WO2017213140A1 - Polyether polymer, composition containing same, and molded article - Google Patents

Abstract

Provided are: a polyether polymer which has a surface resistance value reduced to a predetermined value or less, and has superior shape stability; a composition containing the polyether polymer; and a molded article. The polyether polymer is characterized by satisfying at least one of the conditions of: the water absorption percentage is 1.5 wt% or less and the surface resistance value is 1.0 × 10¹² (Ω/sq.) or less at 23°C and 50% RH; and the surface resistance value is 1.0 × 10⁸ to 1.0 × 10¹² (Ω/sq.) either at 10°C and 15% RH or at 35°C and 85% RH.

Description

Polyether polymer, composition containing the same, and molded article

The present invention (hereinafter sometimes referred to as the present invention) relates to a polyether polymer, a composition containing the polyether polymer, and a molded body. In particular, the present invention relates to a polyether polymer having a surface resistance value within a certain range under a predetermined condition and having a suppressed appearance change, that is, excellent in shape stability, a composition containing the polyether polymer, and a molded article. About. For example, the present invention shows a single polyether polymer (hereinafter, referred to as a rubber roll material for OA equipment such as a copying machine or the like, an excellent surface resistance value suitable as an antistatic material, and an excellent balance property with water absorption. (Sometimes referred to as “polyether copolymer”). The “single polyether polymer” means one polyether copolymer, and is distinguished from a blend of a plurality of polyether copolymers such as Patent Document 1 described later. The present invention also relates to a polyether polymer having a stable surface resistance value under low temperature / low humidity conditions and high temperature / high humidity conditions, and an antistatic material using the polyether polymer.

The polyether copolymer having ionic conductivity is widely used as a rubber roll material for office automation equipment, and is also used as an antistatic material that is mixed with a resin and other rubber to maintain its function semipermanently. In general, polymer materials such as resins and rubbers are easily charged, and thus have a problem of attracting dust and dust and deteriorating the beauty. It is also known that static electricity causes malfunction of electronic devices, and in order to prevent malfunction, the surface resistance value of rubber or plastic is set to 1.0 × 10 ¹⁰ to 1.0 × 10 ¹² (Ω / Sq.) Or less (Non-Patent Document 1).

Conventionally, ethylene oxide homopolymers or copolymers of ethylene oxide and propylene oxide have been used as polyether materials for antistatic materials (Patent Document 1). Specifically, Patent Document 1 proposes a method of blending a propylene oxide homopolymer having a low water absorption rate with respect to an ethylene oxide copolymer as a method for achieving a balance between surface resistance and water absorption.

JP-A-8-183901

Polyether materials such as polyether copolymers are excellent in ionic conductivity, but at the same time have the problem of high water absorption, lack of dimensional stability, and change in color tone such as becoming cloudy with water absorption. There is a problem to cause. Moreover, the same problem may arise also in the composition which mixed these as an antistatic material, and the molded object obtained using this composition.

As the polyether material, the material of Patent Document 1 is cited. However, in this method, two types of polyether polymers are required, and in addition, it is an essential condition to mix polymers having different characteristics. Therefore, uneven surface resistance and water absorption in the same material due to poor dispersion. May occur.

In addition, there is a problem that the surface resistance value greatly fluctuates under low temperature / low humidity conditions, and high temperature / high humidity conditions. Polyimides having stable surface resistance values under low temperature / low humidity conditions and high temperature / high humidity conditions. There is a need for ether polymers.

The present invention has been made by paying attention to the above-mentioned circumstances, and the purpose thereof is the conditions of 23 ° C. and 50% RH; and the conditions of 10 ° C., 15% RH and 35 ° C., 85% RH. At least one of the following: satisfying a predetermined surface resistance value (hereinafter, this characteristic is sometimes referred to as “excellent in semiconductivity”), and the appearance change is suppressed, that is, excellent in shape stability ( Hereinafter, this property may be referred to as “excellent in dimensional stability”) a polyether polymer, a composition containing the same, and a molded product produced using the polyether polymer or the composition Is to provide. More specifically, the object of the present invention is to provide, for example, a single polyether polymer excellent in semiconductivity and dimensional stability that is suitable as a rubber roll for OA equipment, an antistatic material, and an antistatic material alone, and a crosslinked product thereof. A polyether polymer having a stable surface resistance value in a low temperature / low humidity condition and a high temperature / high humidity condition in which an antistatic material is used, and the polyether polymer An object is to provide an antistatic material.

In order to solve the above problems, the present inventors have made various studies. As a result, the water absorption at 23 ° C. and 50% RH is 1.5% by weight or less, and the surface resistance value is 1.0 × 10 ^12. (Ω / sq.) Or less; and the surface resistance value at 10 ° C. and 15% RH and the surface resistance value at 35 ° C. and 85% RH are both 1.0 × 10 ⁸ to 1.0 ×. 10 ¹² (Ω / sq.); A polyether polymer characterized by satisfying at least one of the above, and further a cross-linked product thereof has found that the above-mentioned problems can be solved. .

That is, the present invention can be described as follows.
Item 1 The water absorption at 23 ° C. and 50% RH is 1.5% by weight or less and the surface resistance value is 1.0 × 10 ¹² (Ω / sq.) Or less; and 10 ° C., 15% The surface resistance value at RH and the surface resistance value at 35 ° C. and 85% RH are all 1.0 × 10 ⁸ to 1.0 × 10 ¹² (Ω / sq.). A polyether polymer characterized by the above.
Item 2 (A) 65 to 99 mole percent of structural units derived from ethylene oxide, (B) 35 to 1 mole percent of structural units derived from an oxirane monomer composed of 4 or more carbon atoms, (C) having a crosslinkable functional group Item 2. The polyether polymer according to Item 1, which contains 0 to 10 mole percent of structural units derived from an oxirane monomer.
Item 3 (A) 65 to 90 mole percent of structural units derived from ethylene oxide, (B) 30 to 5 mole percent of structural units derived from an oxirane monomer composed of 4 to 10 carbon atoms, (C) a crosslinkable functional group Item 3. The polyether polymer according to Item 1 or 2, which contains 1 to 8 mole percent of structural units derived from an oxirane monomer.
Item 4 The polyether polymer according to Item 2, wherein the (B) oxirane monomer having 4 or more carbon atoms is an oxirane monomer having an alkyl group or an alkoxy group.
Item 5 The polyether polymer according to any one of Items 2 to 4, wherein the oxirane monomer having a crosslinkable functional group (C) is glycidyl methacrylate or allyl glycidyl ether.
Item 6. A composition comprising the polyether polymer according to any one of Items 1 to 5, or a crosslinked product thereof; and at least one selected from a conductivity-imparting agent, rubber, resin and solvent.
Item 7 A molded article produced using the polyether polymer or composition according to any one of Items 1 to 6.

Further, the present invention can be described as in the following items 1a to 5a.
Item 1a Polyether polymer characterized by having a water absorption of 1.5 wt% or less at 23 ° C. and 50% RH and having a surface resistance of 1.0 × 10 ¹² (Ω / sq.) Or less. .
Item 2a (A) 65 to 99 mol% (mol percent) of structural units derived from ethylene oxide, (B) 35 to 1 mol% of structural units derived from an oxirane monomer composed of 4 or more carbon atoms, (C) crosslinkability The polyether polymer according to Item 1a, comprising 0 to 10 mol% of a structural unit derived from an oxirane monomer having a functional group.
Item 3a The polyether polymer according to Item 2a, wherein the oxirane monomer having 4 or more carbon atoms is an oxirane monomer having an alkyl group or an alkoxy group.
Item 4a The polyether polymer according to Item 2a or 3a, wherein the oxirane monomer having a crosslinkable functional group is glycidyl methacrylate or allyl glycidyl ether.
Item 5a A crosslinked product obtained by crosslinking the polyether polymer according to any one of Items 1a to 4a.

