JP2010006871A - Saponified polymer or polymer composition, excellent in antistatic property - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a saponified polymer having flexibility, excellent in processability and moldability, excellent in also miscibility with other resins, and also equipping an excellent non-charging property (antistatic property), and a polymer composition obtained by blending an olefinic polymer with the saponified polymer, further improved in flexibility, processability, moldability and miscibility. <P>SOLUTION: This saponified polymer obtained by alkaline-saponifying an ethylene-unsaturated carboxylic acid ester copolymer is provided by having a 0.1 to 5.8 mol/kg range alkali metal ion concentration in the saponified polymer and an excellent non-charging property. The polymer composition excellent in the non-charging property comprises (A) &lt;100 and &le;2 pts.mass saponified polymer and (B) &gt;0 and &le;98 pts.mass olefinic polymer. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a polymer saponified (saponified) product excellent in non-charging properties (antistatic properties) or a polymer composition containing the saponified product, and more specifically, an ethylene / unsaturated carboxylic acid ester copolymer having specific properties. A polymer composed of an alkaline saponification product of a polymer, which has excellent antistatic properties such as static elimination performance and antistatic performance, and is flexible and has excellent miscibility with other resins, or a polymer composition containing the saponification product Related to things.

As electrical elements become widespread in consumer materials and industrial products made of various plastics, synthetic fibers, synthetic paper, etc., the demand for plastics with antistatic properties and more advanced antistatic performance such as static electricity removal has increased rapidly. is doing.
Among those used as such antistatic (non-charging or static eliminating) plastics are ionomer resins.

  An ionomer is a partially neutralized copolymer of ethylene and unsaturated carboxylic acid with a metal, and alkali metals, especially those containing K, Rb, and Cs ions, exhibit excellent antistatic properties due to their ionic conduction. It is known that even if it is not treated with an antistatic agent, the resin itself exhibits electrical conductivity and maintains the antistatic effect semipermanently.

For this reason, many antistatic materials using ionomers, molded products and improved products thereof have already been proposed. For example, Patent Document 1 discloses an ethylene / unsaturated carboxylic acid copolymer using an alkali metal such as potassium as an ion source. An invention of an antistatic material for a polymer comprising an ionomer composition in which a polyhydric alcohol such as glycerin or trimethylolpropane is blended with an ionomer is disclosed.
Patent Document 2 discloses a closed cell type foamed film obtained by foaming an ethylene / unsaturated carboxylic acid copolymer potassium ionomer having a neutralization degree of 70 mol% or more, or a laminated film having the foamed layer. There has been disclosed an invention for an impact buffering film that has good non-charging properties immediately after molding, has little dust adhesion due to charging, and is suitable for packaging electronic parts and the like.
Further, Patent Document 3 discloses that ethylene / unsaturated carboxylic acid copolymer potassium ionomer having a neutralization degree of 60% or more and a small amount of a polyhydric alcohol compound or amino alcohol compound and ethylene / (meth) acrylic acid. An invention of an ionomer composition comprising a mixture having a specific blending ratio with an ester / maleic acid monoester copolymer and having no charge property, in particular, no humidity dependency is disclosed.

By the way, when the main purpose is antistatic or static electricity removal, the ionomer has a higher degree of alkali metal neutralization, that is, the more the amount of alkali ions (alkali ion density) in the ionomer, the more non-chargeable. Large and commonly used.
Japanese Patent Laid-Open No. 08-134295 Japanese Patent Laid-Open No. 08-113661 JP 2002-12722 A

  However, it is not always easy to neutralize the base resin ethylene / unsaturated carboxylic acid copolymer with a high degree of neutralization and obtain a homogeneous ionomer material. Furthermore, depending on the type of ionomer having a high neutralization degree, the flexibility and miscibility with other resins are not necessarily satisfactory, and therefore, the use may be limited.

  For this reason, there has been a strong demand for a new polymer material that has been flexible, excellent in miscibility with other resins, and excellent in antistatic properties.

  As a result of intensive studies to meet the above-mentioned demands, the present inventors have found that a saponified product obtained by alkali saponifying an ethylene / unsaturated carboxylic acid ester copolymer has extremely excellent antistatic properties (non- Based on this finding, the present invention was completed.

