JP2001164041A - Antistatic agent and composition for antistatic agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antistatic agent capable of exhibiting an excellent antistatic activity by the addition of a small amount thereof even under a condition of low temperature and low humidity compared to that of the conventional one, and hardly yellowed even after a long term preservation at 40 deg.C. SOLUTION: This antistatic agent is characterized in that the agent consists essentially of (A) a 10-20C paraffinsulfonic acid salt, and (B) a fatty acid monoglyceride having a 10-22C acyl in a weight ratio of the components A to B regulated so as to be 1:(1-50).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an antistatic agent and an antistatic composition, and more particularly to an antistatic agent and an antistatic composition suitable for a polyolefin resin containing a filler such as an inorganic filler.

[0002]

2. Description of the Related Art Polyolefin resins generate strong static electricity because of their high electrical insulation. For this reason, the polyolefin-based resin product is strongly charged and adsorbs dust, and also has drawbacks such as poor printing, irregularity, discharge, and reduced workability due to dust adhesion in the processing step.

[0003] In order to solve such disadvantages, a method of applying an antistatic agent to a polyolefin resin has been studied. However, the application of the antistatic agent loses its effect in a short time and causes uneven application. And that blocking occurs due to the applied antistatic agent.

In order to avoid such a problem, a method has been proposed in which an antistatic agent is directly kneaded into a polyolefin resin. For example, JP-A-60-58444 discloses a method of kneading a composition containing an alkylamine and / or an alkylamide and a glycerin monoester into an olefin polymer. Is a resin composition of polypropylene and an inorganic filler,
A method of kneading a master batch of a specific higher amine and glycerin monoester, JP-A-48-54155 and JP-A-2-302453, discloses a composition comprising a specific higher amine and a fatty acid monoglyceride as a polyolefin resin. According to these methods, charging of the polyolefin resin product can be prevented to some extent.

However, when these antistatic agents are kneaded with a polyolefin resin and stored at 40 ° C., yellowing occurs, and when stored for a long period of time, dust adheres and the antistatic effect may be reduced. Was.

In particular, polyolefin resins containing a filler such as an inorganic filler tend to adhere to dust under low temperature and low humidity conditions in winter, and the addition of a small amount can effectively suppress the adhesion of dust. The development of antistatic agents has been desired.

The present invention has been made in view of the above circumstances, and does not cause yellowing of a polyolefin resin even when stored at 40 ° C. for a long period of time, and can provide an excellent antistatic effect. Provide antistatic agent and antistatic composition that can maintain performance by adding a small amount of polyolefin resin mixed with filler such as inorganic filler even under low temperature and low humidity conditions in winter. The purpose is to do.

[0008]

Means for Solving the Problems and Embodiments of the Invention To achieve the above object, the present inventor has proposed that a small amount of polyolefin resin is added to a polyolefin resin so that dust does not adhere under low temperature and low humidity conditions. Demonstrates excellent antistatic effect and at 40 ° C
In order to obtain an antistatic agent that does not yellow even when stored at high temperatures for a long period of time, as a result of intensive studies, an antistatic agent containing paraffin sulfonate and fatty acid monoglyceride in a predetermined ratio has an excellent antistatic effect. And it was found that it did not turn yellow even after storage at 40 ° C. for one month.

That is, (A) a paraffin sulfonate having 10 to 22 carbon atoms and (B) an acyl group having 10 to 2 carbon atoms.
By adding an antistatic agent containing the fatty acid monoglyceride 2 as a main component and having a weight ratio of the component (A): the component (B) of 1: 1 to 50 to the polyolefin resin of the component (C). The components (A) to (C) work synergistically to have an excellent antistatic effect even at low temperature and low humidity, and not to yellow even after long-term storage at 40 ° C., especially inorganic fillers It has been found that even a polyolefin resin containing a filler of the type described above does not adhere to dust even under conditions of low temperature and low humidity in winter, and it is possible to effectively suppress the adhesion of dust with a small amount of addition. Was reached.

When only the fatty acid monoglyceride of the component (B) is used as an antistatic agent, an antistatic effect is exhibited, but a sufficient antistatic effect cannot be obtained in a short time.
In addition, the antistatic effect is usually lost within a few weeks. On the other hand, the paraffin sulfonate of component (A) alone takes a long time to exhibit an antistatic effect after molding, and none of them can achieve the objects and effects of the present invention.