Further, the present invention can be described as the following items 1b to 5b.
Item 1b The surface resistance value at 10 ° C. and 15% RH and the surface resistance value at 35 ° C. and 85% RH are both 1.0 × 10 ⁸ to 1.0 × 10 ¹² (Ω / sq.). A polyether polymer characterized by
Item 2b An antistatic material containing the polyether polymer according to Item 1b.
Item 3b (A) 65 to 90 mol% of structural units derived from ethylene oxide, (B) 30 to 5 mol% of structural units derived from alkylene oxide (oxirane monomer) composed of 4 to 10 carbon atoms, (C) cross-linking Item 2. The antistatic material according to Item 2b, which is a polyether polymer containing 1 to 8 mol% of a structural unit derived from an oxirane monomer having a functional functional group.
Item 4b (C) The antistatic material according to Item 3b, wherein the oxirane monomer having a crosslinkable functional group is glycidyl methacrylate or allyl glycidyl ether.
Item 5b An antistatic material-containing composition comprising the antistatic material according to Item 2b to 4b and a resin.
Item 6b An antistatic material-containing composition comprising the antistatic material according to Item 2b to 4b and rubber.
Item 7b An antistatic material-containing composition comprising the antistatic material according to items 2b to 4b, a rubber and a resin.
Item 8b An antistatic material-containing composition comprising the antistatic material according to Item 2b to 4b and a solvent.
Item 9b A molded article obtained by molding the antistatic material-containing composition according to any one of Items 5b to 8b.

According to the present invention, a polyether polymer having a surface resistance value within a certain range under a predetermined condition and having an appearance change suppressed, that is, excellent in shape stability, a composition containing the polyether polymer, and molding Can provide the body. The polyether polymer and its cross-linked product according to the present invention are suitable for uses such as antistatic materials, specifically antistatic materials that require semiconductivity, rubber rolls for OA equipment, and the like.

The polyether polymer of the present invention has a water absorption at 23 ° C. and 50% RH of 1.5% by weight or less and a surface resistance value of 1.0 × 10 ¹² (Ω / sq.) Or less; The surface resistance value at 10 ° C. and 15% RH and the surface resistance value at 35 ° C. and 85% RH are both 1.0 × 10 ⁸ to 1.0 × 10 ¹² (Ω / sq.). Satisfying at least one of the following:

The water absorption at 23 ° C. and 50% RH of the polyether polymer of the present invention is 1.5% by weight or less in that it does not cause a problem of appearance change such as cloudiness or warpage deformation under high temperature and high humidity. It is preferably 1.4% by weight or less, and particularly preferably 1.2% by weight or less. The lower limit of the water absorption rate at 23 ° C. and 50% RH is not particularly limited, but may be 0.01% by weight or more, and may be 0.1% by weight or more. From the viewpoint of securing a certain water absorption rate in order to suppress an increase in the surface resistance value, the water absorption rate is 0.3% by weight or more, further 0.5% by weight or more, and further 0.7% by weight. Can be super.

The water absorption at 23 ° C. and 50% RH can be calculated from the weight of the polyether polymer in a dry state and the weight of the polyether polymer conditioned at a temperature of 23 ° C. and a humidity of 50% RH as follows. .

Water absorption at 23 ° C. and 50% RH (% by weight) = ((weight of polyether polymer conditioned at temperature 23 ° C., humidity 50% RH−weight of polyether polymer in dry state) / in dry state Weight of polyether polymer) x 100

In the present invention, a polyether polymer is laid on a mold and pressed for 2 minutes with a vacuum heating press set at 160 ° C., thereby forming a 1 mm thick molded polymer sheet as a test piece. The weight of the test piece in the dry state after conditioning the test piece in a dry bath adjusted to −50 ° C. for 48 hours is defined as the weight of the polyether polymer in the dry state. The weight of the test piece after conditioning for 48 hours in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and a humidity of 50% RH is adjusted to a temperature of 23 ° C. and a humidity of 50% RH. The weight of the obtained polyether polymer.

The surface resistance value of the polyether polymer of the present invention at 23 ° C. and 50% RH is 1.0 × 10 ¹² (Ω / sq.) Or less, and 1.0 × 10 ¹¹ (Ω / sq.) Or less. And is more preferably 7.0 × 10 ¹⁰ (Ω / sq.) Or less. The lower limit of the surface resistance value at 23 ° C. and 50% RH is not particularly limited, but may be 1.0 × 10 ⁷ (Ω / sq.) Or more, and 1.0 × 10 ⁸ (Ω / sq.) Or more. It may be.

The surface resistance value at 23 ° C. and 50% RH is obtained as follows. That is, a polyether polymer is spread on a mold and pressed for 2 minutes with a vacuum heating press set at a temperature of 160 ° C., so that a 1 mm thick molded polymer sheet is used as a test piece, and the test piece is dew point- Test specimens conditioned for 48 hours in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and a humidity of 50% RH for the test pieces in a dry state after conditioning for 48 hours in a dry bath adjusted to 50 ° C. In a humidity chamber, a voltage of 100 volts is applied using an insulation resistance meter such as Hiresta manufactured by Mitsubishi Chemical Corporation, the resistance value after 1 minute is read, and the surface resistance value is calculated.

The polyether polymer of the present invention satisfies the above characteristics, or the surface resistance value at 10 ° C. and 15% RH and the surface resistance value at 35 ° C. and 85% RH are both 1.0 × It is preferably 10 ⁸ (Ω / sq.) Or more, more preferably 2.0 × 10 ⁸ (Ω / sq.) Or more, and the upper limit is 1.0 × 10 ¹² (Ω / sq.) Or less. It is preferable that it is 5.0 × 10 ¹¹ (Ω / sq.) Or less. Since the surface resistance value at 10 ° C. and 15% RH and the surface resistance value at 35 ° C. and 85% RH are both within this range, the surface resistance value is stable under general temperature and humidity conditions. I can expect that. It is more preferable that the water absorption rate and surface resistance value at 23 ° C. and 50% RH are satisfied, and the surface resistance value at 10 ° C. and 15% RH and the surface resistance value at 35 ° C. and 85% RH are satisfied.

The surface resistance value at 10 ° C. and 15% RH and the surface resistance value at 35 ° C. and 85% RH are obtained as follows. That is, a polyether polymer is spread on a mold and pressed for 2 minutes with a vacuum heating press set at a temperature of 160 ° C., so that a 1 mm thick molded polymer sheet is used as a test piece, and the test piece is dew point- The dried test piece after conditioning for 48 hours in a dry bath adjusted to 50 ° C. was subjected to a temperature of 10 ° C. and humidity of 15% RH (low temperature and low humidity conditions), or a temperature of 35 ° C. and humidity of 85% RH (high temperature and high humidity conditions). The test piece conditioned for 48 hours in the constant temperature and humidity chamber adjusted to) was applied with a voltage of 100 volts in the same constant temperature and humidity chamber using an insulation resistance meter such as Hiresta manufactured by Mitsubishi Chemical Corporation. The resistance value after 1 minute is read to calculate the surface resistance value.

As shown in Comparative Example 3 of the examples described later, if the water absorption rate is excessively reduced to increase the shape stability, the surface resistance value is increased. On the other hand, as described above, the polyether polymer of the present invention has an excellent balance between the surface resistance value and the water absorption that affects the shape stability, and achieves both a low surface resistance value and excellent shape stability. Can be realized.

As the polyether polymer satisfying the above properties, (A) 65 to 99 mole percent of structural units derived from ethylene oxide, (B) 35 to 1 mole percent of structural units derived from an oxirane monomer having 4 or more carbon atoms, ( C) Those containing 0 to 10 mole percent of structural units derived from an oxirane monomer having a crosslinkable functional group are preferred.

As the polyether polymer satisfying the above characteristics, (A) 65 to 90 mole percent of structural units derived from ethylene oxide, (B) 30 to 5 mole percent of structural units derived from an oxirane monomer composed of 4 to 10 carbon atoms, (C) Those containing 1 to 8 mole percent of structural units derived from an oxirane monomer having a crosslinkable functional group are more preferred. Hereinafter, each structural unit will be described.