Accordingly, an object of the present invention is to provide an alkali saponified product which is flexible, excellent in miscibility with other resins, and has excellent non-charging properties (antistatic properties).
Another object of the present invention is to provide a polymer composition obtained by blending an olefin polymer with the alkali saponified polymer and further improving flexibility, processability, moldability and miscibility. It is in.

  According to the present invention, a polymer saponified product obtained by alkali saponifying an ethylene / unsaturated carboxylic acid ester copolymer, wherein the alkali metal ion concentration of the polymer saponified product is 0.1 to 5.8 mol / Non-chargeable polymer saponified product having excellent non-chargeability in the range of kg and non-chargeable polymer saponified product (A) comprising less than 100 to 2 parts by mass and olefin polymer (B) exceeding 0 to 98 parts by mass An excellent polymer composition is provided.

Specific surface resistivity (measured under conditions of applied voltage 500 V × application time 10 seconds after aging a 1 mm thick press sheet under 23 ° C. × 50% RH for 24 hours) is 1.0 × 10 ¹² Ω / □ or less The polymer saponified product or polymer composition according to claim 1 or 2 is a preferred embodiment of the present invention.
In the polymer saponified product or polymer composition of the present invention, the alkali saponified ethylene / unsaturated carboxylic acid ester copolymer is an ethylene / (meth) acrylic acid ester copolymer, and the alkali metal is It is preferably at least one selected from potassium and sodium.

  Furthermore, in the polymer saponified product or polymer composition of the present invention, the unsaturated carboxylic acid ester component content in the alkali saponified ethylene / unsaturated carboxylic acid ester copolymer is in the range of 5 to 50% by mass. It is preferable that it exists in.

The olefin polymer is preferably at least one selected from an ethylene polymer, a propylene polymer, and an ethylene / vinyl ester copolymer.
In the present invention, the polymer saponified product or polymer composition comprising 100 to 2 parts by mass of the polymer saponified product (A) according to claims 1 to 5 and 0 to 98 parts by mass of the olefin polymer (B). An unchargeable molded article comprising a polymer saponified product or a polymer composition having an alkali metal ion concentration of 0.1 to 5.8 mol / kg in the polymer saponified product or polymer composition is provided. Is done. In the present invention, the non-chargeable molded body is preferably a film or a sheet.
Further, in the present invention, a polymer saponified product or a polymer composition comprising 100 to 2 parts by mass of the polymer saponified product (A) and 0 to 98 parts by mass of the olefin polymer (B), wherein the polymer A non-chargeable film comprising a saponified polymer or polymer composition having an alkali metal ion concentration of 0.1 to 5.8 mol / kg in the saponified product or polymer composition, or a sheet or the film layer is heated. There is provided an uncharged laminate obtained by laminating a plastic resin layer.
Furthermore, in the present invention, a polymer composition comprising 100 to 30 parts by mass of the polymer saponified product (A) and 0 to 70 parts by mass of the olefin polymer (B), the alkali metal in the polymer composition There is provided a polymer type antistatic agent comprising a polymer composition having an ion concentration of 0.5 to 5.8 mol / kg.

The polymer saponified product or polymer composition according to the present invention is excellent in antistatic property (non-charging property), and the conditions described later, that is, a 1 mm-thick press sheet under constant temperature and humidity (23 ° C. × 50% RH), 24 When the surface specific resistance measured under the conditions of applied voltage 500 V × applied time 10 seconds after the time aging is usually 1.0 × 10 ¹⁴ Ω / □ or less, preferably 1 0.0 × 10 ¹² Ω / □ to 1.0 × 10 ³ Ω / □, and in the case of the polymer composition according to the present invention, usually 1.0 × 10 ¹⁴ Ω / □ or less, preferably 1.0 × ^{10 12 Ω / □ ~1.0 × 10} 3 Ω / □ is.
However, compared to ionomers with a high alkali neutralization degree, it exhibits superior non-chargeability at the same alkali metal content, and is more flexible and miscible with other resins.
Therefore, the polymer saponified product or polymer composition according to the present invention can be used as various uncharged materials. For example, the polymer saponified product or polymer composition according to the present invention has a surface resistivity of 1.0 × 10 as a laminate of a film, a sheet, various molded articles, or a layer made of other resin (for example, polyolefin resin). Applications required to be about ¹² Ω / □ or less, specifically, construction such as wallpaper, ceiling materials, flooring materials, civil engineering materials, packaging materials such as clothing, automobile parts, OA equipment, home appliance parts, or Not only can it be used widely in its storage and storage cases, stationery, daily necessities, etc., but it can also be used for more advanced static elimination (less than 10 ⁹ Ω / □), such as a polymer antistatic agent. Suitable for antistatic applications such as antistatic containers, conductive plastic corrugated cardboards, IC trays and other precision electronic parts transport / storage cases, and clean room building materials. wear.
In addition, the polymer composition obtained by blending the saponified polymer of the present invention with an olefin polymer such as polyethylene, polypropylene, EVA and the like is not only antistatic but also more flexible and excellent in moldability and workability. Since it is also excellent in miscibility with the resin, various non-chargeable molded products can be obtained.