Therefore, the present invention firstly comprises (A) a paraffin sulfonate having 10 to 22 carbon atoms and (B) a fatty acid monoglyceride having 10 to 22 carbon atoms in an acyl group as main components, And an antistatic agent, wherein the component (A) and the component (B) are in a weight ratio of 1: 1 to 50,
Secondly, there is provided an antistatic composition comprising the above antistatic agent and a polyolefin-based resin as main components.

Hereinafter, the present invention will be described in more detail. The antistatic agent of the present invention comprises (A) a paraffin sulfonate having 10 to 22 carbon atoms and (B) an acyl group having 1 carbon atom.
And 0 to 22 fatty acid monoglyceride as a main component.

Here, the paraffin of the paraffin sulfonate of the component (A) is a straight-chain or branched-chain paraffin having 10 to 10 carbon atoms.
22, particularly preferably 10 to 18. If the number of carbon atoms is less than 10, the antistatic effect cannot be sufficiently exerted under low temperature conditions. On the other hand, if it is too large, it takes a long time before the antistatic effect is exhibited. Examples of the paraffin sulfonic acid salt include alkali metal salts such as lithium, sodium, and potassium, and a sodium salt is particularly preferable.

The paraffin sulfonate of the component (A) may be in the form of powder or pellets, but pellets are particularly preferred in terms of convenience.

The fatty acid monoglyceride of the component (B) has 10 to 22 carbon atoms in the acyl group, and particularly preferably has 1 to 12 carbon atoms.
2-18 are preferred. If the number of carbon atoms is too small, antistatic performance will not be exhibited. On the other hand, if it is too large, the antistatic effect cannot be exhibited at a low temperature.

The fatty acid monoglyceride of the component (B) may contain fatty acid diglyceride and fatty acid triglyceride which are by-products. Even in this case, the fatty acid (acyl group) constituting glyceride is
Fatty acid monoglyceride containing 80% or more of a fatty acid having 10 to 22 carbon atoms is used. If a mixture of fatty acid monoglycerides not satisfying this range is used, the antistatic effect may not be sufficiently exerted under low temperature conditions.

In this case, the fatty acid monoglyceride of the component (B) preferably has a weight ratio of monoglyceride of 80% or more, particularly preferably 90% or more.
The reason for limiting the ratio in this manner is that if the ratio is lower than this ratio, a sufficient antistatic effect cannot be obtained.

The fatty acid monoglyceride of the component (B) may be in the form of powder or pellets, but pellets are particularly preferred in terms of convenience, and polyolefin resins (for example, homopolymers such as ethylene, propylene and butylene, and the like) Master pellets of a high-concentration mixture with these copolymers) can be used, but in this case, it is preferable to contain 7 to 30% by mass of fatty acid glyceride.

In the present invention, the weight ratio of the component (A) paraffin sulfonate to the component (B) fatty acid monoglyceride [component (A): component (B)] may be 1: 1 to 50. It is necessary, preferably 1: 1 to 40. When the ratio of the component (A) to the component (B) is less than 1: 1, the antistatic performance under low-temperature conditions decreases. on the other hand,
If the amount of the component (B) is too large, the antistatic performance during high-temperature storage deteriorates.

The antistatic composition of the present invention comprises an antistatic agent containing as a main component a paraffin sulfonate (A) and a fatty acid monoglyceride (B), and a polyolefin resin (C). As a main component.

Here, the polyolefin resin as the component (C) includes homopolymers such as ethylene, propylene, butylene, and pentene, copolymers of ethylene and propylene, copolymers of ethylene and vinyl acetate, and ethylene and acrylate. Or a mixture of two or more thereof.

In this case, in the present invention, it is preferable to use a polyolefin resin to which a filler such as an inorganic filler is added. Examples of the inorganic filler include calcium carbonate, talc, kaolin, calcium sulfate and the like, and one of these can be used alone or as a mixture of two or more. The amount of the inorganic filler to be added is 0.1 parts by mass or more, preferably 0.2 to 1 part by mass, per 100 parts by mass of the polyolefin resin. Further, a master pellet of a filler and a polyolefin-based resin and a polyolefin resin pellet can be blended and used in the above-mentioned blending ratio.