[(A) Structural unit derived from ethylene oxide]
The structural unit derived from (A) ethylene oxide in the polyether polymer is preferably 65 to 99 mol%, more preferably 65 to 95 mol%, and particularly preferably 65 to 90 mol%. In particular, in order to obtain a polyether polymer having excellent surface stability and having a stable surface resistance value under the low temperature / low humidity conditions and the high temperature / high humidity conditions, (A) a structural unit derived from ethylene oxide The lower limit is preferably 65 mol% or more, more preferably 67 mol% or more, the upper limit is preferably 99 mol% or less, more preferably 95 mol% or less, 90 More preferably, it is at most mol%.

[(B) a structural unit derived from an oxirane monomer composed of 4 or more carbon atoms]
In the polyether polymer, (B) the structural unit derived from an oxirane monomer (alkylene oxide) composed of 4 or more carbon atoms, the lower limit is preferably 1 mol% or more, and 5 mol% or more. More preferably, it is 8 mol% or more, still more preferably 10 mol% or more. The upper limit is preferably 35 mol% or less, and more preferably 30 mol% or less. For example, the range of the structural unit is preferably 35 to 1 mol%, more preferably 35 to 5 mol%, still more preferably 30 to 5 mol%, and more preferably 30 to 10 mol%. Further preferred. Within this range, a sufficiently low surface resistance value can be obtained for the polyether polymer. In particular, in order to easily obtain a polyether polymer having a surface resistance value within a certain range under any of low temperature / low humidity conditions and high temperature / high humidity conditions, the lower limit of the structural unit is: It is preferably 15 mol% or more, and more preferably 20 mol% or more.

Examples of the oxirane monomer having 4 or more carbon atoms include an oxirane monomer having an alkyl group, an oxirane monomer having an alkyloxy group, an oxirane monomer having a cycloalkyl group, and an oxirane having an aromatic group. Examples include monomers, oxirane monomers having an ester group, oxirane monomers having an hydroxy group (epoxy alcohol), oxirane monomers having an alkyl group, and oxirane monomers having an alkyloxy group. Preferably there is.

Examples of oxirane monomers having 4 or more carbon atoms include oxirane monomers having an alkyl group such as epoxybutane, epoxy hexane, and epoxy octane, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, and hexyl glycidyl ether. Oxirane monomers having alkyloxy groups (also referred to as alkoxy groups) such as 2-ethylhexyl glycidyl ether, methoxyethoxyethyl glycidyl ether, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy Oxirane monomers having a cycloalkyl group such as cyclododecane, oxirane monomers having an aromatic group such as styrene oxide and phenylglycidyl ether, and esters such as propyl 2,3-epoxybutanoate And oxirane monomers having a hydroxy group such as 4,5-epoxy-1-pentanol, 3,4-epoxy-1-butanol, and the like. In addition to these, two or more may be used in combination.

Of these, an oxirane monomer having an alkyl group or an alkoxy group is preferable. Among these, 2-ethylhexyl glycidyl ether or alkylene oxides having 4 to 10 carbon atoms, particularly epoxy butane and epoxy hexane, are preferable because they are easily copolymerized with ethylene oxide. In particular, in order to easily obtain a polyether polymer having a surface resistance value within a certain range under both low temperature and low humidity conditions and high temperature and high humidity conditions, it is composed of 4 to 10 carbon atoms. Alkylene oxide is preferable, alkylene oxide having 4 to 8 carbon atoms is more preferable, epoxy butane such as 1,2-epoxybutane, and epoxyhexane such as 1,2-epoxyhexane. Is more preferable.

[(C) a structural unit derived from an oxirane monomer having a crosslinkable functional group]
As the structural unit derived from the oxirane monomer having a crosslinkable functional group (C) in the polyether polymer, the lower limit is preferably 0 mol% or more, more preferably 1 mol% or more, It is more preferably 2 mol% or more, particularly preferably 3 mol% or more, and the upper limit is preferably 10 mol% or less, more preferably 8 mol% or less, and 6 mol% or less. More preferably, it is more preferably 5 mol% or less. For example, the range of the structural unit is preferably 0 to 10 mol%, more preferably 1 to 8 mol%, more preferably 1 to 6 mol%, particularly preferably 1 to 5 mol%. preferable.
In particular, in order to obtain a polyether polymer having excellent surface stability and having a stable surface resistance value under the low temperature / low humidity conditions and the high temperature / high humidity conditions, (C) a crosslinkable functional group is used. The structural unit derived from the oxirane monomer is preferably in the range of 1 to 8 mole percent.

The oxirane monomer having a crosslinkable functional group may be any oxirane monomer capable of crosslinking the polyether copolymer of the present invention, and examples thereof include halogen-containing oxirane monomers. Specific examples include epihalohydrins such as epichlorohydrin, epibromohydrin, epiiodohydrin, epifluorohydrin, p-chlorostyrene oxide, dibromophenylglycidyl ether, m-chloromethylstyrene oxide, p-chloromethylstyrene oxide, chloro Halogen-substituted oxiranes other than epihalohydrins such as glycidyl acetate, chloromethyl glycidate, tetrafluorooxirane, 1,1,2,3,3,3-hexafluoro-1,2-epoxypropane, allyl glycidyl ether, acrylic acid Ethylenically unsaturated group-containing oxiranes such as glycidyl, glycidyl methacrylate, glycidyl crotonate, 3,4-epoxy-1-butene, glycidyl metaglycidate, glycid metaglycidyl ester, etc. Door can be. These oxirane monomers having a crosslinkable functional group may be used alone or in combination of two or more. Preferable in terms of monomer price and availability are allyl glycidyl ether and glycidyl methacrylate. Particularly preferred is glycidyl methacrylate.

A preferred combination of the structural unit derived from the oxirane monomer (B) having 4 or more carbon atoms and the structural unit derived from the oxirane monomer (C) having a crosslinkable functional group is 2-ethylhexyl glycidyl ether. Or a combination of an alkylene oxide composed of 4 to 10 carbon atoms, particularly epoxybutane, epoxyhexane, and an ethylenically unsaturated group-containing oxirane, particularly glycidyl methacrylate, in accordance with the present invention. It is preferable for achieving the value and the water absorption rate.

In particular, the polyether polymer having a water absorption at 23 ° C. and 50% RH and a surface resistance value described above includes (A) ethylene oxide-derived structural units of 65 to 99 mol%, and (B) a carbon number of 4 An example of a polyether polymer containing 35 to 1 mol% of structural units derived from the oxirane monomer constituted as described above and (C) 0 to 10 mol% of structural units derived from an oxirane monomer having a crosslinkable functional group can do.

Further, the surface resistance value at 10 ° C. and 15% RH and the surface resistance value at 35 ° C. and 85% RH described above are both 1.0 × 10 ⁸ to 1.0 × 10 ¹² (Ω / sq. The polyether polymer of (A) includes (A) 65 to 99 mol% of structural units derived from ethylene oxide, (B) 35 to 1 mol% of structural units derived from an oxirane monomer having 4 or more carbon atoms, ( C) A polyether polymer containing 0 to 10 mol% of a structural unit derived from an oxirane monomer having a crosslinkable functional group can be exemplified.

The polymerization composition of the polyether polymer can be determined from the calculation result obtained by dissolving the polyether polymer in deuterated chloroform, obtaining the integral value of each unit by ¹ H-NMR.

The lower limit of the weight average molecular weight of the polyether polymer is preferably 10,000 or more, more preferably 100,000 or more, still more preferably 300,000 or more, and the upper limit is 5 million or less. Preferably, it is 3 million or less, more preferably 2 million or less. For example, the weight average molecular weight of the polyether polymer is preferably 10,000 to 5,000,000, more preferably 100,000 to 3,000,000, and even more preferably 300,000 to 2,000,000. The lower limit of the weight average molecular weight is more preferably 500,000 or more, particularly preferably 900,000 or more, and particularly preferably 1.1 million or more. The weight average molecular weight of the polyether polymer is calculated by gel permeation chromatography (GPC) in terms of standard polystyrene.