Embodiments according to the present invention will be described in detail and specifically below. However, the present invention is not limited to these examples.
As described above, the present invention is a polymer saponified product obtained by alkali saponifying an ethylene / unsaturated carboxylic acid ester copolymer, and an alkali metal existing as a carboxylic acid alkali metal salt per 1 kg of the polymer saponified product. A polymer saponified product (A) having an ion amount (alkali metal ion concentration) in the range of 0.1 to 5.8 mol and excellent in non-chargeability, and less than 100 to 2 parts by mass of the polymer saponified product (A); Olefin polymer (B) is an invention of a polymer composition excellent in non-chargeability comprising more than 0 to 98 parts by mass, all of which are characterized by excellent antistatic properties.

  Examples of the ethylene / unsaturated carboxylic acid ester copolymer, which is a material resin used in the polymer saponified product or polymer composition of the present invention, include ethylene and unsaturated carboxylic acid alkyl esters such as alkyl acrylates and alkyl methacrylates. Ester, alkyl ethacrylic acid, crotonic acid alkyl ester, fumaric acid alkyl ester, maleic acid alkyl ester, maleic acid monoalkyl ester, maleic anhydride alkyl ester, itaconic acid alkyl ester and itaconic anhydride alkyl ester Can be illustrated.

Examples of the alkyl of the alkyl ester group include those having 1 to 12 carbon atoms, and more specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, 2-ethylhexyl, An alkyl group such as isooctyl can be exemplified.
In the present invention, methyl, ethyl, normal butyl and isobutyl esters of acrylic acid or methacrylic acid are particularly preferable as the unsaturated carboxylic acid ester.
Particularly preferred ethylene / unsaturated carboxylic acid ester copolymers in the present invention are ethylene (meth) acrylic acid ester copolymers, especially ethylene / methyl acrylate copolymers, ethylene / ethyl acrylate copolymers, ethylene・ Normal butyl acrylate copolymer, ethylene / isobutyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / normal butyl methacrylate copolymer, ethylene -An isobutyl methacrylate copolymer.

The content of the unsaturated carboxylic acid ester component in the ethylene / unsaturated carboxylic acid ester copolymer before saponification is preferably 5 to 50% by mass, particularly preferably 20 to 35% by mass. That is, it is preferable that the content of the unsaturated carboxylic acid ester component is in this range because of excellent balance of non-chargeability, flexibility, and miscibility with other resins. The ethylene / unsaturated carboxylic acid ester copolymer before saponification (190 ° C., melt flow rate at 2160 g load (JIS K7210-1999)) is preferably in the range of 1 to 1300 g / 10 min. The ethylene / unsaturated carboxylic acid ester copolymer before saponification may be used as a mixture of two or more.
Such an ethylene / unsaturated carboxylic acid ester copolymer is produced, for example, by high-pressure radical copolymerization known per se.

In the present invention, the ethylene / unsaturated carboxylic acid ester copolymer is saponified with alkali. Examples of the caustic metal ion species used for saponification include lithium (Li), sodium (Na), potassium (K), rubidium (Rb ), Cesium (Cs), and the like.
Among these, sodium and potassium are preferable from the viewpoint of non-charging properties, and potassium is particularly preferable.

