JP2002012722A - Antistatic ionomer composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ionomer composition excellent in an antistatic property little dependent on humidity, and a hard polymer composition containing an antistatic agent excellent in mechanical property. SOLUTION: The ionomer composition comprises a mixture component (A) comprising a potassium ionomer (A1) which is a copolymer of ethylene and an unsaturated carboxylic acid with a degree of neutralization of not less than 60% and a polyvalent alcohol compound or an aminoalcohol compound (A2) occupying 1-20 wt.% against the ionomer (A1) and a copolymer (B) of ethylene, (metha)acrylate and maleic monoester, with the (metha)acrylate occupying 20-70 wt.% and the maleic monoester occupying 0.1-10 wt.%, wherein the weight ratio (A)/(B) is 50/50-95/5. Also there is provided an antistatic polymer composition in which a hard polymer (C) and the components of the ionomer composition have a weight ratio (C)/[(A)+(B)]=70/30-95/5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ionomer composition having excellent non-charging properties under low humidity and its use as a non-charging agent. The present invention also relates to a non-chargeable polymer composition comprising a hard polymer containing such a non-charge-providing agent component and having excellent mechanical properties.

[0002]

2. Description of the Related Art An ionomer composition obtained by adding a polyhydric alcohol compound to a potassium ionomer of an ethylene / unsaturated carboxylic acid copolymer having a high degree of neutralization exhibits excellent antistatic properties even at low humidity and has various properties. It is already known to be an antistatic agent for polymers of the formula (I). For example, JP-A-8-1
Japanese Patent No. 34295 discloses that a composition of a potassium ionomer and a polyhydric alcohol having three or more hydroxyl groups exhibits excellent non-charging properties under low humidity, and that by adding these to an ABS resin or polypropylene, It is disclosed that a composition exhibiting sufficient non-charging properties even under humidity and having excellent long-lasting non-charging properties can be obtained.

[0003] In this proposal, the surface resistivity is specifically measured with a relative humidity of 30% as the lower limit of the humidity, and it has been proved that sufficient non-charging property is exhibited. However, even in such a composition, when the humidity is further lowered, sufficient antistatic properties may not be exhibited depending on the formulation.

[0004] Hard polymers such as ABS resins have the advantage of being excellent in mechanical properties. However, when the above-mentioned ionomer composition is blended, there is also a disadvantage that the properties are impaired to a considerable extent. In order to improve such a defect, for example, a rubber-reinforced styrenic resin such as an ABS resin is mixed with an epoxy group-containing styrenic polymer (JP-A-9-12827) or graft modified. (Japanese Patent Application Laid-Open No. 9-59479), for example, have been proposed, but these modifiers are expensive, and the object of the modification is a rubber-reinforced styrene-based resin. Therefore, it was not applicable to all hard polymers.

[0005]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a non-chargeable ionomer composition comprising a potassium ionomer and a polyhydric alcohol compound, which exhibits sufficient non-chargeability even at lower humidity. Accordingly, it is an object of the present invention to provide an improved prescription capable of providing more excellent non-charging performance as a non-charging agent for various polymers.

A second object of the present invention is to provide a system in which such a non-charge-imparting component is blended with a hard polymer, while exhibiting excellent non-chargeability even at a lower humidity, and at the same time exhibiting excellent properties of the hard polymer. It is an object of the present invention to provide an improved formulation capable of suppressing the tendency of reduced mechanical properties.

[0007]

As a result of the investigation, it was found that by adding a small amount of an ethylene copolymer having a specific composition,
It has been found that the non-chargeable ionomer composition has a further reduced non-humidity dependence on the non-chargeability, and has an effect of exhibiting more excellent non-chargeability in a very low humidity state. At the same time, even in a system in which the above-mentioned non-chargeable ionomer composition is blended with a hard polymer, by adding a small amount of an ethylene copolymer having this specific composition, the effect that the humidity dependency of the non-chargeability is similarly reduced further becomes smaller. In addition, it has been found that the tendency to decrease the mechanical properties can be suppressed. .