The glass transition temperature of the polyether polymer is preferably −35 ° C. or lower, more preferably −40 ° C. or lower, still more preferably −44 ° C. or lower, and preferably −49 ° C. or lower. More preferably, it is more preferably −54 ° C. or less, still more preferably −59 ° C. or less, and particularly preferably −61 ° C. or less. The lower limit of the glass transition temperature of the polyether polymer can be, for example, −80 ° C. or higher. The heat of crystal fusion of the polyether polymer is preferably 25 J / g or less, more preferably 22 J / g or less, still more preferably 19 J / g or less, and 16 J / g or less. Particularly preferred is 8 J / g or less in terms of lowering the environmental variation index. The lower limit of the heat of crystal fusion of the polyether polymer can be, for example, 0 J / g or more. The glass transition temperature of the polyether polymer is a value obtained by differential scanning calorimetry (DSC), and the heat of crystal melting is a value obtained from the melting peak.

[Method for producing polyether polymer]
(A) 65 to 99 mol% of structural units derived from ethylene oxide, (B) 35 to 1 mol% of structural units derived from an oxirane monomer composed of 4 or more carbon atoms, (C) an oxirane unit having a crosslinkable functional group The production of a polyether polymer containing 0 to 10 mol% of a structural unit derived from a monomer uses a solution capable of ring-opening polymerization of an oxirane compound as a catalyst, and a solution polymerization method at a temperature in the range of −20 to 100 ° C. It can be carried out by a slurry polymerization method or the like. As such a catalyst, for example, a catalyst system in which organic aluminum is mainly used and this is reacted with an oxoacid compound of water or phosphorus, acetylacetone, etc., a catalyst system in which organic zinc is mainly used and water is reacted with this, organic tin- Examples include phosphate ester condensate catalyst systems. For example, the polyether copolymer of the present invention can be produced using the organotin-phosphate ester condensate catalyst system described in US Pat. No. 3,773,694 by the present applicant. In addition, when making it copolymerize by such a manufacturing method, it is preferable to copolymerize these components substantially randomly.

In the present invention, in addition to using the polyether polymer in a polymerized state, a crosslinked product obtained by crosslinking the polyether polymer may be used.

The cross-linked product obtained by cross-linking the polyether polymer of the present invention may be obtained by cross-linking by reacting the polyether polymer itself, or by cross-linking by heating together with a cross-linking agent suitable for the cross-linkable functional group. Alternatively, it may be obtained by crosslinking using a thermal polymerization initiator or a photoreaction initiator (also referred to as a photopolymerization initiator) suitable for the crosslinkable functional group. The crosslinking can be performed by irradiating active energy rays such as ultraviolet rays in addition to heating. A known crosslinking accelerator, crosslinking accelerator, and crosslinking retarder can be used in the present invention together with the crosslinking agent, and a known crosslinking assistant can be used in the present invention together with the thermal polymerization initiator and the photoreaction initiator. it can.

The following crosslinking agents can be used. First, as an oxirane monomer having a crosslinkable functional group (C) in a polyether polymer, a halogen-containing oxirane monomer, in particular, an epihalohydrin or halogen-substituted oxirane other than this epihalohydrin is used. Usable crosslinking agents include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, p-phenylenediamine, cumenediamine, N, N'-dicinenamylidene-1,6-hexanediamine, ethylenediamine carbamate, hexamethylenediamine Polyamine crosslinking agents such as carbamate, thiourea crosslinking agents such as ethylenethiourea, 1,3-diethylthiourea, 1,3-dibutylthiourea, trimethylthiourea, 2,5-dimercap 1,3,4-thiadiazole, 2-mercapto-1,3,4-thiadiazole-5-thiobenzoate and other thiadiazole-based crosslinking agents, 2,4,6-trimercapto-1,3,5-triazine, 2 -Methoxy-4,6-dimercaptotriazine, 2-hexylamino-4,6-dimercaptotriazine, 2-diethylamino-4,6-dimercaptotriazine, 2-cyclohexaneamino-4,6-dimercaptotriazine, 2 -Mercaptotriazine-based crosslinking agents such as dibutylamino-4,6-dimercaptotriazine, 2-anilino-4,6-dimercaptotriazine, 2-phenylamino-4,6-dimercaptotriazine, pyrazine-2,3- Dithiocarbonate, 5-methyl-2,3-dimercaptopyrazine, 5-ethylpyrazine- , 3-dithiocarbonate, 5,6-dimethyl-2,3-dimercaptopyrazine, pyrazine-based crosslinking agents such as 5,6-dimethylpyrazine-2,3-dithiocarbonate, quinoxaline-2,3-dithiocarbonate, 6 -Methylquinoxaline-2,3-dithiocarbonate, 6-ethyl-2,3-dimercaptoquinoxaline, 6-isopropylquinoxaline-2,3-dithiocarbonate, 5,8-dimethylquinoxaline-2,3-dithiocarbonate, etc. Quinoxaline-based crosslinking agent, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone (bisphenol S), 1,1-cyclohexylidene-bis (4-hydroxybenzene), 2-chloro-1,4 -Cyclohexylene-bis (4-hydroxybenzene), 2,2-isopropylidene-bis (4-hydroxybenzene) (bisphenol A), hexafluoroisopropylidene-bis (4-hydroxybenzene) (bisphenol AF) and 2-fluoro-1,4-phenylene-bis (4- And bisphenol-based crosslinking agents such as hydroxybenzene).

When an oxirane monomer having an ethylenically unsaturated group such as allyl glycidyl ether or glycidyl methacrylate is used as the oxirane monomer having a crosslinkable functional group (C) in the polyether polymer, the diene series is usually used as a crosslinking agent. What is used for rubber can be applied, for example, sulfur-based cross-linking agents such as sulfur, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, morpholine disulfide, parabenzoquinone dioxime, benzoylquinone dioxime, etc. Examples thereof include resin-based crosslinking agents such as quinonedioxime-based crosslinking agents, polymethylolphenol, alkylphenol formaldehyde resins, and bromated alkylphenol formaldehyde resins.

The amount of the crosslinking agent is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyether polymer.

Regarding the conditions for crosslinking using a crosslinking agent, the heating temperature is 100 to 200 ° C., and the heating time is usually 0.5 to 300 minutes, although it varies depending on the temperature. As a heating method, any method such as compression molding using a mold, injection molding, steam, infrared rays, or microwave heating can be used.

Examples of the thermal polymerization initiator that can be used in the present invention include radical initiators selected from organic peroxide initiators, azo compound initiators, and the like.
As organic peroxide initiators, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and the like that are usually used for crosslinking are used. 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- Examples include di (t-butylperoxy) hexane, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, and the like.

As the azo compound-based initiator, those usually used for crosslinking such as an azonitrile compound, an azoamide compound, an azoamidine compound, etc. are used. 2,2′-azobisisobutyronitrile, 2,2′-azobis ( 2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2 , 2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis ( 2-methylpropane), 2,2′-azobis [2- (hydroxymethyl) propionitrile] and the like.
These compounds can be used alone or in combination of two or more. Preferably, an organic peroxide-based initiator is used.

Activating energy rays can be ultraviolet rays, visible rays, electron beams or the like. In particular, ultraviolet rays are preferable because of the price of the apparatus and ease of control.

As photoreaction initiators that can be used in the present invention, alkylphenone initiators, benzophenone initiators, acylphosphine oxide initiators, titanocene initiators, triazine initiators, bisimidazole initiators, oxime esters And system initiators. Preferably, an alkylphenone-based initiator, a benzophenone-based initiator, or an acyl phosphine oxide-based initiator is used. In addition to using the above-mentioned compounds alone as a photoreaction initiator, two or more types can be used in combination.

Specific examples of the alkylphenone initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane. -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, etc. It is done. 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- (4-Methylthiophenyl) -2-morpholinopropan-1-one is preferred.

Specific examples of the benzophenone initiator include benzophenone, 2-chlorobenzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dimethylamino) benzophenone, methyl-2-benzoylbenzoate, and the like. . Benzophenone, 4,4′-bis (diethylamino) benzophenone, and 4,4′-bis (dimethylamino) benzophenone are preferred.

Specific examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferred.

In the case of using a heat, the crosslinking reaction can be carried out by heating at a temperature setting from room temperature to about 200 ° C. for about 10 minutes to 24 hours.
In the case of using ultraviolet rays, a xenon lamp, a mercury lamp, a high-pressure mercury lamp, and a metal halide lamp can be used. For example, by irradiating a cumulative exposure dose of 1 to 10000 mJ / cm ² with a UV irradiator using a high-pressure mercury lamp as a light source. It can be carried out.

