JPS6169884A - Antistatic agent composition - Google Patents

Abstract

PURPOSE:To provide a high performance compsn. for antistatic agent made from (a) polymer consisting mainly of a specified quaternary ammonium salt and (b) guanidine salt and/or inorg. salt. CONSTITUTION:The compsn. is made from (A) about 0.001-30pts.wt. (by solid) (co)polymer and (B) about 0.1-30pts.wt. (by solid) guanidine salt (e.g. guanidine hydrochloride) and/or inorg. salt (e.g. lithium chloride). The (co)polymer consists mainly of a quaternary ammonium salt of formula I [where R1 is H or a methyl group; R2-R6 are a 1-18C (oxy)alkyl group or aralkyl group; A is -COO-, formula II (R7 is H or a methyl group); B is formula III (n is 2-4), formula IV (X and Y are Cl, Br or I)]. Antistatic finishing of textile goods, etc. is performed in a processing bath prepd. by adding water to the compsn. to make a total of 1,000pts.wt.

Description

[Detailed description of the invention]

The present invention relates to an antistatic agent composition, and more particularly to an antistatic agent composition that imparts an excellent antistatic effect to textile products made of synthetic fibers or fibers containing the same, 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 considerable problems when used. For example, in the finishing process of textile products and the HL manufacturing process, quality and work efficiency are degraded due to electrostatic shock, adhesion of dust and thread waste, and clinging to hands and machines. Furthermore, a similar phenomenon occurs during use, giving the user psychological and physical discomfort. 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 even cationic,
Anion type. 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;
8-70771). 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. Therefore, the present inventors aimed to improve these drawbacks (as a result of extensive research, the present inventors found that the main component is at least one type of heptamer containing two quaternary ammonium nitrogen atoms as shown in the general formula (1)). The present invention was completed based on the discovery that the combination of a polymer (hereinafter referred to as "bis quaternary ammonium salt polymer 1") with a guanidine salt or various inorganic salts showed extremely excellent antistatic properties. The antistatic agent composition of the present invention has a large antistatic effect even when added in a small amount to the treatment bath, does not reduce the abrasion fastness of the dyed fabric, has a good texture, and is flexible. Even when used in combination with finishing agents such as water repellent agents and fluororesins, they do not affect each other and produce excellent effects.The general formula (1) is shown here. , in formula (1), R1 is hydrogen or a methyl group, R2, R3, R4, R5 and R6 each have 1 carbon number
-18 alkyl group, oxyalkyl group or aralkyl group, A is -CO〇- or -CONR7- (however, 8
B is either +CH2 (however, n is an integer of 2, 3 or 4) or -0 H2CH(OH) CH2- , X and Y each represent one of CI, Br, and I, respectively. However, the bis-quaternary ammonium salt polymer alone does not exhibit a very large antistatic effect even when used in small amounts. In addition, guanidine salts and inorganic salts alone have a small antistatic effect. However, it has been found that when these guanidine salts or inorganic salts are used in combination with a bis-quaternary ammonium salt polymer, the antistatic effect can be dramatically improved even when a small amount is used due to a synergistic effect. A treatment bath for the antistatic agent composition of the present invention is prepared in the following five 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) Bis-quaternary ammonium salt polymer: 0.001 to 30 parts by weight (solid content)
30 parts by weight (solid content) Add water to make the total 1000 parts by weight. (If necessary, add various finishing agents and make the whole
00 parts by weight. ). Synthetic fiber products are dipped in this treatment bath and squeezed to remove guanidine salt or inorganic salt and bisquaternary ammonium salt polymer.
