JP3474285B2 - Ionomer composition and use thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ionomer composition having excellent antistatic property and its use. More specifically, a compound containing multiple hydroxyl groups, that is, having 3 hydroxyl groups in the molecule
The present invention relates to a non-chargeable ionomer composition containing a compound having one or more compounds and use of the composition as an antistatic agent.

[0002]

2. Description of the Related Art Ionomer, an ethylene / unsaturated carboxylic acid copolymer containing an alkali metal such as potassium, rubidium or cesium as an ion source and containing a considerable amount of these ions, has been excellent in antistatic property. Was known from. It has also been known that impregnation of such a film of a non-charged ionomer with liquid polyoxyethylene glycol can further enhance the non-charged property. However, the surface resistivity of these compositions is highly dependent on humidity, and the antistatic effect was insufficient in a low humidity atmosphere where non-charging performance is most required for practical use. Further, a polymer composition having semipermanent antistatic property obtained by blending the above-mentioned nonchargeable ionomer with a polymer also has a problem that the antistatic effect is similarly insufficient in a low humidity atmosphere. Therefore, it has been desired to develop an ionomer or a polymer having less humidity dependency and excellent antistatic performance.

Therefore, the inventors of the present invention are keenly aware of an alkali metal ionomer and a method for a polymer composition obtained by blending an alkali metal ionomer with a polymer to exhibit good antistatic property even in a low humidity atmosphere. As a result of investigation, it has been found that this object can be achieved by blending an aliphatic polyhydric alcohol having three or more hydroxyl groups in the molecule and a molecular weight of 400 or less with a potassium ionomer.

Therefore, an object of the present invention is to provide an ionomer composition and a polymer composition which have excellent antistatic performance even in a low humidity atmosphere in various molding applications.

[0005]

Means for Solving the Problems] The present invention, Cali
Using potassium metal as the ion source , potassium gold in the ionomer
The genus content is 0.4 to 4 mol per 1 kg of ionomer
0.1 to 30 parts by weight of an aliphatic polyhydric alcohol having a molecular weight of 400 or less and having 3 or more hydroxyl groups in the molecule per 100 parts by weight of an ionomer of an ethylene / unsaturated carboxylic acid copolymer in the range of Is an ionomer composition.

The present invention also relates to the use of such ionomer composition components as antistatic agents.

The ionomer used in the present invention has a structure in which part or all of the carboxyl groups of the ethylene / unsaturated carboxylic acid random copolymer are neutralized with potassium metal. The above-mentioned ethylene / unsaturated carboxylic acid random copolymer includes other unsaturated monomer components such as methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic acid. Acrylic acid ester or methacrylic acid ester such as n-butyl, or unsaturated ester such as vinyl acetate may be copolymerized.

In the ethylene / unsaturated carboxylic acid random copolymer, the ethylene component is 60 to 90% by weight, particularly 70 to 88% by weight, and the unsaturated carboxylic acid component is 10 to 4% by weight.
It is preferable that 0% by weight, particularly 12 to 30% by weight, and other unsaturated monomer components are copolymerized at a rate of 0 to 30% by weight, particularly 0 to 20% by weight. Such a copolymer can be obtained by randomly copolymerizing each polymerization component under high temperature and high pressure. Also, as long as the sum meets the above requirements,
Two or more different unsaturated carboxylic acid component units may be used.

Potassium is used as the ion source of the ionomer in the present invention . Further, as the unsaturated carboxylic acid component in the ionomer, acrylic acid, methacrylic acid, fumaric acid, maleic acid monomethyl ester,
Examples thereof include maleic acid monoethyl ester and maleic anhydride. Potassium Io in ionomers
The ion content is 1 kg of ionomer from the viewpoint of antistatic property.
The amount is 0.4 to 4 mol , and preferably 0.6 to 2 mol.

As an ionomer, 190 ° C. and 21
The melt flow rate under a load of 60 g is 0.01 to
It is preferable to use 1000 g / 10 minutes, particularly 0.1 to 100 g / 10 minutes.

The aliphatic polyhydric alcohol having 3 or more hydroxyl groups in the molecule used in the present invention has a molecular weight of 400 or less,
It is preferably 80 to 300 and may be liquid or solid at room temperature. The improvement effect is small even if the molecular weight exceeds 400.

Specific examples of such aliphatic polyhydric alcohol include glycerol, diglycerol, trimethylolpropane, 1,1,1-tris (hydroxylmethyl) ethane and 2,2-di (hydroxymethyl) -1. , 3
-Propanediol, sorbitol and the like can be exemplified.
Among these, glycerol or trimethylol
Most preferably, lopan is used.

