JPH0259189B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an antistatic composition, and more particularly to an antistatic composition that imparts an excellent antistatic effect to synthetic fibers or textile products made of fibers containing synthetic fibers, plastic films, paper, etc. through simple processing. . Generally, textile products made of synthetic fibers or fibers containing synthetic fibers tend to be charged with static electricity, which often causes various problems when used. For example, in the finishing and sewing processes of textile products, static electricity can cause electric shocks, and dust and lint can adhere to hands and machines, reducing quality and work efficiency.
Furthermore, a similar phenomenon occurs during use, causing psychological and physical discomfort to the user. Incidentally, plastic films are also susceptible to dust, and paper such as copy paper is becoming more and more averse to the generation of static electricity, but prevention of static electricity on textile products will be explained below. Conventionally, in order to remove these problems from textile products, they have been treated with highly hygroscopic calcium chloride, lithium chloride, calcium nitrate, magnesium nitrate, or guanidine hydrochloride, or treated with highly water-soluble acrylic ester polymers. Treated with molecular compounds, or further treated with cationic, anionic,
Treatment with various nonionic or amphoteric surfactants has been carried out. However, these methods have drawbacks, such as deteriorating the texture, decreasing color fastness, and poor compatibility with finishing agents such as fabric softeners and water repellents. There are also many things that are inadequate. To improve these shortcomings, a monoquaternary ammonium salt polymer (a polymer whose main component is a monomer containing one quaternary ammonium nitrogen atom) is used in combination with various salts and polyhydric alcohol higher fatty acid esters. Several antistatic agents and methods have been proposed (for example, Japanese Patent Publication No. 54-8800, Japanese Patent Publication No. 58-144176, and Japanese Patent Publication No. 58-70771). However, these also have the disadvantage that their antistatic properties are still insufficient (especially when used in combination with finishing agents) and that the treated fabric has a poor feel. As a result of extensive research to improve these drawbacks, the present inventors have developed a polymer (hereinafter referred to as
The present invention was completed by discovering that when this polymer is used in combination with a guanidine salt or various inorganic salts, extremely excellent antistatic properties are exhibited. The antistatic agent composition of the present invention has a large antistatic effect just by adding a small amount to the processing bath.
It does not reduce the abrasion fastness of dyed fabrics and has a good texture, and even when used in combination with finishing agents such as fabric softeners and water repellents such as fluororesin, they do not affect each other and produce excellent effects. It is something. Furthermore, here the general formula [] is It is indicated by. In the formula [], R ₁ is hydrogen or a methyl group, R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent an alkyl group, oxyalkyl group or aralkyl group having 1 to 18 carbon atoms, and A is −COO− or −CO−
NR ₇ - (wherein R ₇ represents either hydrogen, methyl group or ethyl group), B is (-CH ₂ ) - _o
(However, n indicates an integer of 2, 3 or 4) or -
_CH2CH (OH) _CH2- , X and Y each represent Cl, Br, or I. However, the bis-quaternary ammonium salt polymer alone does not exhibit a very large antistatic effect even when used in small amounts. Also, guanidine salts and inorganic salts,
When used alone, the antistatic effect is small. However, it has been found that when these guanidine salts or inorganic salts are used in combination with a bisquaternary ammonium salt polymer, the antistatic effect can be dramatically improved even when a small amount is used due to a synergistic effect. For the antistatic agent composition of the present invention, a treatment bath is prepared in the following proportions, and this treatment bath is used to antistatically process textile products in a conventional manner. Guanidine salt or inorganic salt...0.1 to 30 parts by weight (solid content) Bisquaternary ammonium salt polymer...0.001 to 30 parts by weight (solid content) Water is added to this to make the total 1000 parts by weight. (If necessary, add various finishing agents to bring the total to 1000 parts by weight.) The synthetic fiber product is immersed in this treatment bath and squeezed, and the guanidine salt or inorganic salt and bis-quaternary ammonium salt polymer are Solid content per dry fiber weight
0.001 to 3% by weight is deposited and dried. If a resin such as a water repellent is used in combination, heat treatment is further performed at 150 to 170°C. Hereinafter, the present invention will be explained in detail with reference to examples, but first, a synthesis example of the bis-quaternary ammonium salt polymer used in the present invention and the compounds used in the synthesis will be described. In the following, all parts indicate parts by weight. In addition, the performance test was conducted using the following method. Antistatic property Frictional charging voltage: Conforms to JIS L-1094B law. A Kyoto University Scientific Research Rotary Static Tester (manufactured by Kowa Shokai) was used. A sample was prepared by leaving the treated cloth in an atmosphere with a room temperature of 20°C and a relative humidity of 40±2% for 24 hours or more. The cloth to be rubbed is cotton cloth. The measured values are shown in voltage (V), and the numerical values in each table below are the average values of six measurements, and the smaller the numerical value, the better the antistatic property is. Half-life: Compliant with JIS L-1094A law. Statistic Honest Meter, HOTAC S-
Uses model 4104 (manufactured by Nippon Static Co., Ltd.). Measured values are given in seconds (S). Color fastness: Rubbing fastness: Compliant with JIS L-8049 method. Uses Gakushin type friction fastness tester. A cotton gold cloth was used as the target cloth and rubbed 100 times under a load of 200 g. The evaluation is on a 5-level scale.
The larger the value, the better the condition. Water repellency: Evaluated by JIS L-1079 spray method. The larger the value, the better the condition. Texture: Sensory test by touch. ○ indicates good texture, △ indicates slightly good texture, and × indicates poor texture. Synthesis example 1

