JPH05320624A - Antistatic agent and resin composition containing the same - Google Patents

Abstract

PURPOSE:To obtain an antistatic agent giving an immediate effect and scattering little during mixing into a resin, etc., and during molding by using a specific amine or amide compd. as the effective component. CONSTITUTION:An amine or amide compd. of formula I [wherein R<1> is 12-22C alkyl, alkenyl, or hydroxyalkyl; R<2> is 10-21C alkyl, alkenyl, or hydroxyalkyl; and X is CO, or CH2CH(OH)] (e.g. N-dodecyl-N-hydroxyethyldodecanamide or N-dodecyl-N-hydroxyethyl-2-hydroxydodecylamine) is used as the effective component to prepare an antistatic agent. The compd. is obtd. by reacting an amine represented by R-NH2 with ethylene oxide and reacting the resulting compd. of formula II with a compd. of formula III or IV.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel kneading-type antistatic agent, and more specifically, it has a fast-acting effect, and when it is blended with, for example, a resin, it has a small dissipation loss during molding. The present invention relates to an inhibitor, a resin composition containing the same, and a film-shaped molded product made of the resin composition.

[0002]

2. Description of the Related Art Synthetic resins are widely used as materials for films, fibers, and other molded articles, and generally have excellent electric insulating ability, but on the other hand, they are easily charged with electricity, and thus they are easily charged. It is a cause of electrostatic damage and dust adhesion to the surface. Therefore, an antistatic agent is usually added to and blended with the resin.

The basic performance required for such an antistatic agent is: (1) after molding of a resin compound, the resin compound exudes on its surface to improve the surface electric conductivity and to exhibit an antistatic property. 2) Good miscibility with resins, especially hydrophobic resins such as polyolefins, (3) does not promote deterioration of the resin, (4) has high heat resistance, and itself modifies even during molding of the resin Can maintain its performance without
(5) It has a fast-acting effect, and (6) its performance lasts semipermanently.

However, almost none of them satisfy all of these various conditions, and Japanese Patent Publication No. 52-30015 and Japanese Patent Laid-Open No. 60-2 disclose that these conditions are relatively satisfied.
40781, JP-A-60-240782 and JP-A-6
There is an antistatic composition described in 1-28537. However, since these also contain a large amount of low molecular weight components, leaching and volatilization from inside the resin during heat molding are significant, and this causes a large loss due to dissipation during processing, and also adheres to and accumulates on the inner walls of molds and processing machines. The antistatic agent has a drawback that it is denatured and decomposed during repeated molding and adversely affects the surface properties of the resin molded product. And, in a molded product having a large specific surface area such as a film molded product, the dissipation loss of the antistatic agent was particularly remarkable.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an antistatic agent which satisfies the above conditions (1) to (6) and has a small dissipation loss during resin processing. It is a thing.

[0006]

Under such circumstances, as a result of intensive studies, the present inventor found that the compound represented by the following general formula (1) is an antistatic agent having the above-mentioned object, The present invention has been completed.

That is, the present invention provides the following general formula (1):

[0008]

[Chemical 2]

(In the formula, R ¹ represents an alkyl, alkenyl or hydroxyalkyl group having 12 to 22 carbon atoms, and R ²
Is an alkyl, alkenyl or hydroxyalkyl group having 10 to 21 carbon atoms, X is -CO- or -CH ₂ CH
The present invention provides an antistatic agent containing an amine compound or an amide compound represented by (OH)-) as an active ingredient, a resin composition containing the same, and a film-shaped molded article made of the resin composition. ..

Examples of the compound of the formula (1) of the present invention include N-dodecyl-N-hydroxyethyldodecane amide, N- (2-hydroxydodecyl) -N-hydroxyethyldodecane amide, N-dodecyl-N- Hydroxyethyl octadecane amide, N- (2-hydroxydodecyl) -N-hydroxyethyl octadecane amide, N
-Dodecenyl-N-hydroxyethyl octadecane amide, N-hydroxyethyl-N-octadecyl dodecane amide, N-hydroxyethyl-N-octadecyl tetradecane amide, N-hydroxyethyl-N-octadecyl hexadecane amide, N-hydroxyethyl-N-
Octadecyl octadecanoamide, N-hydroxyethyl-N- (2-hydroxyoctadecyl) octadecane amide, N-hydroxyethyl-N-octadecylicosanoamide, N-hydroxyethyl-N-octadecyl docosaneamide, N-hydroxyethyl-N -Icosyldodecane amide, N-hydroxyethyl-N-icosyl tetradecanamide, N-dodecyl-N-hydroxyethyl-2-hydroxydodecylamine, N-dodecyl-
N-hydroxyethyl-2-hydroxytetradecylamine, N, N-bis (2-hydroxytetradecyl) ethanolamine, N-dodecyl-N-hydroxyethyl-2-hydroxyhexadecylamine, N-dodecyl-
N-hydroxyethyl-2-hydroxyoctadecylamine, N-dodecyl-N-hydroxyethyl-2-hydroxyicosylamine, N-hydroxyethyl-N-octadecyl-2-hydroxyoctadecylamine, N,
Examples thereof include N-bis (2-hydroxyhexadecyl) ethanolamine and N, N-bis (2-hydroxyoctadecyl) ethanolamine.