The amount of the aliphatic polyhydric alcohol used in the present invention is 0. 0 per 100 parts by weight of the ionomer component.
It is 1 to 30 parts by weight, preferably 1 to 20 parts by weight. Fat
If the amount of the aliphatic polyhydric alcohol is less than the above range, the effect of improving the antistatic property is not sufficient. In addition, aliphatic polyvalent
If the amount of rucor is greater than the above range, the preparation of the formulation becomes difficult and surface contamination due to bleeding tends to occur, which is not preferable.

3 hydroxyl groups in the molecule found in the present invention
A polyhydric aliphatic alcohol with a molecular weight of 400 or less
The mechanism of exhibiting excellent antistatic properties even in a low humidity atmosphere by adding it to the potassium metal ionomer will be explained as follows. That is, it is considered that the reason why the alkali metal ionomer originally shows non-chargeability in a high-humidity atmosphere is that a part of the metal salt is dissociated by moisture absorption and the hydrated metal cation becomes easy to move, so that charge accumulation does not occur. To be Therefore, conversely, in a low-humidity atmosphere, such coordination of water molecules to metal cations is less likely to occur, and charge accumulation is likely to occur. However, when a compound having a relatively small molecular weight and a large number of hydroxyl groups in the molecule is blended, the molecule promotes dissociation of the metal salt, and the metal cation coordinated with the hydroxyl group moves sufficiently to prevent the accumulation of charges. Since it is easy, it is considered that excellent non-charging performance is exhibited without being affected by humidity so much.

In such an ionomer composition, any additive such as an antioxidant, a weather resistance stabilizer, an ultraviolet absorber, a slip agent, a pigment, a cross-linking agent, a foaming agent, a tackifier, an inorganic substance is added depending on the purpose. Fillers and the like can be added.

Such an ionomer composition may also optionally be blended with other polymers. Further, such a combination component composed of an ionomer and an aliphatic polyhydric alcohol can be used as an antistatic agent for other polymers. In such an embodiment in which the polymer is mixed with another polymer, for example, 100 parts by weight of an ionomer and an aliphatic polyhydric alcohol are used.
0.1 to 30 parts by weight of coal and 1 to 1000 of other polymers
It can be added in a proportion such as 0 part by weight. In particular, when it is desired to improve the antistatic property by minimizing the influence on the physical properties of other polymers, the ionomer is 1 to 30 parts by weight, preferably 5 to 2 per 100 parts by weight of the other polymer.
5 parts by weight, 0.1 to 9 parts by weight of aliphatic polyhydric alcohol , preferably 0.1 to 2 parts by weight are blended.

Examples of the other polymer include polyolefin resin, styrene resin, polyamide, polyester, polycarbonate, polyacetal, polymethylmethacrylate, polyphenylene oxide, polyphenylene sulfide, polysulfone, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol. , A polyolefin elastomer, various rubbers, and the like, or a combination of two or more thereof. More specifically, as the polyolefin resin, high-pressure polyethylene, linear medium
Representative examples include low density polyethylene, high density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / vinyl acetate copolymer, ethylene / unsaturated carboxylic acid ester, and the like. it can.

The styrene resin is a homopolymer or copolymer of styrene, of which AB is representative.
S resin and polystyrene can be illustrated. ABS here
Resin can be blended, grafted, or grafted
It is a general term for rubber-reinforced styrene polymers synthesized by various manufacturing methods such as a blending method.Styrene, acrylonitrile and methyl are used as rubber components such as polybutadiene, styrene-butadiene rubber and ethylene-propylene-diene rubber. Representative examples include those obtained by graft-polymerizing other monomers such as methacrylate, α-methylstyrene, ethylenebisimide, and maleimide.

Further, polystyrene is not only general-purpose polystyrene synthesized by a production method such as suspension polymerization method or continuous polymerization method, but also impact-resistant polystyrene obtained by graft-polymerizing styrene to a rubber component such as butadiene rubber. Etc. are collectively referred to.

As polyamide, nylon 6, nylon 66, nylon 6.66, nylon 11, nylon 1
2. Polyethylene terephthalate, polybutylene terephthalate, polyester elastomer and the like can be exemplified as polyesters such as 2, nylon 6T and 6I.

Also in the blending system with such other polymer, the above-mentioned optional additives can be blended.
Also, a compatibilizer may be used to increase the compatibility with the ionomer.

The composition of the present invention can be prepared by melt mixing using a melt kneading device such as an extruder. Molding from the composition may be carried out immediately after melt mixing, or may be carried out after pelletization after melt mixing and then molding with another melt molding machine.