The amount of the thermal polymerization initiator used for the crosslinking reaction is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, with respect to 100 parts by weight of the polyether polymer. The upper limit is preferably 10 parts by weight or less, and more preferably 4 parts by weight or less.
The amount of the photoinitiator used for the crosslinking reaction is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, with respect to 100 parts by weight of the polyether polymer. The upper limit is preferably 6 parts by weight or less, and more preferably 4 parts by weight or less.

In the present invention, a crosslinking aid may be used in combination with a photoreaction initiator. Crosslinking aid is usually polyfunctional compound _{(e.g., CH 2 = CH-, CH 2} = CH-CH 2 -, CF 2 = CF-, a compound containing at least two HS- a) is. Specific examples of the crosslinking aid include triallyl cyanurate, triallyl isocyanurate, triacryl formal, triallyl trimellitate, N, N′-m-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthal Amides, triallyl phosphate, hexafluorotriallyl isocyanurate, N-methyltetrafluorodiallyl isocyanurate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedi Thiol, 1,10-decanedithiol, 1,12-dodecanedithiol, 2,2-dimethyl-1,3-propanedithiol, 3-methyl-1,5-pentanedithiol, 2-methyl-1,8-octanedithiol 1,4-cyclohexanedithiol, 1,4-bis (mercaptomethyl) cyclohexane, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, bicyclo [2,2,1] hepta-exo-cis-2,3 A dithiol compound such as dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate); 1 , 1,1-Tris (mercaptomethyl) eta 2-ethyl-2-mercaptomethyl-1,3-propanedithiol, 1,2,3-propanetrithiol, trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate) , Trithiol compounds such as tris ((mercaptopropionyloxy) -ethyl) isocyanurate; pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutanate) Aliphatic polythiol compounds such as thiol compounds having 4 or more SH groups such as dipentaerythritol hexa-3-mercaptopropionate, 1,2-dimercaptobenzene, 1,3-dimer Ptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (2 -Mercaptoethyl) benzene, 1,3-bis (2-mercaptoethyl) benzene, 1,4-bis (2-mercaptoethyl) benzene, 1,2-bis (2-mercaptoethyleneoxy) benzene, 1,3- Bis (2-mercaptoethyleneoxy) benzene, 1,4-bis (2-mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5- Trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene , 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (2-mercaptoethyl) benzene, 1,2,4-tris (2-mercaptoethyl) benzene, 1,3,5 -Tris (2-mercaptoethyl) benzene, 1,2,3-tris (2-mercaptoethyleneoxy) benzene, 1,2,4-tris (2-mercaptoethyleneoxy) benzene, 1,3,5-tris ( 2-mercaptoethyleneoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3 4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercap) Methyl) benzene, 1,2,3,4-tetrakis (2-mercaptoethyl) benzene, 1,2,3,5-tetrakis (2-mercaptoethyl) benzene, 1,2,4,5-tetrakis (2- Mercaptoethyl) benzene, 1,2,3,4-tetrakis (2-mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (2-mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (2-mercaptoethyleneoxy) benzene, 2,2′-dimercaptobiphenyl, 4,4′-thiobis-benzenethiol, 4,4′-dimercaptobiphenyl, 4,4′-dimercaptobibenzyl, 2,5 -Toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphth Rangethiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol, 1,3-bis (2-mercaptoethylthio) benzene, 1,4-bis (2-mercaptoethylthio) benzene, 1,2-bis (2-mercaptoethylthiomethyl) benzene, 1,3-bis (2-mercaptoethylthiomethyl) ) Benzene, 1,4-bis (2-mercaptoethylthiomethyl) benzene, 1,2,3-tris (2-mercaptoethylthio) benzene, 1,2,4-tris (2-mercaptoethylthio) benzene, 1,3,5-tris (2-mercaptoethylthio) benzene, 1,2,3,4-tetrakis (2-mercaptoethylthio) ) Benzene, 1,2,3,5-tetrakis (2-mercaptoethyl thio) benzene, and the like aromatic polythiol such as 1,2,4,5-tetrakis (2-mercaptoethyl thio) benzene. These compounds can be used alone or in combination of two or more.

The shape of the polyether polymer of the present invention or a cross-linked product thereof is not limited, and examples thereof include lumps, fibers, films, sheets, pellets, and powders.

The polyether polymer of the present invention or a crosslinked product thereof is used in fields where non-chargeability is required, such as automobile parts, OA equipment, parts for home appliances, electric / electronic fields, or storage / storage cases, tubes, etc. Used in The polyether polymer of the present invention or a cross-linked product thereof can be preferably used as an antistatic material in the above field. Below, an antistatic material is demonstrated to an example as a use.

The polyether polymer or a cross-linked product thereof can be used as a base (base material). In this case, in addition to the case of using only the polyether polymer or a crosslinked product thereof, the following additives may be included in the polyether polymer or the crosslinked product thereof.

In other words, in the present invention, as long as the effects of the present invention are not impaired, according to the purpose or necessity, usual additives to be blended in a general rubber composition, for example, fillers, processing aids, plasticizers, acid acceptors. Agent, softener, anti-aging agent, colorant, stabilizer, adhesion aid, release agent, thermal conductivity-imparting agent, surface non-adhesive agent, tackifier, flexibility agent, heat resistance improver, flame retardant Various additives such as an ultraviolet absorber, an oil resistance improver, a foaming agent, a scorch inhibitor, and a lubricant may be blended in the polyether polymer of the present invention and its cross-linked product.

The antistatic material may be an antistatic material containing the above polyether polymer, may be an antistatic material consisting only of the above polyether polymer, and may be pelletized or powdered. Good.

In the present invention, the polyether polymer or a crosslinked product thereof can be used as an additive for at least one selected from a conductivity-imparting agent, rubber, resin and solvent. That is, the present invention also includes a composition containing the polyether polymer or a crosslinked product thereof; and at least one selected from a conductivity imparting agent, rubber, resin and solvent.

For example, the antistatic material can be used as an antistatic material-containing composition by being used together with a conductivity imparting agent, a resin, rubber, and a solvent.

Examples of the conductivity-imparting agent used in the composition of the present invention, for example, an antistatic material-containing composition, include organic sulfonic acid alkali metal salts.

Examples of the alkali metal constituting the alkali metal sulfonic acid alkali metal salt include alkali metals such as lithium, sodium, potassium, rubidium and cesium, among which sodium, potassium and cesium are preferable, and potassium and sodium are particularly preferable. .

The organic sulfonic acid alkali metal salt is selected from the group consisting of alkali metal salts of bis (fluoroalkylsulfonyl) imide, alkali metal salts of tris (fluoroalkylsulfonyl) methide, and alkali metal salts of trifluoroalkylsulfonic acid. It is preferable that

Specific examples of the organic sulfonic acid alkali metal salt include bis (trifluoromethanesulfonyl) imide lithium Li (CF ₃ SO ₂ ) ₂ N, bis (trifluoromethanesulfonyl) imidopotassium K (CF ₃ SO ₂ ) ₂ N, Bis (trifluoromethanesulfonyl) imide sodium Na (CF ₃ SO ₂ ) ₂ N, tris (trifluoromethanesulfonyl) methide lithium Li (CF ₃ SO ₂ ) ₃ C, tris (trifluoromethanesulfonyl) methide potassium K (CF ₃ SO ₂ ) ₃ C, sodium tris (trifluoromethanesulfonyl) methide Na (CF ₃ SO ₂ ) ₃ C, lithium trifluoromethanesulfonate Li (CF ₃ SO ₃ ), potassium trifluoromethanesulfonate K (CF ₃ SO ₃ ), trifluoromethanesulfone Sodium Na (CF ₃ SO ₃ ). These compounds can be used alone or in combination of two or more.