Among them, those having 3 or less hydroxyl groups in one molecule are preferable in view of compatibility with polyolefin. In addition, those having a molecular weight of about 400 to 800 are preferable in that they have fast-acting properties and less scattering during resin processing.

The compound (1) of the present invention is obtained by converting the R ¹ amine (2) into ethylene oxide (3) according to the following reaction formula.
To give N-hydroxyethyl-R ¹ amine (4)
That is, it is produced by reacting this with an oxide (5) or a carboxylic acid (6).

[0013]

[Chemical 3]

(In the formula, R ¹ , R ² and X have the same meanings as described above.) Further, in the formula (1), X is —CH ₂ CH (O
The compound represented by H)-can also be produced by a method of reacting R ¹ amine (2) with oxide (5) and then reacting the product with ethylene oxide.

The resin composition of the present invention is obtained by adding 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight of the antistatic agent of the formula (1) to 100 parts by weight of the resin. Be done. If the compounding amount of the antistatic agent is less than 0.05 parts by weight, a sufficient antistatic effect cannot be obtained, and if the compounding amount exceeds 5 parts by weight, the surface of the molded article may be sticky.

Examples of the resin include homopolymers of olefins such as polyethylene, polypropylene, polybutene, polyisobutene, polybutadiene and polypentene, copolymers of olefins such as ethylene and propylene, ethylene and vinyl acetate, ethylene and vinyl chloride, ethylene and acrylic. Examples thereof include acid esters, copolymers of olefin and polar vinyl compounds such as propylene and vinyl chloride, and mixtures thereof, and polystyrene, poly (acrylic acid ester), poly (methacrylic acid ester), ABS resin and the like.

The antistatic resin composition of the present invention may further contain an antioxidant, an ultraviolet absorber, a nucleating agent, a colorant, a filler, and other additives, if necessary.

The film-shaped molded product of the present invention is a molded product having an excellent antistatic property obtained by molding the above resin composition into a film or a thin film. For example, a biaxially oriented polypropylene film, T Examples thereof include a polypropylene film and a polyethylene film formed by die-extrusion molding or inflation molding. These can be manufactured by a known film forming method.

[0019]

Since the compound (1) of the present invention has a molecular weight of 1000 or less, it can be exuded to the surface immediately after being mixed with a resin and molded, and the surface electric conductivity can be improved and the antistatic performance can be exhibited. In addition, since the molecular weight is 400 or more, the proportion of scattering and scattering from the resin surface during heat molding of a resin composition containing this is extremely small. Further, since the basic skeleton is a tertiary amine or an N-disubstituted amide, the stability is excellent and the heat resistance is extremely high. Therefore, deterioration of the resin is not promoted, and the resin itself does not deteriorate during molding. The performance can be maintained without denaturation. Since it has two aliphatic chains having 12 or more carbon atoms in one molecule, it has extremely high miscibility with a highly hydrophobic resin such as polyolefin.

[0020]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below, but these are illustrative and the present invention is not limited to these Examples. Synthesis example of antistatic agent

Compound A1: Octadecylamine melted at 160 ° C. under a nitrogen atmosphere was vigorously stirred at 1.0
5 equivalents of ethylene oxide are introduced over 2 hours. After the introduction is completed, after holding at 160 ° C. for 30 minutes,
Unreacted octadecylamine is distilled off under reduced pressure. The white solid obtained has a melting point of 44-62 ° C. and consists of 64% N-octadecylethanolamine and 36% N, N-bishydroxyethyloctadecylamine. This product can be used as it is in the next reaction to obtain an antistatic agent, but N-octadecylethanolamine (A0) was isolated by vacuum distillation. A0 and equimolar lauric acid were reacted in a nitrogen stream at 165 ° C. for 3 hours, and then dehydrated under reduced pressure at 165 ° C. for 2 hours to give N-hydroxyethyl-N-octadecyldodecane amide [ν _{C = O} ( KB
r) = 1616 cm ^-1 ], 90% or more of A1 was obtained.

Compounds A2 and A3: By the same reaction as above, stearic acid and icosanoic acid were respectively converted into A2 (N-
Hydroxyethyl-N-octadecyl octadecane amide is 85% or more), A3 (N-hydroxyethyl-N-
Octadecyl icosanamide was obtained (83% or more).