[0023]

EFFECT OF THE INVENTION The ionomer composition of the present invention and the polymerizable composition containing the same have a good antistatic property, and the deterioration of the antistatic effect in a low humidity atmosphere is small.
Since it has excellent durability and no stickiness on the surface of the molded product is observed over time, it can be used as a film, sheet, or various molded products in fields requiring non-electrostatic properties, such as automobile parts, office automation equipment, and home appliances. It can be widely used for product parts, storage / storage cases, stationery, daily necessities, etc.

[0024]

EXAMPLES The present invention will be specifically described with reference to the following examples. The compositions and physical properties of the ionomer, the aliphatic polyhydric alcohol , and the thermoplastic resin used for blending the compositions of Examples and Comparative Examples, and the methods for measuring the physical properties of the obtained compositions are as follows.

1. material (1) Ionomer

[Table 1]

(2) Aliphatic polyhydric alcohol Glycerol (Reagent manufactured by Kanto Kagaku; molecular weight 9
2) Trimethylolpropane (Kanto Chemical Reagent; molecular weight 1
34) Polyethylene glycol PEG600 (Kanto Chemical reagent; average molecular weight 500)

[0027] (3) Thermoplastic resin         ABS resin ABS NP15 manufactured by Japan Synthetic Rubber Co., Ltd.         Polypropylene Mitsui Petrochemical Co., Ltd. Hipol L840         Low Density Polyethylene Mitsui Petrochemical Co., Ltd. Mirason 23H

2. Measuring method (1) MFR JIS K6760 (190 ° C, 2160g load)

(2) Surface resistivity test piece at 23 ° C., relative humidity of 30%, 40%, and 50%
After aging for 24 hours, the surface resistivity was measured with a high resistance resistivity meter (HIRESTA-IP) manufactured by Mitsubishi Yuka.

[Examples 1 and 2] Ionomer A and glycerol or trimethylolpropane were mixed at 90:10.
After mixing at a blending ratio of (weight), the mixture was melt-kneaded at 200 ° C. for 10 minutes using a small mixer (Labo Plastomill manufactured by Toyo Seiki). The obtained ionomer composition was dried overnight at 100 ° C. and 10 torr using a vacuum dryer, and then pressure-molded at 180 ° C. to obtain a sheet having a thickness of 1 mm. Table 2 shows the measurement results of the surface resistivity of this test piece at 23 ° C., relative humidity of 30%, 40%, and 50%.
The surface resistivity of each of the obtained ionomer compositions had a small humidity dependence and a sufficiently small value showing non-charging property.

Example 3 In Example 1, ionomer B was used in place of ionomer A, and ionomer B was used.
An ionomer composition was obtained by melt-kneading in the same manner as in Example 1 except that the mixing ratio of glycerol and glycerol was 95: 5. A test piece having a thickness of 1 mm was pressure-molded from the obtained ionomer composition by the same treatment as in Example 1. 23 ° C., relative humidity 30%, 40%, and 50% of this test piece
Table 2 shows the measurement results of the surface resistivity in. The surface resistivity of the obtained ionomer composition had a small humidity dependency and a sufficiently small value to exhibit non-charging property.

[0032]

[Table 2]

[Comparative Example 1] A pressure-molded test piece containing ionomer A alone was prepared in the same manner as in Example 1 except that glycerol was not added. The sample was prepared at 23 ° C and 30% relative humidity and 40% relative humidity. And the surface resistivity at 50% was measured. The results are shown in Table 3. Low humidity (30% relative humidity)
On the side, the value of the surface resistivity was large, and the humidity dependency of the surface resistivity tended to be large.

[Comparative Examples 2 and 3] In Examples 1 and 3, polyethylene glycol P was used instead of glycerol.
An ionomer composition was prepared in the same manner as in Example 1 and Example 3 except that EG600 was used in the same blending ratio, and the pressure-molded test piece had a temperature of 23 ° C. and a relative humidity of 30%.
The surface resistivity at 0% and 50% was measured. The results are shown in Table 3. The value of the surface resistivity was large on the low humidity (30% relative humidity) side, and the humidity dependency of the surface resistivity tended to increase.

[0035]

[Table 3]

Example 4 The ionomer composition A used in Example 1 (ionomer A / glycerol = 90/10 (w /
w)) is mixed with ABS resin NP15 manufactured by Nippon Synthetic Rubber Co., Ltd. at a mixing ratio shown in Table 4 and supplied to a twin-screw extruder (screw diameter 29 mm, L / D = 25) to obtain a resin temperature of 23
The mixture was melt-kneaded and granulated at 0 ° C. and an extrusion rate of 6 kg / h. A test piece having a thickness of 2 mm was prepared from the above composition by an injection molding method (resin temperature 230 ° C.). Table 4 shows the measurement results of the surface resistivity of this test piece at 23 ° C. and relative humidity of 30%, 40%, and 50%. The surface resistivity of the obtained ABS / ionomer composition had a small humidity dependency and a sufficiently small value for showing non-charging property.

