2 to
12% by weight is preferred.

The cationic surfactants that can be used in the present invention include the following quaternary ammonium salts (V
1), imidazolinium salt (VII), quaternary amido ammonium salt (VIII, IX, X), cationic polyamide (X
I) and the like are exemplified, but not limited to these. In addition, cationic surfactants derived from urea or burette can also be used.

[0030]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

In the above formula, R ₅ , R ₆ , R ₁₀ and R ₁₁ are each an alkyl group having 11 to 22 carbon atoms or a β-hydroxyalkyl group having 13 to 24 carbon atoms. R
₇ , R ₈ and R ₉ are each an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, a benzyl group or — (CH ₂ CH ₂ O) _n H, and R ₁₂ is ₁₂ carbon atoms.
~ 24 aliphatic groups. o is 1 to 3, p is 2 or 3
And X is an anion.

More preferable cationic surfactants that can be used in the present invention have low solubility and have a total carbon number of 25 to 60, particularly preferably 30 to 50.

Since cationized pullulan forms a uniform and strong film, this physical property can be applied to an excellent sizing agent for fibers. Further, by using cationized pullulan, it is possible to prevent yellowing and graying of fibers, which has been a phenomenon peculiar to cationic surfactants. Although the yellowing and graying and its mechanism are not clear, the cause of discoloration is that metal ions and colloidal metal compounds in tap water, especially iron, are adsorbed or deposited on the fibers, and cationic surface active It is thought that the agent promotes this. On the other hand, cationized pullulan is effective for preventing discoloration because it has a function of hindering adhesion to fibers by dispersing causative metal ions and colloidal metal compounds.

The antistatic sizing agent for fibers of the present invention contains, in addition to the cationized pullulan and the cationic surfactant,
The following various components can be appropriately blended as necessary. Examples of the compounding ingredients include antifreezing agents such as ethylene glycol, propylene glycol and ethanol; fragrances; germicides; preservatives; fluorescent dyes; pigments. In addition, nonionic surfactants such as polyoxyethylene type and polyhydric alcohol ester type; amphoteric surfactants such as betaine structure type and imidazoline derivative can be added.

The antistatic sizing agent for fibers of the present invention can be used in both the washing step and the rinsing step at the time of washing, and by adding an appropriate amount, an excellent sizing effect and an antistatic function are imparted. Further, since the fiber material, which has been subjected to the sizing treatment with the composition of the present invention, has a strong film fixing property, the effect is maintained even if the sizing treatment is performed once and then washed several times.

[0036]

EXAMPLES In Examples 1 to 3 below, various tests performed on the cationized pullulan used in the antistatic sizing agent for fibers of the present invention and the results thereof will be shown.

Example 1 Cationized pullulan, cationized cellulose and cationized starch were subjected to a sizing test and an adhesion rate measurement. First, cationized pullulan (cation substitution degree 0.6), cationized cellulose (hydroxyethyl substitution degree 2.0,
A 0.4 wt% aqueous solution of a cation group substitution degree of 0.4) and a cationized starch (cation group substitution degree of 0.5) were prepared as test solutions. 25 g of cotton cloth was dipped in 100 g of each of the test liquids, and washed by rubbing by hand for 30 seconds. After dehydrating this cotton cloth for 30 seconds with a dehydrator,
It was dried for 1 minute and further heat-set at 130 ° C. for 1 minute with a pin tenter. For each of the test cloths thus obtained, according to JIS-1005-1959,
Tensile hardness was measured by the cantilever method. Furthermore, in order to investigate the adhesion rate, a constant temperature layer of 65% RH was applied with 20
The sample was left at 24 ° C. for 24 hours, and the weight change before and after sizing was measured. The results are as shown in Table 1. According to this, cationized pullulan showed the best tensile strength and adsorptivity.

[0038]

[Table 1]

Example 2 An antistatic test was conducted on cationized pullulan, cationized cellulose and cationized starch. Cationized pullulan (cationic group substitution degree 0.6), cationized cellulose (hydroxyethyl group substitution degree 2.0, cation group substitution degree 0.4), cationized starch (cation group substitution degree 0.
5) 0.4% by weight each, cationic surfactant (di-hardened tallow alkyl dimethyl ammonium chloride) 5.0% by weight, nonionic surfactant (polyoxyethylene alkyl ether) 0.5% by weight. Such aqueous solutions were prepared and used as test solutions. Using a polyester georgette weight-reduced product (075 denier) for the test cloth, the subsequent sizing treatment is
The same procedure as in Example 1 was performed except for the measurement of the adhesion rate. next,
Using a rotary static tester of the Kyoto University Chemical Research Institute, a friction cloth was rubbed with a cotton cloth No. 3 for 1 minute to measure the charged voltage. The results are as shown in Table 2. This revealed that the cationized pullulan has an excellent antistatic effect.

[0040]

[Table 2]

Example 3 A yellowing prevention test was conducted on cationized pullulan, cationized cellulose and cationized starch. 1 g of each test solution prepared in Example 2 was diluted with 1000 ml of tap water and used as a test solution. Diastase-treated cotton cloth (reflectance 92%) was used as the test cloth, and the subsequent sizing treatment was
The same procedure as in Example 1 was performed except for the measurement of the adhesion rate. After repeating this gluing process 30 times, Elrefo (Elrep
ho) The whiteness was obtained from the reflectance of the treated cloth when the reflectance of magnesium oxide was set to 100% with a reflectance meter (manufactured by Carl Zeiss), and the yellowing prevention property was evaluated by this. The results are as shown in Table 3. From this, it was found that the cationized pullulan has an excellent effect of preventing yellowing.

[0042]

[Table 3]

In the antistatic sizing agent for fibers according to the present invention, as shown in each of the above examples, the cationized pullulan to be blended has excellent film physical properties, and the characteristics of the cationic group in the molecule. Therefore, it has good gluing effect and adhesiveness, and also has excellent antistatic effect and anti-yellowing effect.

[0044]

As is clear from the above, according to the present invention, the fibers are not discolored, the dyeing fastness is maintained,
It is possible to provide an antistatic agent having excellent antistatic properties at low humidity and exhibiting an excellent gluing effect without impairing good texture.

Claims (3)

[Claims] 1. An antistatic sizing agent for fibers, which contains cationized pullulan. 2. An antistatic sizing agent for fibers, containing 0.005 to 5% by weight of cationized pullulan and 2 to 12% by weight of a cationic surfactant. 3. A compound represented by the general formula (I) (Chemical formula 1) and a compound represented by the general formula (II) (Chemical formula 2) [in the above general formulas (I) and (II) R ₁ ,
R ₂ and R ₃ are hydrocarbon groups, and X and Y are halogen atoms], and cationized pullulan obtained by reacting with at least one cationizing agent selected from the group consisting of Item 1. An antistatic sizing agent for fibers according to 1 or 2. [Chemical 1] [Chemical 2]