[Synthesis of bis-quaternary ammonium salt monomer]

In a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube, 22 g (0.14 mol) of dimethylaminoethyl methacrylate as a tertiary amine monomer and (2
-Hydroxy-3-chloropropyl)trimethylammonium chloride (28 g (0.15 mol)) and 50 g of water as a solvent were added and heated while mixing.
The reaction was carried out at ±2°C for 5 hours. Thus, R ₁ , R ₂ , R ₃ , R ₄ in the general formula [],
Both R ₅ and R ₆ are CH ₃ , A is -COO-,
A bisquaternary ammonium salt monomer (monomer containing two quaternary ammonium nitrogen atoms) in which B is (-CH ₂ )- ₂ and X and Y are both Cl was obtained. To confirm this reaction, the turbid dispersion becomes clear and
This can be determined by the fact that the pH of the 7% aqueous solution of the reactant has changed from about 10 to 6, but the end point cannot be determined with certainty.
This was done by quantifying Cl ^- ions. The Cl ^- ion concentration at this time was 10.1% (theoretical value Cl ^- % = 10.3).

[Synthesis of bis-quaternary ammonium salt polymer]

Subsequently, the above reaction solution was once cooled, 100 g of water was added to make a 25% aqueous solution, and the solution was diluted for 50±2 hours in a nitrogen gas atmosphere.
The mixture was reacted at 2° C. for 3 hours and polymerized to obtain a polymer solution having a viscosity of 360 cP (centipoise). At this time, 0.1 g of potassium persulfate (0.26 mol % vs. bis quaternary ammonium salt monomer) was added as a polymerization catalyst. Synthesis Examples 2 to 5 Copolymers were synthesized using the bisquaternary ammonium salt monomer obtained in Synthesis Example 1 and other monomers. The synthesis method was carried out according to the second half of Synthesis Example 1 (synthesis of polymer). Table A shows the monomers used in the synthesis, the ratio of the monomers, and the viscosity of the resulting composite (polymer). The ratio of monomers in Table A indicates the molar concentration, and the viscosity is 30% by weight of a 25% by weight copolymer aqueous solution.
It is the value in °C (cP).