Further, this test piece was heated at 50 ° C. for 2 weeks, and the presence or absence of bleeding on the surface of glycerol was examined by touch, but no sign of bleeding was observed.

Example 5 The ionomer composition B used in Example 3 in place of the ionomer composition A in Example 4 (ionomer B / glycerol = 95/5 (w / w))
In the same manner as in Example 4 except that was used, an ABS / ionomer composition composition having a blending ratio shown in Table 4 was obtained. Further, a test piece having a thickness of 2 mm was injection-molded from the obtained polymer composition by the same treatment as in Example 4. Table 4 shows the measurement results of the surface resistivity of this test piece at 23 ° C. and relative humidity of 30%, 40%, and 50%. The surface resistivity of the polymer composition obtained in Example 5 was such that the humidity dependence was small and the charge resistance was close to the upper limit but showed non-charging property.

[Example 6] Polypropylene (Hypol L840 manufactured by Mitsui Petrochemical Co., Ltd.) and ionomer composition B (ionomer B / glycerol = 95/5 (w / w)) at the compounding ratios shown in Table 4. Mix and feed to a twin-screw extruder (screw diameter 29 mm, L / D = 25), resin temperature 18
The mixture was melt-kneaded at 0 ° C. and an extrusion rate of 8 kg / h and granulated. A test film having a thickness of 50 μm was prepared from the above composition by an inflation film molding method (resin temperature 180 ° C.). This test film 23 ° C, relative humidity 30%, 40
Table 4 shows the measurement results of the surface resistivity at 50% and 50%. The surface resistivity of the composition film obtained in Example 6 had a small humidity dependency and a sufficiently small value for showing non-charging property. Moreover, the obtained film was transparent.

[Example 7] The same as Example 6 except that low density polyethylene (Mirason 23H manufactured by Mitsui Petrochemical Co., Ltd.) was mixed in place of polypropylene in Example 6 in the mixing ratio shown in Table 4. Thus, a polyethylene ionomer composition was obtained. Further, an inflation film having a thickness of 50 μm was prepared from the obtained polymer composition by the same treatment as in Example 6. Table 4 shows the measurement results of the surface resistivity of this test film at 23 ° C., relative humidity of 30%, 40%, and 50%. The surface resistivity of the composition film obtained in Example 7 had a small humidity dependency and a sufficiently small value for showing non-charging property. Moreover, the obtained film was transparent.

[0041]

[Table 4] Ionomer Composition A: Ionomer A / Glycerol = 90/10 (w / w) Ionomer Composition B: Ionomer B / Glycerol = 95/5 (w / w)

[Comparative Examples 4 to 7] In Examples 4 to 7,
PEG the glycerol in the ionomer composition A and B
Polymer-ionomer compositions were prepared in the same manner as in Examples 4 to 7 except that the ionomer compositions C and D, which were replaced by 600, were used in the same blending ratio, and injection-molded test pieces or test film 23 were prepared. ℃, relative humidity 30%,
The surface resistivity at 40% and 50% was measured. The results are shown in Table 5. The surface resistivity of each polymer / ionomer composition showed a large value in comparison with those obtained in Examples 4 to 7.

[0043]

[Table 5] Ionomer Composition C: Ionomer A / PEG600
= 90/10 (w / w) Ionomer composition D: Ionomer B / PEG600
= 95/5 (w / w)

─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-59-47243 (JP, A) JP-A-58-149950 (JP, A) JP-A-3-246442 (JP, A) JP-A-4- 170450 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (3)

(57) [Claims] 1. A potassium metal and ion source, Aiono
The potassium metal content in the mer is equivalent to 1 kg of ionomer.
Or ethylene-unsaturated carboxylic acid copolymer ionomer 100 parts by weight per a molecular weight of 400 or less of aliphatic having 3 or more hydroxyl groups in the molecule in the 0.4 to 4 mols
An ionomer composition comprising polyhydric alcohol in an amount of 0.1 to 30 parts by weight. 2. An antistatic agent for a polymer, which comprises the ionomer composition according to claim 1 . 3. An ionograph using potassium metal as an ion source.
The potassium metal content in the mer is equivalent to 1 kg of ionomer.
Or 100 parts by weight ionomer of ethylene-unsaturated carboxylic acid copolymer in 0.4 to 4 mols, aliphatic molecular weight of 400 or less with 3 or more hydroxyl groups in the molecule polyhydric
A polymer composition comprising 0.1 to 30 parts by weight of rucol and 1 to 10000 parts by weight of a polymer other than the ionomer.