A total of 0.001 to 3% by weight of solids per dry fiber weight is deposited and dried. When a resin such as a water repellent agent 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 frictional charging voltage: Based on JIS L-1094B method. A Kyoto University Scientific Research Rotary Static Tester (manufactured by Koa 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. Measured values are shown in voltage (V), but the numbers in each table below are 6
This is the average value of measurements taken twice, and the smaller the value, the better the antistatic property is. Half-life: Compliant with JTS L-1094A law. A static honest meter, model ll0TACS-4104 (manufactured by Nippon Static A) was used. Measured value is in seconds (S)
Indicated by Color fastness: Rubbing fastness: Based on JIS L-0849 method. A Gakushin type friction fastness tester was used. The clamping cloth was used as a target cloth and rubbed 100 times under a load of 200 g. The evaluation is on a 5-level scale, with higher numbers indicating better quality. Water repellency: Evaluated by JIS L-1079 spray method. The larger the value, the better. Sensual test using two hands. ○ indicates good texture (, Δ indicates slightly good texture, × indicates poor texture. Synthesis example 1

[Synthesis of bis-quaternary ammonium cyclic compound] Stirrer,
In a four-lobe flask equipped with a temperature needle, a condenser and a nitrogen gas inlet tube, 22 g (0.14 mol) of dimethylaminoethyl methacrylate as a tertiary amine heptamer and (2-hydroxy-3-chloro) as a quaternized compound were added. 28g (propyl)trimethylammonium chloride (
0.15 mol) and 50 g of water as a solvent were added, heated while mixing, and reacted at 70±2° C. for 5 hours. Thus, R1, R2+ R3+R, in general formula (1),
Both R5 and R6 are CH3, and A is -COO-1
A bis-quaternary ammonium ring-based polymer (septadumer containing two quaternary ammonium nitrogen atoms) in which B is +CH2)2 and X and Y are both Cl was obtained. Confirmation of this reaction can be determined by the fact that the turbid dispersion becomes transparent and the pH of the 7% aqueous solution of the reactant changes from about 10 to 6, but the end point can be definitely determined by quantifying CI ions. . The CI ion concentration at this time was 10.1%
(Theoretical value CX%=10.3). [Synthesis of bis-quaternary ammonium salt polymer] Next,
The above reaction solution was once cooled, 100 g of water was added to make a 25% aqueous solution, and the solution was reacted in a nitrogen gas atmosphere at 50±2° C. for 3 hours to polymerize to obtain a polymer solution with 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 ring polymer 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 monomer ratios in Table A indicate molar concentrations, and the viscosity is the value (cP) of a 25% by weight aqueous copolymer solution at 30°C. Table 8 Synthesis Examples 6 to 12 Using the same synthesis method as in Synthesis Example 1, the tertiary amine monomer shown in Table B was reacted with a quaternized compound to obtain a bisquaternary ammonium salt monomer, followed by polymerization. A bis-quaternary ammonium salt polymer was obtained. In addition to those used in Synthesis Examples 6 to 12 in Table B, various compounds exemplified below can be used as tertiary amine monomers. One drawback is that A in formula CI) is -CO〇-. Tertiary amine monomers include dimethylaminoethyl acrylate,
3-(dimethylamino)propyl methacrylate, 2-
(dimethylamino)propyl acrylate or methacrylate, 4-(dimethylamino)butyl methacrylate, 5-(dimethylamino)pentyl acrylate or methacrylate, 6-(dimethylamino)hexyl acrylate or methacrylate, 2-(dimethylamino) Butyl acrylate or methacrylate, 3-(
dimethylamino)butyl acrylate or methacrylate, 2-(dimethylamino)pentyl acrylate or methacrylate, 3-(dimethylamino)pentyl acrylate or methacrylate, 4-(dimethylamino)pentyl acrylate or methacrylate, 2-(
dimethylamino)hexyl acrylate or methacrylate, 3-(dimethylamino)hexyl acrylate or methacrylate, 4-(dimethylamino)hexyl acrylate or methacrylate, 5-(dimethylamino)hexyl acrylate or methacrylate, 3