That is, according to the present invention, a potassium ionomer (A1) of an ethylene / unsaturated carboxylic acid copolymer having a degree of neutralization of 60% or more and a polyhydric alcohol compound in an amount of 1 to 20% by weight based on (A1). Ethylene / (meth) having a mixed component (A) composed of an amino alcohol compound (A2) and (meth) acrylic acid ester content of 20 to 70% by weight and maleic acid monoester content of 0.1 to 10% by weight.
It is composed of an acrylate / maleic acid monoester copolymer (B), which has a weight ratio of (A) / (B) = 50.
The present invention relates to a non-chargeable ionomer composition characterized by being blended in a ratio of / 50 to 95/5 and its use as a polymer additive.

The present invention also relates to a potassium ionomer (A1) of an ethylene / unsaturated carboxylic acid copolymer having a degree of neutralization of 60% or more and a polyhydric alcohol compound or amino alcohol in an amount of 1 to 20% by weight based on (A1). The mixed component (A) composed of the base compound (A2), ethylene (meth) acrylate having a (meth) acrylate content of 20 to 70% by weight and a maleic acid monoester content of 0.1 to 10% by weight. It is composed of a maleic acid monoester copolymer (B) and a hard polymer (C), which are (A) /
(B) = 50 / 50-95 / 5, (C) / [(A) +
(B)] = 70/30 to 95/5.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The potassium ionomer (A) of the ethylene / unsaturated carboxylic acid copolymer used in the present invention
1) is a copolymer obtained by neutralizing a part or all of the carboxyl groups in an ethylene copolymer composed of ethylene and an unsaturated carboxylic acid, or further optionally another monomer with potassium ions. Here, as the unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic anhydride, monomethyl maleate, monoethyl maleate and the like can be exemplified, and acrylic acid or methacrylic acid is particularly preferable. Other monomers that can be copolymer components include vinyl esters such as vinyl acetate, methyl acrylate,
Examples include unsaturated carboxylic esters such as ethyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, and methyl methacrylate, and carbon monoxide.

The above-mentioned ethylene / unsaturated carboxylic acid copolymer has an unsaturated carboxylic acid content of, for example, 13 to 30% by weight, preferably 15 to 25% by weight in order to impart sufficient antistatic property. Can be mentioned. Alternatively, a blend of two or more copolymers having different unsaturated carboxylic acid contents, wherein the average acid content is 10 to 30% by weight,
It is preferably 11 to 20% by weight, and the difference in acid content between those having the highest acid content and those having the lowest acid content is 1% by weight or more, preferably 2 to 20% by weight. The other monomer may be contained, for example, at a ratio of 0 to 30% by weight. Such a copolymer can be easily obtained by radical copolymerization under high temperature and high pressure.

The potassium ionomer (A1) has a degree of neutralization (average degree of neutralization when two or more ethylene-unsaturated carboxylic acid copolymers are used) of 60% or more from the viewpoint of non-charging properties. Preferably, 70% or more is used, but in consideration of easiness of production, workability, and the like, it is desirable to limit the upper limit of the degree of neutralization to about 95% or less. As the potassium ionomer, considering the miscibility with various polymers and various physical properties of the composition, 190 ° C., 2160 ° C.
The melt flow rate under a g load is 0.1 to 100.
It is preferable to use one having g / 10 minutes.

[0013] Of the component (A2) used in the present invention,
As the polyhydric alcohol compound, specifically, various molecular weights, preferably a molecular weight of 2000 or less, more preferably a molecular weight of 1000 or less, such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene / polyoxypropylene glycol Polyoxyalkylene glycol, glycerin,
Examples include polyhydric alcohols such as trimethylolpropane, pentaerythritol, sorbitol, diglycerin, triglycerin, and polyglycerin, and ethylene oxide adducts and partial esters thereof.

The amino alcohol compounds include:

An alkanolamine represented by R ′ _(3-n) N (ROH) _n (where R is an alkylene group, R ′ is a hydrogen atom or an alkyl group, and n is an integer of 1 to 3), Include diethanolamine, dipropanolamine, dipentanolamine, N-methylethanolamine, N-ethylpropanolamine, etc.