The content of the conductivity imparting agent is not particularly limited, but is 0.1 to 30 parts by weight, preferably 0.5 parts by weight or more, more preferably 1.0 parts by weight with respect to 100 parts by weight of the polyether polymer. Part or more, more preferably 1.5 parts by weight or more, particularly preferably 2.0 parts by weight or more, and preferably 25 parts by weight or less, more preferably 20 parts by weight or less, still more preferably 15 parts by weight or less. Preferably there is.

The resin used in the composition of the present invention, for example, an antistatic material-containing composition, is preferably a thermoplastic resin or a thermoplastic elastomer. The thermoplastic resin is a polyester resin such as polyethylene terephthalate or polybutylene terephthalate. Polycarbonate resin, polystyrene resin, ABS resin, AS resin, polyamide resin, polyphenylene ether resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyoxymethylene resin, acrylic resin, and the like can be used. As the thermoplastic elastomer, a styrene thermoplastic elastomer, a polyamide thermoplastic elastomer, a polyolefin thermoplastic elastomer, a polyester thermoplastic elastomer, a polyvinyl chloride thermoplastic elastomer, a polyurethane thermoplastic elastomer, or the like can be used. These may be used alone or in combination of two or more.

The composition of the present invention, for example, an antistatic material-containing composition, is not particularly limited in the amount of the resin and the polyether polymer, but the amount of the polyether polymer is 0 with respect to 100 parts by weight of the resin. 0.01 parts by weight or more is preferably blended, 0.05 parts by weight or more is more preferred, 1 part by weight or more is more preferred, 900 parts by weight or less is preferred, 600 More preferably, it is blended in an amount of up to 400 parts by weight. The blending method is not particularly limited, and a commonly used method can be used, and examples thereof include a roll, an extruder, and a kneader.

Examples of the rubber used in the composition of the present invention such as an antistatic material-containing composition include butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), acrylic rubber, and 2 Examples of mixed rubbers of more than one species can be given.

In the composition of the present invention, such as an antistatic material-containing composition, the blending amount of rubber and polyether polymer is not particularly limited, but the blending amount is 0 for the polyether polymer with respect to 100 parts by weight of rubber. 0.01 parts by weight or more is preferably blended, more preferably 0.05 parts by weight or more, more preferably 1 part by weight or more, still more preferably 30 parts by weight or less, More preferably, it is blended in an amount of not more than 15 parts by weight, still more preferably not more than 15 parts by weight. The blending method is not particularly limited, and a commonly used method can be used, and examples thereof include a roll, an extruder, and a kneader.

Examples of the solvent used in the composition of the present invention such as an antistatic material-containing composition include methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, acetone, toluene, tetrahydrofuran, ethyl acetate, chloroform, methylene chloride and the like. These solvents may be used alone or in combination of two or more.

The composition of the present invention, for example, an antistatic material-containing composition, is not particularly limited in the amount of the solvent and the polyether polymer, but the amount of the polyether polymer is 0 with respect to 100 parts by weight of the solvent. 0.01 parts by weight or more is preferably blended, more preferably 0.05 parts by weight or more, more preferably 1 part by weight or more, still more preferably 80 parts by weight or less, More preferably, it is blended in an amount of not more than 50 parts by weight, still more preferably not more than 50 parts by weight.

When a solvent is used as the composition of the present invention, for example, an antistatic material-containing composition, the antistatic material-containing composition is a liquid in which a polyether polymer is dissolved in a solvent. In this case, as described later, it can be used as a coating solution.

Examples of the composition of the present invention, such as an antistatic material-containing composition, further include antioxidants, stabilizers, ultraviolet absorbers, antistatic materials other than those defined in the present invention, lubricants, plasticizers, colorants, A foaming agent, a filler, a pigment, a fragrance, a flame retardant, and a thermal polymerization initiator, a photoreaction initiator, a crosslinking aid and the like can be blended as described later. Among these, it is preferable to use a thermal polymerization initiator, a photoreaction initiator, a crosslinking aid, an antioxidant, or a lubricant.

(Molded body)
The molded body produced using the said polyether polymer, its crosslinked material, or the composition containing the said polyether polymer is also contained in this invention. For example, the polyether polymer of the present invention or a cross-linked product thereof may be molded, for example, into a fiber, a film, a sheet, a pellet, a powder or the like after adding the above-mentioned additives alone.

The composition of the present invention can be used as a molded article by molding as exemplified below. Examples of the molded body include fibers, films, sheets, pellets, powders, and coating films on substrates. These molded bodies may be molded bodies that exhibit elasticity (elastic molded bodies) or may be hard molded bodies that do not exhibit elasticity. Examples of the elastic molded body include elastic rolls.

The composition using the solvent and the polyether polymer, for example, the antistatic material-containing composition using the polyether polymer as the solvent and the antistatic material can be used as a coating liquid. Examples of the coating method include a roll coating method, a gravure coating method, a dip coating method, and a spray coating method. By these methods, the resin, for example, polyester resin such as polyethylene terephthalate, polycarbonate resin, polystyrene resin, ABS resin, AS resin, polyamide resin, polyphenylene ether resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyoxymethylene It is also possible to form a molded body as a coating film by coating a substrate with a composition containing a resin, an acrylic resin, or a mixture of two or more of these and a polyether polymer.

In addition, the antistatic material-containing composition of the present invention can contain a thermal polymerization initiator, a photoreaction initiator, and a crosslinking aid, and can undergo a crosslinking reaction during molding or after molding to obtain a molded body. Crosslinking can be carried out by heating or irradiation with active energy rays such as ultraviolet rays.

In the case of using a heat, the crosslinking reaction can be carried out by heating at a temperature setting from room temperature to about 200 ° C. for about 10 minutes to 24 hours.
In the case of ultraviolet rays, a xenon lamp, a mercury lamp, a high-pressure mercury lamp, and a metal halide lamp can be used. For example, by irradiating with a UV irradiation machine using a high-pressure mercury lamp as a light source, an integrated exposure dose of 1 to 10,000 mJ / cm ^{2 is} irradiated. It can be carried out.

Examples of the thermal polymerization initiator that can be used in the present invention include radical initiators selected from organic peroxide initiators, azo compound initiators, and the like.
As organic peroxide initiators, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy esters, and the like that are usually used for crosslinking are used. 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- Examples include di (t-butylperoxy) hexane, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, and the like.

As the azo compound-based initiator, those usually used for crosslinking such as an azonitrile compound, an azoamide compound, an azoamidine compound, etc. are used. 2,2′-azobisisobutyronitrile, 2,2′-azobis (2 -Methylbutyronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2, 2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2 -Methylpropane), 2,2'-azobis [2- (hydroxymethyl) propionitrile] and the like.
Preferably, an organic peroxide-based initiator is used. These compounds can be used alone or in combination of two or more.

Activating energy rays can be ultraviolet rays, visible rays, electron beams or the like. In particular, ultraviolet rays are preferable because of the price of the apparatus and ease of control.

As photoreaction initiators that can be used in the present invention, alkylphenone initiators, benzophenone initiators, acylphosphine oxide initiators, titanocene initiators, triazine initiators, bisimidazole initiators, oxime esters And system initiators. Preferably, an alkylphenone-based initiator, a benzophenone-based initiator, or an acyl phosphine oxide-based initiator is used. In addition to using the above-mentioned compounds alone as a photoreaction initiator, two or more types can be used in combination.

Specific examples of the alkylphenone initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane. -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, etc. It is done. 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- (4-Methylthiophenyl) -2-morpholinopropan-1-one is preferred.

Specific examples of the benzophenone initiator include benzophenone, 2-chlorobenzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dimethylamino) benzophenone, methyl-2-benzoylbenzoate, and the like. . Benzophenone, 4,4′-bis (diethylamino) benzophenone, and 4,4′-bis (dimethylamino) benzophenone are preferred.

Specific examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferred.

The amount of the thermal polymerization initiator used for the crosslinking reaction is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, with respect to 100 parts by weight of the polyether polymer. The upper limit is preferably 10 parts by weight or less, and more preferably 4 parts by weight or less.
The amount of the photoinitiator used for the crosslinking reaction is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, with respect to 100 parts by weight of the polyether polymer. The upper limit is preferably 6 parts by weight or less, and more preferably 4 parts by weight or less.