-(dimethylamino)-2-hydroxypropyl acrylate or methacrylate, 2-methyl-3-(dimethylamino)propyl acrylate or methacrylate,
Diethylaminoethyl acrylate, dipropylaminoethyl acrylate, or methacrylate, dibutylaminoethyl acrylate. Or methacrylate, diisopropylaminoethyl acrylate, or methacrylate. In addition, examples of the tertiary amine monomer in which A in formula (1) is -Co-NR fu include dimethylaminoethyl acrylamide, 3-(dimethylamino)propylacrylamide, methacrylamide, and 2-(dimethylamino)propylacrylamide. . or methacrylamide, 4-(dimethylamino)butylacrylamide, or methacrylamide, 5-(dimethylamino)pentylacrylamide. or methacrylamide, 6-(dimethylamino)hexylacrylamide, or methacrylamide, 2-(dimethylamino)butylacrylamide. or methacrylamide, 3-(dimethylamino)butylacrylamide, or methacrylamide, 2-(dimethylamino)pentylacrylamide. or methacrylamide, 3-(dimethylamino)pentylacrylamide, or methacrylamide, 4-(dimethylamino)pentylacrylamide. or methacrylamide, 2-(dimethylamino)hexylacrylamide, or methacrylamide, 3-(dimethylamino)hexylacrylamide. or methacrylamide, 4-(dimethylamino)hexylacrylamide, or methacrylamide, 5-(dimethylamino)hexylacrylamide. or methacrylamide, 3-(dimethylamino)-2-
Hydroxypropylacrylamide, 2-methyl-3-
(dimethylamino)propylacrylamide, or methacrylamide, diethylaminoethyl acrylamide,
Or methacrylamide, dipropylaminoethyl acrylamide, methacrylamide, dibutylaminoethyl acrylamide, methacrylamide, diisopropylaminoethyl acrylamide, or methacrylamide. Next, the following quaternized compounds are used in the same manner as in Synthesis Examples 6 to 12. Mass, (2-hydroxy-3-chloropropyl) tripropylammonium chloride, (2-hydroxy-3-
(Chloropropyl) triisopropylammonium chloride, (2-hydroxy-3-chloropropyl)tributylammonium chloride, (2-hydroxy-3-chloropropyl)ethyldimethylammonium chloride, (
(2-hydroxy-3-chloropropyl)diethylmethylammonium chloride, (2-hydroxy-3-chloropropyl)ethylbutylmethylammonium chloride,
(2-hydroxy-3-chloropropyl)lauryldimethylammonium chloride, (2-hydroxy-3-chloropropyl)benzyldimethylammonium chloride, etc., (2-hydroxy-3-chloropropyl)trimethylammonium bromide, (2-hydroxy -3-chloropropyl)triethylammonium bromide, (2-hydroxy-3-chloropropyl)tripropylammonium bromide)', (2-hydroxy-3-chloropropyl)triisopropylammonium bromide, (2-hydroxy-3-chloropropyl)triisopropylammonium bromide, -chloropropyl)tributylammonium bromide, (2-hydroxy-3-chloropropyl)ethyldimethylammonium bromide, (2-hydroxy-3-chloropropyl)diethylmethylammonium bromide, (2-hydroxy-3-chloropropyl) ) ethylbutylmethylammonium bromide, etc., (2-hydroxy-3-bromopropyl)tripropylammonium chloride, (2-hydroxy-3-bromopropyl) triisopropylammonium chloride,
(2-Hydroxy-3-bromopropyl)tributylammonium chloride, (2-hydroxy-3-bromopropyl)ethyldimethylammonium chloride, (2-
Hydroxy-3-bromopropyl)diethylmethylammonium chloride, (2-hydroxy-3-bromopropyl)ethylbutylmethylammonium chloride, etc., and (2-hydroxy-3-bromopropyl)trimethylammonium bromide, (2-hydroxy- 3-bromopropyl) triethylammonium bromide, (
2-Hydroxy-3-bromopropyl)tripropylammonium bromide, (2-hydroxy-3-bromopropyl)triisopropylammonium bromide, (2
-hydroxy-3-bromopropyl)tributylammonium bromide, (2-hydroxy-3-bromopropyl)ethyldimethylammonium bromide, (2-hydroxy-3-bromopropyl)diethylmethylammonium bromide, (2-hydroxy- 3-bromopropyl)ethylbutylmethylammonium bromide and the like are used. On the other hand, guanidine salts used in combination with bis-quaternary ammonium salt polymers include various organic and inorganic salts such as guanidine hydrochloride, guanidine phosphate, guanidine carbonate, and guanidine sulfamate. The most preferred of these guanidine salts is guanidine hydrochloride. Further, as the inorganic salt, lithium chloride, sodium chloride, magnesium chloride, calcium chloride, zinc chloride, barium chloride, magnesium nitrate, calcium nitrate, lithium nitrate, diammonium phosphate, etc. are used. Next, the present invention will be explained