[0015]

Embedded image (Wherein, R is an alkyl group having about 12 to 22 carbon atoms, m,
n is any integer) alkylene oxide adduct of an alkylamine represented by

[0016]

Embedded image (Wherein, R is an alkyl group having about 12 to 22 carbon atoms, m,
and n is an arbitrary integer).

Among these, particularly preferred polyhydric alcohol compounds are polyethylene glycol, glycerin and the like, and amino alcohol compounds are diethanolamine and the like.

Potassium ionomer (A1) and polyhydric alcohol compound or amino alcohol compound (A2)
(A2) is a mixed component (A) consisting of (A1)
To 1 to 20% by weight, preferably 2 to 15% by weight. The component (A2) is a very effective component for the ionomer composition of the present invention to exhibit excellent antistatic properties under low humidity. It is used in the above-mentioned range because it causes contamination and stickiness on the surface.

The ethylene / (meth) acrylate / maleic acid monoester copolymer (B) used in the present invention has a (meth) acrylate content of 20-7.
0% by weight, preferably 25 to 65% by weight, maleic acid monoester content of 0.1 to 10% by weight, preferably 1 to
7% by weight. By blending such a copolymer (B), the non-charging property of the mixed component (A) under low humidity can be improved. When blended with the hard polymer (C) together with the mixed component (A), a decrease in the mechanical strength of the hard polymer (C) caused by the blend of the mixed component (A) is suppressed, and the non-charging property is reduced. Can also be improved.

The (meth) acrylate in the copolymer (B) includes methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate,
Isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like can be exemplified, and among these, any one of methyl acrylate and ethyl acrylate can be selected. preferable.

As the maleic acid monoester in the copolymer (B), an alkyl ester having an alkyl moiety of about 1 to 6 carbon atoms can be used, but a monomethyl ester or a monoethyl ester is particularly preferable. As the copolymer (B), the mixed component (A)
Considering miscibility and mechanical strength with
Melt flow rate at 2160 g load is 0.1 to
It is preferable to use one having 100 g / 10 min, especially 1 to 50 g / 10 min.

In the ionomer composition of the first invention of the present invention, the potassium ionomer (A1) and a polyhydric alcohol compound or an amino alcohol compound (A
The mixed component (A) composed of 2) and the copolymer (B) are in a weight ratio of 50/50 to 95/5, preferably 60/40 to 9/50.
It is blended at a ratio of 0/10. By blending the component (B), the non-charging property of the component (A) under low humidity can be improved. However, if the amount is too large, the effect of increasing the amount is lost, so that it is used in the above range. The ionomer composition can be prepared by kneading the polymer component under the melting condition. Generally, the composition of the component (A1) and the component (A2) is prepared in advance, and the composition is prepared by kneading the copolymer and the copolymer (B).
It can also be prepared by dry-blending (A2) and (B) and then melt-kneading.

The ionomer composition thus obtained comprises:
It can be used as it is as a molded article of various shapes. Alternatively, it can be used as a non-charging agent for various polymers. As the polymer to be compounded, (A
A polymer other than 1) and (B), preferably a hard polymer (C) described later, can be exemplified, but the polymer is not limited thereto. (A) and (B) in that case
It is effective to add so as to account for 5 to 30% by weight of the total.

The present invention also provides a non-chargeable polymer composition containing a hard polymer (C) in addition to the components (A) and (B). The hard polymer (C) used here is a thermoplastic or thermosetting polymer having a flexural rigidity of 300 MPa or more, preferably 500 to 10,000 MPa.