The antistatic composition of the present invention contains 0.2 to 10 parts by weight, preferably 0.3 to 8 parts by weight, of an antistatic agent per 100 parts by weight of the polyolefin resin (C). Preferably, 0.6 to 7 parts by mass is added. If the added amount of the antistatic agent is too large, the antistatic performance under low temperature conditions may be insufficient.
Even if it is added in excess of parts by mass, the antistatic effect is not improved, and instead, stickiness may occur on the surface of the molded article, or mechanical properties may decrease.

According to the present invention, an antistatic agent mainly composed of the paraffin sulfonate of the component (A) and the fatty acid monoglyceride of the component (B) is blended with the polyolefin resin of the component (C), These (A) to (C)
The components work synergistically to have both antistatic performance and storage stability under low temperature and low humidity, and almost no yellowing during long-term storage at 40 ° C.

In addition to the components (A) to (C), the antistatic composition of the present invention may further contain, if necessary, oils and fats such as higher alcohols and amides, and lubricants such as fatty acid metal soaps. , An antioxidant, an ultraviolet absorber, a silicone derivative, an antiblocking agent, a coloring agent, a filler, and other additives.

As a method for preparing the antistatic composition of the present invention, for example, the paraffin sulfonate of the component (A) and the fatty acid monoglyceride of the component (B) or the polyolefin resin master pellet of the fatty acid monoglyceride are mainly used. The mixture and the polyolefin resin of the component (C) may be mixed, or they may be mixed separately. In this case, it is preferable that the polyolefin-based resin as the component (C) is processed into hemispherical pellets, square pellets, strand pellets, and the like, and at the time of mixing, these are dry-blended and kneaded with an extruder. Further, kneading can be performed after melting.

The antistatic composition of the present invention can be prepared by press molding, injection molding,
Extrusion molding, blow molding, calendar molding and the like can be performed to form molded articles of various shapes including sheets and films.

[0028]

The antistatic agent of the present invention has no yellowing of the polyolefin resin even when stored for a long time at 40.degree. In particular, even a polyolefin-based resin in which a filler such as an inorganic filler is blended can maintain its performance with a small amount of addition even under low temperature and low humidity conditions in winter.

[0029]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Examples 1 to 6] After weighing at the composition ratios shown in Table 1, they were mixed with a supermixer, and the resulting mixture was formed into strand-like pellets using a twin-screw extruder.
Was prepared.

The obtained antistatic composition was molded into a 76 mm × 76 mm × 1.6 mm plate-like sample at a cylinder temperature of 230 ° C. by using a TS-150 type injection molding machine of Nissei Plastic Industry Co., Ltd. After the sample was removed from the mold and stored in a constant temperature room at a temperature of 5 ° C. and a humidity of 50%, a dart chamber test was performed on the sample after one day and after one month storage according to the following method.

After forming the plate-like sample, the temperature was set at 20 ° C.
The surface resistivity was measured according to the following method for the samples stored one day after storage in a constant temperature room at 60 ° C. and a humidity of 60%, and one month after storage. Further, the yellowness of the samples stored one day after storage in a constant temperature room at 40 ° C. and one month after storage was measured according to the following method. Table 1 shows the results. The dirt chamber test plate-like sample was blown with the toner for a copying machine for 2 minutes in the chamber, and then visually observed and evaluated according to the following criteria. <Evaluation Criteria> わ ず か: A small amount of carbon is uniformly attached or not attached at all. Δ: Carbon is uniformly and slightly attached, or a slight flower pattern (unevenly attached) is present. ×: Carbon is unevenly attached to the whole. Surface resistivity The surface resistivity was measured at an applied voltage of 500 V using a Hiresta H-210 type resistance measuring device manufactured by Mitsubishi Yuka Corporation. When the surface resistivity is less than 1 × 10 ¹³ Ω, the antistatic effect is good. Yellowness (YI value) Measured by a method according to JIS K7103.

[0033]

[Table 1] a-1: sodium paraffin sulfonate (C = 12)
Pellet a-2: sodium paraffin sulfonate (C = 13 to
17) Pellet a-3: sodium paraffin sulfonate (C = 18 to
22) Pellet b-1: Fatty acid monoglyceride (C = 12) pellet b-2: Fatty acid monoglyceride (C = 18) pellet b-3: Fatty acid monoglyceride (C = 16-18) 20
C-1: 100 parts by mass of polypropylene + 20 parts by mass of calcium carbonate c-2: 100 parts by mass of polypropylene + 30 parts by mass of ctal: 100 parts by mass of high-density polyethylene + calcium carbonate 45 parts by mass The melt index of each of the polypropylenes b-3, c-1, and c-2 is in the range of 10 to 12.