In the polymer saponified product (A) of the present invention, the concentration of alkali metal ions such as potassium and sodium present in the saponified product as the carboxylic acid alkali salt is 0.1 to 5.8 mol / kg, more preferably 1 to It is in the range of 3 mol / kg. Those whose alkali metal ion concentration is below the above lower limit cannot obtain a surface resistivity of about 10 ¹⁴ Ω / □ or less required for antistatic, while those exceeding the above upper limit are too high in melt viscosity. This is not preferable because the moldability and workability deteriorate, such as difficulty in extrusion molding.
The saponified product of the present invention has a melt flow rate of 0.01 to 100 g / 10 min, particularly 0.1 to 50 g / 10 at 230 ° C. and 10 kg load (based on JIS K7210-1999) in terms of moldability and workability. Minutes are preferred.

In the present invention, among the saponified polymers, the saponification is carried out after the saponification with respect to the molar amount of all unsaturated carboxylic acid ester group units in the ethylene / unsaturated carboxylic acid ester copolymer to be alkali saponified. A saponified polymer having a molar ratio of the amount of alkali metal ions present as an acid alkali salt in the range of 0.1 to 0.6, that is, a saponification degree in the range of 10 to 60% is not charged. From the viewpoints of properties, flexibility, moldability / workability, and miscibility with other resins.
Incidentally, in the present invention, since the ester component in the copolymer is partially changed to an alkali salt component by an alkali saponification reaction, the saponified product contains an ethylene unit, an unsaturated carboxylic acid ester unit, and an unsaturated carboxylic acid alkali salt unit. It contains a copolymer and does not contain free carboxyl group units.

  The alkali saponification of the ethylene / unsaturated carboxylic acid ester copolymer may be carried out by a method known per se with caustic alkali or the like. For example, the ethylene / unsaturated carboxylic acid ester copolymer and a predetermined amount of potassium hydroxide or the like may be used. Caustic alkali is melt-mixed in a kneading apparatus such as an extruder, kneader or Banbury mixer at a temperature of, for example, 100 to 250 ° C., or an ethylene / unsaturated carboxylic acid ester copolymer is melted and homogenized by the kneading apparatus. Then, a method of reacting the ester portion of the ethylene / unsaturated carboxylic acid ester copolymer with the caustic alkali by adding a predetermined amount of caustic alkali such as potassium hydroxide can be exemplified.

In this invention, the polymer composition formed by mix | blending less than 2 mass parts of this saponified product (A) and more than 0-98 mass parts of olefinic polymers (B) as a polymer component is also provided.
In this embodiment, in addition to being excellent in non-charging properties, the resin itself is more flexible, excellent in moldability and processability, and is excellent in miscibility with other resins. In the present invention, from the viewpoint of moldability of the material, workability, and miscibility with other resins, 99-2 parts by mass of the saponified product (A) and 1-98 parts by mass of the olefin polymer (B), particularly the saponified product. 90 to 10 parts by mass of the compound (A) and 10 to 90 parts by mass of the olefin polymer (B) are preferable. Moreover, when using the polymer saponified product and the polymer composition of the present invention as a polymer antistatic agent, from 100 to 30 parts by mass of the polymer saponified product (A) and 0 to 70 parts by mass of the olefin polymer (B). It is preferable to use a polymer composition having an alkali metal ion concentration of 0.5 to 5.8 mol / kg in the polymer composition.

  Examples of the olefin polymer blended in combination with the polymer saponified product of the present invention include ethylene homopolymer (ethylene homopolymer) and ethylene and an α-olefin having 3 to 20 carbon atoms (propylene, 1-butene, 1 -Pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like), Specifically, metallocene-catalyzed ethylene (co) polymers (polymerized in the presence of a metallocene catalyst, such as high-pressure low-density polyethylene, linear low-density polyethylene, medium / high-density polyethylene, and metallocene-catalyzed low-density polyethylene) Ethylene polymers such as ethylene (co) polymer), polypropylene homopolymers and propylene , 1-butene, 2-butene 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, and other propylene polymers such as random or block copolymers In addition to butene polymers such as polybutene, polyisobutene, and polybutadiene, methylpentene polymers such as 4-methyl-1-pentene, polyisoprene polymers, and ethylene / vinyl acetate such as ethylene / vinyl acetate copolymers Examples thereof include an ester copolymer, an ethylene / (meth) acrylic acid ester copolymer, an ethylene / (meth) acrylic acid copolymer, or an ionomer thereof.