Examples of such thermoplastic polymers include:
High pressure polyethylene, medium, high density polyethylene, linear low density polyethylene, ultra low density linear polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-
Pentene, olefin polymers such as cyclic olefin polymers, styrene polymers such as rubber-reinforced styrene resins such as polystyrene, high impact polystyrene and ABS resin, nylon 6, nylon 66, nylon 1
1. Nylon 12, nylon 6/66, amorphous nylon, polyamide such as polyamide elastomer, polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, cyclohexane dimethanol copolymerized polyethylene terephthalate, polyether Ester elastomers, polyesters such as wholly aromatic polyesters, vinyl alcohol polymers such as ethylene-vinyl alcohol copolymer and polyvinyl alcohol, halogenated olefin polymers such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl fluoride , Polycarbonate, polyacetal, polymethyl methacrylate, polyphenylene oxide, polyphenylene sulfide, polysulfone, polyimide There can be exemplified a mixtures of two or more of these, compositions based on these polymers.

Examples of the thermosetting polymer include phenol resins, epoxy resins, unsaturated polyester resins, polyurethanes, urea resins, and melamine resins.

The potassium ionomer / polyhydric alcohol compound mixture component (A), the copolymer (B) and the hard polymer (C) in the non-chargeable polymer composition of the present invention are compounded by weight. (A) / (B) = 50 /
50-95 / 5, preferably 60 / 40-90 / 10,
(C) / [(A) + (B)] = 70/30 to 95 /
5, preferably 75/25 to 90/10. If the blending ratio of the hard polymer (C) is less than the above range, the excellent mechanical properties are impaired, which is not preferable. In addition, the mixed component (A) imparts a desired non-charging property, and the copolymer (B) suppresses a decrease in mechanical properties due to the blending of the component (A). In order to improve synergistically, it is effective to mix them in the above ratios.

In preparing the non-chargeable polymer composition, it can be obtained by blending the hard polymer (C) with the composition comprising (A) and (B) obtained in the first invention. However, the present invention is not necessarily limited thereto. For example, a method of simultaneously blending (A), (B) and (C) or a method of simultaneously blending (A1), (A2), (B) and (C) Various methods such as a method can be adopted.

Various additives can be added to the non-chargeable ionomer composition or non-chargeable polymer composition of the present invention. Examples of such additives include antioxidants, anti-aging agents, light stabilizers, heat stabilizers, UV absorbers, lubricants, anti-blocking agents, plasticizers, adhesives, inorganic fillers, glass fibers, carbon Examples include reinforcing fibers such as fibers, pigments, dyes, flame retardants, flame retardant auxiliaries, foaming agents, foaming auxiliaries, and the like. If the amount is small, an ordinary antistatic agent can be added.

[0030]

Next, the present invention will be described in more detail with reference to examples. In addition, the evaluation method of the raw material used in the Example and the comparative example and the obtained polymer composition is as follows.

1 Raw Materials Used (A) Mixed component A-1: ethylene / methacrylic acid content of 12.5% by weight
Polyethylene glycol having a molecular weight of 600 was added to a potassium ionomer (a neutralization degree of 92%) of a methacrylic acid copolymer.
A-2: ethylene / methacrylic acid content of 12.5% by weight
Methacrylic acid copolymer potassium ionomer (neutralization degree 82%) blended with 9% by weight of glycerin (B) Copolymer B-1: 55% by weight of methyl acrylate content, 4% by weight of monomethyl maleate content, MFR 12 g / 10 min ethylene / methyl acrylate / monomethyl maleate copolymer (C) Hard polymer C-1: ABS resin, manufactured by Nippon Synthetic Rubber Co., Ltd., ABS
NP15 C-2: Polypropylene, manufactured by Mitsui Chemicals, Inc., Hypol L840 C-3: Polyamide, manufactured by Toray Industries, Inc., Amilan CM10
17C C-4: polystyrene, Asahi Kasei Corporation, Styron 6
85

2 Methods for evaluating physical properties (1) DuPont impact test (1 / 4R punch) An impact test at 23 ° C. was performed. ：: Decrease in impact resistance is 10% of the original resin
% Or less ×: Decrease in impact resistance is 10% of the original resin
%that's all

(2) Antistatic performance A 2 mm thick square plate was placed in a constant temperature and humidity chamber at each humidity (15, 20, 3).
After aging for 24 hours at 0% RH), the surface resistivity was measured using an electric resistance meter Hiresta manufactured by Mitsubishi Chemical Corporation.