Compound A4 (method 1): A0 and 1.05 equivalent of 1,2-epoxyoctadecane were added to 100 parts in a nitrogen stream.
The reaction was carried out at -135 ° C for 10 hours. Unreacted substances were distilled off at 180 ° C. under reduced pressure to give N-hydroxyethyl-N-octadecyl-2-hydroxyoctadecylamine [purity> 95.
%; Melting point: 29-35 ° C.].

Compound A4 (Method 2): Octadecylamine and 1.05 equivalent of 1,2-epoxyoctadecane were reacted at 160 ° C. for 10 hours in a nitrogen stream. Unreacted substances were distilled off at 160 ° C. under reduced pressure, and then distillation was continued under high vacuum to obtain N-octadecyl-2-hydroxyoctadecylamine (melting point: 80-91 ° C.). In a nitrogen atmosphere, 1.05 equivalent of ethylene oxide was added at 160 ° C. for 2 hours, and after aging for 30 minutes, unreacted ethylene oxide was distilled off under reduced pressure at 120 ° C. Was obtained.

Compound A5: From N-laurylethanolamine and 1,2-epoxydodecane in the same manner as in A4 (method 1), N-dodecyl-N-hydroxyethyl-2-
Hydroxydodecylamine (purity 92% or more) was obtained.

Compound A6: From N-docosylethanolamine and 1,2-epoxydocosane in the same manner as in A4 (method 1), N-docosyl-N-hydroxyethyl-2-
Hydroxydocosylamine (purity 87% or more) was obtained.

Compounds used in Comparative Examples R1: stearylamine R2: N, N-ditetracosylethanolamine R3: N-octadecyldiethanolamine R4: daspar 125B (Miyoshi fats and oils; reaction product of α-olefin epoxide and monoethanolamine )

Examples 1-9, Comparative Examples 1-5 Compound A1-A6 and Compounds R1 and R2 were added to polypropylene resin [Mitsui Toatsu; BEB-G] in 0.3 parts by weight respectively, and polystyrene resin [Mitsubishi Monsanto]. Then, 1.0 part of DIALEX HT88] was added and kneaded, and then the surface specific resistance of a sample piece pressed into a 2 mm thick sheet was measured. The results are shown in Tables 1 and 2.

[0029]

[Table 1]

[0030]

[Table 2]

Examples 10 to 11 and Comparative Example 6 Compounds A2 and A5 were mixed with ABS resin [Toray; Toyolac 10].
0], ethylene-vinyl acetate copolymer [Sumitomo Chemical; Evatate D2011 (vinyl acetate content: 5% by weight)] was added and kneaded, and the surface specific resistance of the sample piece (thickness 2 mm) after 3 days was measured. The results are shown in Table 3.

[0032]

[Table 3]

Examples 12 to 17 and Comparative Examples 7 to 9 Antistatic agents A1 to A6 and control agents R1 to R5 were used as polypropylene resins [Showa Denko; Shuaromer FA-5].
31] to 3.00 parts, and a film molded product having a thickness of 0.2 mm was obtained by a T-die method at 230 ° C. 50g each
With respect to the resin composition film sample of No. 3, the residual reagent was removed with a Soxhlet extractor using chloroform as a solvent, and the residual ratio of each reagent after film formation was determined by comparison with the same treated product of additive-free polypropylene. The results are shown in Table 4.

[0034]

[Table 4]

[0035]

The resin composition containing the antistatic agent of the present invention is 10 ⁸ to 10 depending on the shape and the mixing ratio.
^It has a surface resistivity of ¹¹ Ω / □ and does not accumulate a large amount of static electricity on the surface, so it does not cause various electrostatic troubles due to dust adhesion or discharge. Further, the antistatic agent is gradually exuded from the inside of the resin composition to the surface, so that the antistatic ability is quickly regenerated even after the surface is washed,
In addition, its performance lasts semipermanently. Further, the antistatic agent of the present invention has a property of being less likely to volatilize during resin processing, and therefore, for a molded article having a large specific surface area such as a film-shaped or thin-film resin composition and in which an additive easily scatters during heating processing. Is particularly effective, has a small dissipation loss, and has an extremely high antistatic ability per unit compounding amount.

Claims (3)

[Claims] 1. The following general formula (1): (In the formula, R ¹ represents an alkyl, alkenyl or hydroxyalkyl group having 12 to 22 carbon atoms, and R ² represents 10 carbon atoms.
No. 21 to an alkyl, alkenyl or hydroxyalkyl group, and X represents —CO— or —CH ₂ CH (OH) —), which is an antistatic agent containing an amine compound or an amide compound as an active ingredient. 2. A resin composition containing 0.05 to 5 parts by weight of the antistatic agent according to claim 1 with respect to 100 parts by weight of the resin. 3. A film-shaped molded product comprising the resin composition according to claim 2.