  Of these, ethylene polymers, propylene polymers and ethylene / vinyl ester copolymers are preferred, and metallocene-catalyzed low density polyethylene, propylene / ethylene / 1-butene random copolymers and ethylene / vinyl acetate copolymers are particularly preferred. Polymers are preferred.

  As a method for obtaining the polymer composition, a predetermined amount of each of the ethylene / unsaturated carboxylic acid ester copolymer and the olefin polymer is melted with a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or the like. Examples thereof include a method of saponification using a predetermined amount of caustic alkali or the like after mixing by heating, or a method of melting and mixing a saponified polymer and an olefin polymer prepared in advance.

Various additives can be further blended in the saponified polymer or polymer composition of the present invention as necessary.
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 thereof include reinforcing fibers such as fibers, pigments, dyes, flame retardants, flame retardant aids, foaming agents and foaming aids.
Moreover, if it is a small quantity, a normal antistatic agent can also be mix | blended.
The uncharged polymer saponified product or polymer composition of the present invention can be used after being molded into various forms such as a film, a sheet, a molded product, an aqueous dispersion, etc., for example, the uncharged polymer saponified product of the present invention. A monolayer film or sheet comprising a saponified product or a polymer composition can be obtained by forming the saponified product or the composition of the saponified product and an olefin polymer into a film by means such as extrusion molding. The thickness of the film or sheet is usually in the range of 5 μm to 5 mm.
When the uncharged polymer saponified product or polymer composition of the present invention is used on a film, it is laminated on various substrate layers and thermoplastic resin layers by coextrusion, dry lamination, etc. It can be used as a chargeable laminate. Base material and thermoplastic resin include woven fabric, non-woven fabric, paper, metal foil such as aluminum, stretched or unstretched polypropylene, high, medium and low density polyethylene, metallocene polyethylene (linear low density polyethylene) Examples include various synthetic resins such as ethylene (co) polymers, polyolefins such as poly-4-methyl-1-pentene, polyesters, and polyamides. The thickness of the base material layer and the thermoplastic resin layer is preferably 5 to 500 μm, and the thickness of the uncharged polymer saponified product or polymer composition layer is usually preferably in the range of 20 to 1000 μm.
Examples of the layer structure of the laminate include a two-layer structure of a thermoplastic resin layer and an uncharged polymer saponified product or polymer composition layer of the present invention, or a thermoplastic resin layer / uncharged polymer saponified product or heavy layer. Examples of the combined composition include a three-layer structure of an intermediate layer / thermoplastic resin layer.

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
In addition, the raw material used for the following Example and comparative example, and the evaluation method of the obtained polymer saponification thing or polymer composition are as follows.

1. Raw materials used i) Ethylene / methyl acrylate copolymer (EAC1): Methyl acrylate (MA) content; 24% by mass, MFR; 20 g / 10 min (190 ° C. × 2160 g load, conforming to JIS K7210-1999)
ii) Ethylene / methyl acrylate copolymer (EAC2): Methyl acrylate (MA) content: 30% by mass, MFR: 15 g / 10 min (190 ° C. × 2160 g load)
iii) Ethylene / ethyl acrylate copolymer (EAC3): Ethyl acrylate (EA) content: 25% by mass, MFR: 800 g / 10 min (190 ° C. × 2160 g load)
iv) Ethylene / ethyl acrylate copolymer (EAC4): ethyl acrylate (EA) content: 34% by mass, MFR: 25 g / 10 min (190 ° C. × 2160 g load)
v) Propylene / ethylene / 1-butene ternary random copolymer (r-PP): propylene component 92 mol%, ethylene component 5 mol%, 1-butene component 3 mol%, MFR 7.3 g / 10 min (230 ℃ × 2160g load)
vi) Metallocene-catalyzed polymerization low density polyethylene (m-PE): density 915 kg / m ³ , MFR; 4.0 (190 ° C. × 2160 g load) (trade name SP1540, manufactured by Prime Polymer Co., Ltd.)
vii) Ethylene / vinyl acetate copolymer (EVA): vinyl acetate (VA) content 10% by mass, MFR; 9 g / 10 minutes (190 ° C. × 2160 g load, according to JIS K7210-1999)
2. Evaluation item and evaluation method i) Antistatic performance: measurement of surface resistivity, 1 mm thick press sheet after aging for 24 hours under constant temperature and humidity (23 ° C. × 50% RH), and then electric resistance measuring instrument Hiresta manufactured by Mitsubishi Chemical Was used to measure the surface resistivity of the sample under the conditions of an applied voltage of 500 V and an applied time of 10 seconds.
ii) Melt flow rate (MFR) In Table 1, * marks are measured at 230 ° C. × 10 kg load, and others are measured at 190 ° C. × 2160 g load. In Table 2, ** marks are measured at 230 ° C. × 2160 g load), and the others were measured at 190 ° C. × 2160 g load. (All comply with JIS K7210-1999)
iii) In the present invention, the amount of alkali metal ions (metal ion concentration) in the saponified product or polymer composition was measured by the following method.
The sample was demetallized with hydrochloric acid using a mixed solvent of xylene / butanol, titrated with a thymol blue indicator, and the amount (molar amount) of the produced carboxylic acid group (COOH) was measured. The amount of the generated carboxylic acid group (COOH) (molar amount) from equal to the molar amount of COOM ^+, the molar amount (metal ion concentration of COOM ⁺ per sample 1kg than the molar amount of the product carboxylic acid group (COOH) ) Was calculated.