[Examples 7 to 12] After weighing and melt-mixing at the composition ratios shown in Table 2, pelletizing was performed.
Was prepared. The obtained composition was measured for dirt chamber test, surface resistivity, and yellowness in the same manner as described above. Table 2 shows the results.

[0035]

[Table 2] a-1: sodium paraffin sulfonate (C = 12)
Pellets a-2: sodium paraffin sulfonate (C = 15)
Pellet a-3: sodium paraffin sulfonate (C = 12 to
16) Pellet b-1: Master pellet of fatty acid monoglyceride (C = 10) 10 parts by mass + polypropylene 100 parts by mass b-2: Fatty acid monoglyceride (C = 18) 15 parts by mass + master of linear low density polyethylene 100 parts by mass Pellets b-3: fatty acid monoglyceride (C = 16 to 18) 20
C-1: 100 parts by mass of polypropylene + 20 parts by mass of calcium carbonate c-2: 100 parts by mass of polypropylene + 30 parts by mass of ctal: 100 parts by mass of high-density polyethylene + calcium carbonate 45 parts by mass The melt index of each of the polypropylenes of b-1, b-3, c-1, and c-2 is 15.

Examples 13 to 18 The composition ratios shown in Table 3 were weighed, dry-blended, and then melt-mixed to prepare the antistatic compositions of Examples 13 to 18. The obtained composition was measured for dirt chamber test, surface resistivity, and yellowness in the same manner as described above. Table 3 shows the results.

[0037]

[Table 3] a-1: sodium paraffin sulfonate (C = 12)
Pellet a-2: sodium paraffin sulfonate (C = 13 to
17) Pellet a-3: sodium paraffin sulfonate (C = 18 to
22) Pellet b-1: Fatty acid monoglyceride (C = 12) pellet b-2: Fatty acid monoglyceride (C = 18) pellet b-3: Fatty acid monoglyceride (C = 16-18) 20
C-1: 80 parts by mass of polypropylene + 20 parts by mass of polypropylene + 20 parts by mass of calcium carbonate c-2: 70 parts by mass of polypropylene + (30 parts by mass of polypropylene + talc) Master pellets of 30 parts by mass) The melt index of polypropylene of each of b-3, c-1, and c-2 is 12.

[Comparative Examples 1 to 4] After weighing at the composition ratios shown in Table 4, the mixture was mixed with a super mixer, and the mixture was formed into strand-like pellets using a twin-screw extruder.
Was prepared. The obtained composition was measured for dirt chamber test, surface resistivity, and yellowness in the same manner as described above. Table 4 shows the results.

[0039]

[Table 4] a-1: sodium paraffin sulfonate (C = 12)
Pellet a-2: sodium paraffin sulfonate (C = 13 to
17) Pellet a-3: sodium paraffin sulfonate (C = 18 to
22) Pellet b-1: Fatty acid monoglyceride (C = 12) pellet b-2: Fatty acid monoglyceride (C = 18) pellet b-3: Fatty acid monoglyceride (C = 16-18) 20
Mass part + master pellet of 100 parts by mass of polypropylene c-1: 100 parts by mass of polypropylene + 20 parts by mass of calcium carbonate c-2: 100 parts by mass of polypropylene + 30 parts by mass of talc b-3, c-1, c-2 Each of the polypropylenes has a melt index of 8 to 10.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshihiro Okada 1-37 Honjo, Sumida-ku, Tokyo F-term in Lion Corporation (reference) 4J002 BB031 BB041 BB061 BB071 BB121 BB141 BB151 BB171 BB261 BB262 EH056 FD010 FD170 GT00

Claims (2)

[Claims] 1. A composition comprising (A) a paraffin sulfonate having 10 to 22 carbon atoms and (B) a fatty acid monoglyceride having 10 to 22 carbon atoms in an acyl group as main components, and (A) a component: (B) 2.) An antistatic agent, wherein the components are in a weight ratio of 1: 1 to 50. 2. An antistatic composition comprising the antistatic agent according to claim 1 and a polyolefin-based resin as main components.