In the present invention, a crosslinking aid may be used in combination with a photoreaction initiator. Crosslinking aid is usually polyfunctional compound _{(e.g., CH 2 = CH-, CH 2} = CH-CH 2 -, CF 2 = CF-, a compound containing at least two HS- a) is. Specific examples of the crosslinking aid include triallyl cyanurate, triallyl isocyanurate, triacryl formal, triallyl trimellitate, N, N′-m-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthal Amides, triallyl phosphate, hexafluorotriallyl isocyanurate, N-methyltetrafluorodiallyl isocyanurate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedi Thiol, 1,10-decanedithiol, 1,12-dodecanedithiol, 2,2-dimethyl-1,3-propanedithiol, 3-methyl-1,5-pentanedithiol, 2-methyl-1,8-octanedithiol 1,4-cyclohexanedithiol, 1,4-bis (mercaptomethyl) cyclohexane, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, bicyclo [2,2,1] hepta-exo-cis-2,3 A dithiol compound such as dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate); 1 , 1,1-Tris (mercaptomethyl) eta 2-ethyl-2-mercaptomethyl-1,3-propanedithiol, 1,2,3-propanetrithiol, trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate) , Trithiol compounds such as tris ((mercaptopropionyloxy) -ethyl) isocyanurate; pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutanate) Aliphatic polythiol compounds such as thiol compounds having 4 or more SH groups such as dipentaerythritol hexa-3-mercaptopropionate, 1,2-dimercaptobenzene, 1,3-dimer Ptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (2 -Mercaptoethyl) benzene, 1,3-bis (2-mercaptoethyl) benzene, 1,4-bis (2-mercaptoethyl) benzene, 1,2-bis (2-mercaptoethyleneoxy) benzene, 1,3- Bis (2-mercaptoethyleneoxy) benzene, 1,4-bis (2-mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5- Trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene , 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (2-mercaptoethyl) benzene, 1,2,4-tris (2-mercaptoethyl) benzene, 1,3,5 -Tris (2-mercaptoethyl) benzene, 1,2,3-tris (2-mercaptoethyleneoxy) benzene, 1,2,4-tris (2-mercaptoethyleneoxy) benzene, 1,3,5-tris ( 2-mercaptoethyleneoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3 4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercap) Methyl) benzene, 1,2,3,4-tetrakis (2-mercaptoethyl) benzene, 1,2,3,5-tetrakis (2-mercaptoethyl) benzene, 1,2,4,5-tetrakis (2- Mercaptoethyl) benzene, 1,2,3,4-tetrakis (2-mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (2-mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (2-mercaptoethyleneoxy) benzene, 2,2′-dimercaptobiphenyl, 4,4′-thiobis-benzenethiol, 4,4′-dimercaptobiphenyl, 4,4′-dimercaptobibenzyl, 2,5 -Toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphth Rangethiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol, 1,3-bis (2-mercaptoethylthio) benzene, 1,4-bis (2-mercaptoethylthio) benzene, 1,2-bis (2-mercaptoethylthiomethyl) benzene, 1,3-bis (2-mercaptoethylthiomethyl) ) Benzene, 1,4-bis (2-mercaptoethylthiomethyl) benzene, 1,2,3-tris (2-mercaptoethylthio) benzene, 1,2,4-tris (2-mercaptoethylthio) benzene, 1,3,5-tris (2-mercaptoethylthio) benzene, 1,2,3,4-tetrakis (2-mercaptoethylthio) ) Benzene, 1,2,3,5-tetrakis (2-mercaptoethyl thio) benzene, and the like aromatic polythiol such as 1,2,4,5-tetrakis (2-mercaptoethyl thio) benzene. These compounds can be used alone or in combination of two or more.

As described above, the molded product of the present invention can be formed into a shape such as a coating film on a substrate, in addition to fibers, films, sheets, pellets, and powders. The molded body of the present invention is used as various molded articles in fields where non-chargeability is required, such as automobile parts, OA equipment, home appliance parts, electrical / electronic fields, or storage / storage cases, tubes, etc. It is done. In particular, a polyether polymer having a stable surface resistance value under the low temperature / low humidity conditions and the high temperature / high humidity conditions is preferably used as an antistatic material.

This application claims the benefit of priority based on Japanese Patent Application No. 2016-112994 filed on June 6, 2016 and Japanese Patent Application No. 2016-203895 filed on October 17, 2016 To do. The entire contents of the specification of Japanese Patent Application No. 2016-112994 filed on June 6, 2016 and the entire specification of the Japanese Patent Application No. 2016-203895 filed on October 17, 2016 The contents are incorporated by reference for this application.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. However, the present invention is not limited to the following examples without departing from the gist thereof.

<Analysis of polymer>
The copolymer composition of the polyether polymers obtained in the examples and comparative examples was obtained by dissolving the polyether polymer in deuterated chloroform, determining the integral value of each unit by ¹ H-NMR, and calculating the composition ratio from the calculation results. Asked. As the apparatus, JNM GSX-270 type manufactured by JEOL Ltd. was used.
The weight average molecular weights of the polyether polymers obtained in Examples and Comparative Examples were determined by gel permeation chromatography (GPC) by the following method.
Equipment: GPC system column manufactured by Shimadzu Corporation Column: Shodex KD-807, KD-806M, KD-806, KD-803 manufactured by Showa Denko KK
Detector: Differential refractometer Solvent: Dimethylformamide (Lithium bromide 1 mmol / L)
Flow rate: 1 mL / min
Column temperature: 60 ° C
Molecular weight reference material: Showa Denko Co., Ltd. standard polystyrene

(Measurement of glass transition temperature (Tg) and heat of crystal melting (ΔHc))
The glass transition temperature (Tg) and the heat of crystal fusion (ΔHc) of the polyether polymers obtained in Examples and Comparative Examples were measured as follows. That is, using a differential scanning calorimeter “DSC 6220” manufactured by SII Technology Co., Ltd., a sample of 10 mg was packed in an aluminum pan for measurement, the heating rate was raised to 180 ° C. at 10 ° C./min, and the same temperature was maintained for 3 minutes. After being held, the temperature was lowered to −100 ° C. at a cooling rate of 10 ° C./min, held at the same temperature for 3 minutes, and then again from the thermogram when heated to 180 ° C. at 10 ° C./min, the glass transition temperature (Tg) Asked. The amount of heat of crystal melting (ΔHc) was determined from the area of the exothermic peak accompanying melting in the second temperature raising process.

<Manufacture of polymerization catalyst>
Production of polymerization catalyst A three-necked flask equipped with a stirrer, a thermometer, and a condenser was charged with 10 g of tributyltin chloride and 35 g of tributyl phosphate and heated at 250 ° C. for 20 minutes with stirring under a nitrogen stream. The product was distilled off and a solid condensate was obtained as a residue at room temperature. Thereafter, this was used as a polymerization catalyst (hereinafter referred to as a condensate catalyst).

Example 1
The inside of a jacketed stainless steel reactor with an internal volume of 10 L was purged with nitrogen, 10 g of the condensate catalyst, 443 g of 2-ethylhexyl glycidyl ether (also described as EHGE), 70 g of glycidyl methacrylate (also described as GMA), and a solvent 4126 g of normal hexane was charged, and 355 g of ethylene oxide (also referred to as EO) was sequentially added while monitoring the polymerization rate of 2-ethylhexyl glycidyl ether by gas chromatography. The polymerization reaction was stopped by adding 16 g of methanol after 8 hours while maintaining the reaction temperature at 28 ° C. After taking out the particulate polymer by decantation, it was dried at 40 ° C. under reduced pressure for 8 hours to obtain 251 g of a polyether copolymer. The copolymer composition of the obtained polyether copolymer was 86 mol% of structural units derived from ethylene oxide, 11 mol% of structural units derived from 2-ethylhexyl glycidyl ether, and 3 mol% of structural units derived from glycidyl methacrylate. The copolymer composition and weight average molecular weight of the obtained polyether copolymer are shown in Table 1.