"Example 1"
Feed 10 kg of ethylene / methyl acrylate copolymer (EAC1) and 470 g of KOH as raw material resin (base resin) for saponification preparation, and melt, react and extrude EAC1 and KOH in the kneading apparatus. As a result, a polymer saponified product (Ex. 1) was obtained.
The K ion concentration (K ion amount) present in the form of potassium acrylate in the saponified product is 0.84 mol / kg, and the total acrylic acid of the ethylene / methyl acrylate copolymer (EAC1) before saponification is obtained. The ratio of the molar amount of alkali metal ions present in the saponified product to the molar amount of the ester group unit (percentage: hereinafter referred to as saponification rate) was 30%.
The MFR of this saponified product was 82 g / 10 min (230 ° C. × 10 kg load).
And the surface resistivity of the sample press sheet obtained from this polymer saponified product was measured.
The results are shown in Table 1.

"Examples 2 to 8"
Polymers similar to those of Example 1 except that the base resins shown in Examples 2 to 8 of Table 1 were used, respectively, and the KOH addition amount was changed according to the base resin and the target saponification rate. A quarrel was obtained, and the surface resistivity of each sample press sheet on which it was molded was measured. The results are shown in Table 1.

"Examples 9 to 14"
Except for replacing KOH with NaOH, a polymer saponified product was obtained in substantially the same manner as in Examples 2 to 8, and the surface resistivity of each press sheet on which it was molded was measured.
The results are shown in Table 1.

“Comparative Example 1”
The base resin EAC1 was formed as it was without saponification, and the surface resistivity of the press sheet (ratio-1) was measured.
The results are shown in Table 1.

"Comparative Examples 2-4"
Without saponifying the base resins EAC2 to 4, the respective press sheets were formed as they were (ratio-2 to ratio-4), and their surface resistivity was measured.
The results are shown in Table 1.

"Example 15"
EAC2 was used as the base resin, and the saponification rate obtained by saponifying this with KOH was 60%, and 20 parts by mass of a polymer saponified product having a K ion concentration of 2.09 mol / kg in the saponified product and propylene. 80 parts by weight of ethylene / butene ternary random copolymer (r-PP) was melt kneaded using a single screw extruder to obtain a polymer composition (Ex. 15; MFR = 5 g / 10 min ( 230 ° C. × 2160 g load)).
The concentration of K ions present in the form of acrylate in the polymer composition (Ex. 15) was 0.42 mol / kg.
The surface resistivity of a press sheet obtained by press-molding this composition was measured.
The results are shown in Table 2.

"Example 16"
10 parts by mass of a polymer saponified product having a saponification rate of 60% and a K ion concentration of 2.09 mol / kg obtained by saponifying EAC2 with KOH and 90 parts by weight of a metallocene-catalyzed polymerized low-density polyethylene (m-PE) The polymer composition was obtained by melt-kneading using an extruder (Ex. 16; MFR = 3 g / 10 min (190 ° C. × 2160 g load)).
The concentration of K ions present in the form of acrylate in the polymer composition (Ex. 16) was 0.21 mol / kg.
The surface resistivity of a press sheet obtained by press-molding this composition was measured.
The results are shown in Table 2.