【table】

【table】

[Preparation of test cloth]

Sample fabric: Polyester processed yarn fabric (Amundsen) Dyeing conditions Dye: Dianix Orange B-SE 6%
owf (Mitsubishi Kasei Corporation) Temperature x time: 130℃ x 60 minutes Bath ratio: 1:20 Reduction cleaning Reduction cleaning agent: Bisnol SK (Reduction cleaning agent: Ipposha Yushi Kogyo Co., Ltd.) 1g/hydroxide Sodium 1g/Hydrosulfite 1g/Temperature x Time: 80°C x 20 minutes Bath Ratio: 1:20 Washing/Drying: Washed with running water for 20 minutes, then air-dried Example 2 Bis-quaternary obtained in Synthesis Examples 2 to 12 ammonium salt

【table】

[Table] Weight ratio of each polymer to guanidine hydrochloride: 50:
Mix at a ratio of 50% and dilute to 0.5% to prepare a treatment bath (sample numbers 5 to 15). Each test fabric was treated in the same manner as in Example 1, and the antistatic properties and abrasion fastness of the treated fabrics were measured. The results are shown in Table-2. It can be seen that the antistatic agent composition shown in Table 2, which uses a bisquaternary ammonium salt polymer and guanidine hydrochloride in combination, exhibits excellent antistatic properties and abrasion fastness. Example 3 The bisquaternary ammonium salt polymer obtained in Synthesis Example 2 was mixed with various guanidine salts and water-soluble inorganic salts shown in Table 3 at a weight ratio of 50:50 (sample numbers 16 to 3). 29), a polyester textured yarn fabric was treated in the same manner as in Example 1. The antistatic performance of the obtained treated cloth was extremely excellent as shown in Table 3. Example 4 Bis-quaternary ammonium salt polymer obtained in Synthesis Example 1 and guanidine hydrochloride in a weight ratio of 50:50

【table】

【table】

[Table] Test fabrics were treated using the antistatic agent composition of the present invention mixed in Example 1 (Sample 2 of Example 1: sample numbers 30 to 31) together with a softener and a water/oil repellent. .
Similarly, as comparative examples, comparative samples 1 and 5 of Example 1 were also added (comparative sample numbers 7 to 12). The formulation of the treatment bath is as shown in Table 4, with Vicron E-64 (softener for polyester, manufactured by Ipposha Yushi Kogyo Co., Ltd.) as a softener and Asahi Guard AG-710 (fluorocarbon softener) as a water and oil repellent. Water and oil repellent finishing agent:
(manufactured by Asahi Glass Co., Ltd.) were used. Then, the test cloth prepared in the same manner as in Example 1 was immersed in the treatment bath in the same manner as in Example 1, squeezed to a squeezing rate of 80%, dried at 110°C for 2 minutes, and then heat-treated at 150°C for 3 minutes. I went there. Table 4 shows the various performances of the obtained treated fabric. Table 4 shows that the antistatic agent composition of the present invention exhibits extremely excellent antistatic properties even when used in combination with softeners or water/oil repellents, does not impair the texture, and does not adversely affect the performance of these finishing agents. It turns out that it has no effect.

Claims (1)

[Claims] 1. General formula [] [Formula [], R ₁ is hydrogen or a methyl group, R ₂ , R ₃ ,
R ₄ , R ⁵ and R ₆ are each an alkyl group having 1 to 18 carbon atoms,
An oxyalkyl group or an aralkyl group, A is -COO- or -CO-NR ₇ - (wherein R ₇ is hydrogen, methyl group or ethyl group), B is (-
CH ₂ ) − _o (where n indicates an integer of 2, 3 or 4)
or _-CH2CH (OH) _CH2- , and X and Y each represent Cl, Br, or I. An antistatic agent composition comprising a polymer containing at least one quaternary ammonium salt monomer as a main component, and a guanidine salt and/or an inorganic salt.