in more detail with reference to Examples. Example 1 The bisquaternary ammonium salt polymer obtained in Synthesis Example 1, guanidine hydrochloride, and lithium chloride were mixed in the weight proportions shown in Table 1 to obtain an antistatic agent composition of the present invention (Sample No. 1). ~4 hours.These 0.5% aqueous solutions were used as treatment baths, and a test cloth (dyed cloth of polyester processed yarn fabric obtained under the following conditions) was immersed in each treatment bath at room temperature, and the squeeze rate was 80% with a mangle. The treated cloth was dried at 110°C for 2 minutes. The results of measuring the antistatic properties and abrasion fastness of each treated cloth are shown in Table 1. Comparative products were prepared using the above compounds alone and dimethylamino. The dimethyl sulfate quaternary compound of ethyl methacrylate polymer alone (referred to as "compound aJ" in Table 1), and the mixture of the quaternary compound (compound a) with guanidine hydrochloride and lithium chloride (comparative sample numbers 1 to 1) 6), treatment baths were prepared in the same manner, treated fabrics were prepared, and the physical properties were measured in the same manner.From Table 1, the antistatic agent composition of the present invention showed extremely excellent antistatic properties, It is also seen that there is little decrease in the color fastness of the dyed product. [Preparation of test fabric] Sample fabric: Polyester processed yarn fabric (Amundsen) Dyeing condition dye: Dianix Orange B-S
R6% o, w, f. (manufactured by Mitsubishi Kasei ■) Temperature x time = 130°C x 60 minutes bath ratio: 1:20 Reduction cleaning Reduction cleaning agent: Bisnor SK (reduction cleaning agent manufactured by Nichisha Yushi Kogyo ■) Ig/j! Sodium hydroxide 1 g/l Hydrosulfide 1 g/l Temperature x time: 80°C x 20 minutes Bath ratio: 1:20 Water washing/drying: After washing with running water for 20 minutes, air dry Example 2 Bis obtained in Synthesis Examples 2 to 12 Quaternary ammonium salt 1 Table 2 Polymers and guanidine hydrochloride in a weight ratio of 50:5
Mix at a ratio of 0.0% and dilute to 0.5% to make a treatment bath (
Sample numbers 5-15). 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 bis-quaternary 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, respectively, for sample numbers 16 to 29. ), a polyester textured yarn fabric was treated in the same manner as in Example 1. The antistatic performance of the obtained treated fabric is
As shown in Table 3, it is extremely excellent. Example 4 An antistatic agent composition of the present invention (Sample 2 of Example 1) was prepared by mixing the bisquaternary ammonium salt polymer obtained in Synthesis Example 1 and guanidine hydrochloride at a weight ratio of 50:50.
: Sample numbers 30 to 31) were used in combination with a softener and a water/oil repellent to treat the test fabric. 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 Viclon E-64 (fabric softener for polyester manufactured by Ichisha Yushi Kogyo) as a softener and Asahi Guard AC-71 as a water and oil repellent.
0 (fluorine-based water- and oil-repellent finishing agent manufactured by Asahi Glass GFA) were used in each case. Then, a 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, and the reduction rate was 80%.
After drying at 110°C for 2 minutes, heat treatment was further performed at 150°C for 3 minutes. 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 [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I
] [In the formula [I], R_1 is hydrogen or a methyl group, R_2,
R_3, R_4, R_5 and R_6 each have 1 to 1 carbon atoms
8 represents an alkyl group, oxyalkyl group or aralkyl group, A is -COO- or -CO-NR_7- (however, R_7 represents either hydrogen, methyl group or ethyl group), B is -(CH_2)- _n (where n represents an integer of 2, 3 or 4) or -CH_2CH(OH)CH_2-,
X and Y each represent one of Cl, Br, and 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.