"Example 17"
The polymer composition (Ex. 17) was the same as Example 16 except that the blending ratio in Example 16 was 20 parts by mass of polymer saponified product and 80 parts by mass of metallocene-catalyzed polymerized low density polyethylene (m-PE). (Potassium ion concentration 0.42 mol / kg, MFR = 2 g / 10 min (190 ° C. × 2160 g load)), press sheet molding was conducted in the same manner as in Example 16, and the surface resistivity was measured. .
The results are shown in Table 2.

"Example 18"
In Example 17, a polymer composition (in the same manner as in Example 16) except that 80 parts by mass of an ethylene / vinyl acetate copolymer (EVA) was used instead of the metallocene-catalyzed polymerization low-density polyethylene (m-PE). Actual -18: A potassium ion concentration of 0.42 mol / kg, MFR = 1.5 g / 10 min (190 ° C. × 2160 g load)) was prepared, press sheet-molded in the same manner as in Example 16, and its surface resistivity The rate was measured.
The results are shown in Table 2.

“Comparative Example 5”
The propylene / ethylene / butene ternary random copolymer (r-PP) used in Example 15 was directly press-molded, and the surface resistivity of the press sheet (ratio-5) was measured.
The results are shown in Table 2.

“Comparative Example 6”
The metallocene-catalyzed polymerized low-density polyethylene (m-PE) used in Example 16 was press-molded as it was, and the surface resistivity of the press sheet (ratio-6) was measured.
The results are shown in Table 2.

“Comparative Example 7”
The ethylene / vinyl acetate copolymer (EVA) used in Example 18 was press-molded as it was, and the surface resistivity of the press sheet (ratio-7) was measured.
The results are shown in Table 2.

Claims (10)

  A polymer saponified product obtained by alkali saponifying an ethylene / unsaturated carboxylic acid ester copolymer, wherein the alkali metal ion concentration in the polymer saponified product is in the range of 0.1 to 5.8 mol / kg. Polymer saponified product with excellent non-charging properties.   The polymer saponified product (A) according to claim 1, comprising less than 100 to 2 parts by mass and an olefin polymer (B) from more than 0 to 98 parts by mass, wherein the alkali metal ion concentration in the polymer composition is 0.1. Uncharged polymer composition which is ˜5.8 mol / kg. Specific surface resistivity (measured under conditions of applied voltage 500 V × application time 10 seconds after aging a 1 mm thick press sheet under 23 ° C. × 50% RH for 24 hours) is 1.0 × 10 ¹² Ω / □ or less The polymer saponified product or polymer composition according to claim 1 or 2.   The ethylene / unsaturated carboxylic acid ester copolymer to be alkalinized is an ethylene / (meth) acrylic acid ester copolymer, and the alkali metal is at least one selected from potassium and sodium. The polymer saponified product or polymer composition according to any one of the above.   The polymer soap according to any one of claims 1 to 4, wherein the content of the unsaturated carboxylic acid ester component in the alkali saponified ethylene / unsaturated carboxylic acid ester copolymer is in the range of 5 to 50% by mass. Or polymer composition.   The polymer composition according to any one of claims 2 to 5, wherein the olefin polymer is at least one selected from an ethylene polymer, a propylene polymer, and an ethylene / vinyl ester copolymer.   A polymer saponified product or a polymer composition comprising 100 to 2 parts by mass of the polymer saponified product (A) according to claim 1 and 0 to 98 parts by mass of an olefin polymer (B), A non-chargeable molded article comprising a polymer saponified product or a polymer composition having an alkali metal ion concentration of 0.1 to 5.8 mol / kg in the combined saponified product or polymer composition.   The molded article according to claim 7, wherein the non-chargeable molded article is a film or a sheet.   A non-chargeable laminate obtained by laminating the film layer according to claim 8 on a thermoplastic resin layer.   A polymer saponified product or a polymer composition comprising 100 to 30 parts by mass of the polymer saponified product (A) according to claim 1 and 0 to 70 parts by mass of an olefin polymer (B), A polymer type antistatic agent comprising a polymer composition having an alkali metal ion concentration of 0.5 to 5.8 mol / kg in the combined saponified product or polymer composition.