[Examples 1 and 2] The mixed component (A) and the copolymer (B) were mixed in the proportions shown in Table 1, melt-kneaded using a twin-screw extruder, and granulated. Next, a test piece having a thickness of 2 mm was prepared by injection molding, and its surface resistivity was measured. The results are also shown in Table 1.

[Comparative Examples 1-2] Mixed components A-1 and A-
For each of No. 2, a test piece was prepared in the same manner, and the surface resistivity was measured. The results are also shown in Table 1.

[0036]

[Table 1]

[Examples 3 to 7] The mixed component (A), the copolymer (B) and the hard polymer (C) were mixed at the ratio shown in Table 2 and melt-kneaded using a twin-screw extruder. Granulated. Next, a test piece having a thickness of 2 mm was prepared by injection molding and evaluated. The results are also shown in Table 2.

[0038]

[Table 2]

Comparative Examples 3 to 6 Hard Polymers C-1 to C-
For each of No. 4, test pieces were prepared in the same manner, and the physical properties were measured. Table 3 shows the results.

[Comparative Example 7] A test piece was prepared in the same manner as for the mixture containing the mixed component A-1 and the hard polymer C-1 in the proportions shown in Table 3, and the physical properties were measured. Table 3 shows the results
Shown in

[Comparative Example 8] A test piece was prepared in the same manner as described above in which the copolymer B-1 and the hard polymer C-1 were blended at the ratio shown in Table 3, and the physical properties were measured. Table 3 shows the results
Shown in

[0042]

[Table 3] In the table, the value of impact resistance is MPa

When Examples 3 to 6 and Comparative Examples 3 to 6 are compared, it can be seen that the impact resistance of the hard polymer does not decrease so much, and that the non-chargeability is remarkably improved. When Example 3 and Comparative Example 7 are compared, the improvement in impact resistance is remarkable,
In addition, it can be seen that the surface resistivity of Example 3 was lower, even though the amount of the mixed component B-1 was smaller, and the non-charging property under low humidity was better.

[0044]

The ionomer composition of the present invention has excellent non-charging properties under low humidity. Such an ionomer composition can be used not only as various molded articles, but also as an antistatic agent for various polymers, and can provide excellent antistatic properties over a long period of time. In particular, the non-chargeable polymer composition of the present invention blended with the hard polymer, while utilizing the excellent mechanical properties of the hard polymer as it is, exhibits excellent anti-static properties even under low humidity, and Also excellent in sustainability. Therefore, it can be widely used as a film, sheet, or other molded article of various shapes in fields where non-electrification is required, such as automobile parts, OA equipment, home electric appliance parts, or their storage and storage cases, stationery, and daily necessities. it can.

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Claims (3)

[Claims] 1. A potassium ionomer (A1) of an ethylene / unsaturated carboxylic acid copolymer having a degree of neutralization of 60% or more and 1 to 20% by weight of a polyhydric alcohol compound or amino alcohol compound (A1) based on (A1) The mixed component (A) comprising A2) and (meth) acrylate content are 20
~ 70 wt%, maleic acid monoester content is 0.1 ~
10% by weight ethylene (meth) acrylate
A non-chargeable ionomer composition comprising a maleic acid monoester copolymer (B), which is blended at a weight ratio of (A) / (B) = 50/50 to 95/5. . 2. A polymer additive comprising the non-chargeable ionomer composition according to claim 1. 3. A potassium ionomer (A1) of an ethylene / unsaturated carboxylic acid copolymer having a degree of neutralization of 60% or more and 1 to 20% by weight of a polyhydric alcohol compound or amino alcohol compound (A1) based on (A1). The mixed component (A) composed of A2) and (meth) acrylate content are 20 to
70% by weight, maleic acid monoester content 0.1-1
It consists of 0% by weight of an ethylene / (meth) acrylate / maleic acid monoester copolymer (B) and a hard polymer (C), and these are (A) / (B) = 5 by weight ratio.
0/50 to 95/5, (C) / [(A) + (B)] = 7
A non-chargeable polymer composition which is blended at a ratio of 0/30 to 95/5.