(Example 2)
The charge and the amount during the polymerization were carried out except that the condensate catalyst was 10 g, 1,2-epoxyhexane (also referred to as EH) 580 g, glycidyl methacrylate 110 g, and normal hexane 3750 g, and the amount of ethylene oxide was 399 g. In the same procedure as in Example 1, 517 g of a polyether copolymer was obtained. The copolymer composition of the obtained polyether copolymer was 74 mol% of structural units derived from ethylene oxide, 22 mol% of structural units derived from 1,2-epoxyhexane, and 4 mol% of structural units derived from glycidyl methacrylate. . The copolymer composition and weight average molecular weight of the obtained polyether copolymer are shown in Table 1.

(Example 3)
The polymerization charge was charged except that the amount of the charged product and its amount were 10 g of condensate catalyst, 480 g of 1,2-epoxybutane (also referred to as EB), 126 g of glycidyl methacrylate and 3750 g of normal hexane, and the amount of ethylene oxide was 644 g. In the same procedure as in Example 1, 806 g of a polyether copolymer was obtained. Ethylene oxide was sequentially added while monitoring the polymerization rate of 1,2-epoxybutane by gas chromatography. The copolymer composition of the obtained polyether copolymer was 68 mol% of structural units derived from ethylene oxide, 28 mol% of structural units derived from 1,2-epoxybutane, and 4 mol% of structural units derived from glycidyl methacrylate. . The copolymer composition and weight average molecular weight of the obtained polyether copolymer are shown in Table 1.

(Comparative Example 1)
The inside of a jacketed stainless steel reactor with an internal volume of 10 L is purged with nitrogen, charged with 10 g of the above condensate catalyst, 144 g of propylene oxide (also referred to as PO) and 3750 g of normal hexane as a solvent, and 1106 g of ethylene oxide has a polymerization rate of propylene oxide. Sequential additions were made while monitoring by gas chromatography. The polymerization reaction was stopped by adding 16 g of methanol after 8 hours while maintaining the reaction temperature at 28 ° C. After taking out the particulate polymer by decantation, it was dried at 40 ° C. under reduced pressure for 8 hours to obtain 1086 g of a polyether copolymer. The copolymer composition of the obtained polyether copolymer was 9 mol% of a structural unit derived from propylene oxide and 91 mol% of a structural unit derived from ethylene oxide. The copolymer composition and weight average molecular weight of the obtained polyether copolymer are shown in Table 1.

(Comparative Example 2)
The same as in Comparative Example 1 except that the charged product and its amount during polymerization were 10 g of condensate catalyst, 59 g of propylene oxide, 175 g of allyl glycidyl ether (also referred to as AGE) and 3750 g of normal hexane, and the amount of ethylene oxide was 1015 g. According to the procedure, 1007 g of a polyether copolymer was obtained. In addition, ethylene oxide was sequentially added while monitoring the polymerization rate of propylene oxide by gas chromatography. The copolymer composition of the obtained polyether copolymer was 4 mol% of a structural unit derived from propylene oxide, 90% of a structural unit derived from ethylene oxide, and 6 mol% of a structural unit derived from allyl glycidyl ether. The copolymer composition and weight average molecular weight of the obtained polyether copolymer are shown in Table 1.

(Comparative Example 3)
The charge and the amount during polymerization were 10 g of condensate catalyst, 536 g of phenylglycidyl ether (also referred to as PhGE), 68 g of normal glycidyl methacrylate, and 4050 g of normal hexane, and the amount of ethylene oxide was 346 g. In the same procedure, 881 g of a polyether copolymer was obtained. The copolymer composition of the obtained polyether copolymer was 66 mol% of structural units derived from ethylene oxide, 30 mol% of structural units derived from phenylglycidyl ether, and 4 mol% of structural units derived from glycidyl methacrylate. The copolymer composition and weight average molecular weight of the obtained polyether copolymer are shown in Table 1.

In order to measure the surface resistance value and water absorption of the polyether copolymers obtained in Examples 1 to 3 and Comparative Examples 1 to 3 as described later, test pieces were prepared as follows.

<Preparation of test piece>
Each of the polyether copolymers of Examples 1 to 3 and the polyether copolymers of Comparative Examples 1 to 3 was spread on a mold and pressed for 2 minutes with a vacuum heating press set at 160 ° C. A polymer sheet having a thickness of 1 mm was molded to obtain test pieces of Examples 1 to 3 and Comparative Examples 1 to 3.

<Drying of test piece>
For each of the test pieces of Examples 1 to 3 and Comparative Examples 1 to 3, the weight of the test pieces was measured after conditioning for 48 hours in a drive source adjusted to a dew point of −50 ° C. The weight was taken as the weight in the dry state.

<Measurement of surface resistance and water absorption at 23 ° C. and 50% RH>
For each of the dried test pieces of Examples 1 to 3 and Comparative Examples 1 to 3, the temperature is 23 ° C. and the humidity is 50% RH (hereinafter referred to as “23 ° C. × 50% RH” or “23 ° C. 50%”). The temperature was adjusted for 48 hours in the constant temperature and humidity chamber adjusted), and the surface resistance value was measured in the constant temperature and humidity chamber. For the measurement, an insulation resistance meter (manufactured by Mitsubishi Chemical Corporation, Hiresta UX MCP-HT800) was used to apply a voltage of 100 volts, and the resistance value after 1 minute was read to calculate the surface resistance value. The measurement results are shown in Table 1.
In addition, the weight of the test piece conditioned for 48 hours in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and a humidity of 50% RH was measured, and the rate of increase from the weight of the test piece in the dry state was calculated from the following formula. Table 1 also shows the water absorption at 23 ° C. and 50% RH.
Water absorption at 23 ° C. and 50% RH (% by weight) = ((weight of polyether polymer conditioned at temperature 23 ° C., humidity 50% RH−weight of polyether polymer in dry state) / in dry state Weight of polyether polymer) x 100

<Measurement of surface resistance value at 10 ° C. and 15% RH and surface resistance value at 35 ° C. and 85% RH>
For Examples 2 and 3 and Comparative Examples 1 and 2 in Table 1, the surface resistance value at 10 ° C. and 15% RH and the surface resistance value at 35 ° C. and 85% RH were also measured as follows.
That is, for each of the dried test pieces of Examples 2 to 3 and Comparative Examples 1 and 2, the temperature was 10 ° C. and the humidity was 15% RH (low temperature and low humidity condition, hereinafter “10 ° C. × 15% RH” or “10 ° C.”). The temperature was adjusted in a constant temperature and humidity chamber adjusted for 48 hours, and the surface resistance value of each example was measured in the same constant temperature and humidity chamber.
For each of the dried test pieces of Examples 2 to 3 and Comparative Examples 1 to 2, the temperature was 35 ° C. and the humidity was 85% RH (high temperature and high humidity condition, hereinafter “35 ° C. × 85% RH” or “35 ° C. 85” The temperature was adjusted in a constant temperature and humidity chamber adjusted for 48 hours, and the surface resistance value of each example was measured in the constant temperature and humidity chamber.
For the measurement, an insulation resistance meter (manufactured by Mitsubishi Chemical Corporation, Hiresta UX MCP-HT800) was used to apply a voltage of 100 volts, and the resistance value after 1 minute was read to calculate the surface resistance value. The measurement results are shown in Table 2.

<Appearance change evaluation>
The dried specimens of Examples 1 to 3 and Comparative Examples 1 to 3 were conditioned for 48 hours in a constant temperature and humidity chamber adjusted to a temperature of 35 ° C. and a humidity of 85% RH, and the appearance in a high temperature and high humidity environment The change was visually evaluated according to the following criteria. The results are shown in Table 1.
○: No warpage deformation ×: Warpage deformation

Evaluation of each polyether copolymer obtained in Examples and Comparative Examples is as follows. In Table 1, it is clear that the polyether copolymers of Examples 1 to 3 having a water absorption rate of about 1% are excellent in terms of appearance change in a high temperature and high humidity environment. Of the alkyloxiranes copolymerizable with ethylene oxide, the polyether copolymers of Comparative Examples 1 and 2 using propylene oxide having 3 carbon atoms outside the scope of the present invention are the copolymers of Examples 1 to 3. Although the surface resistance is not inferior, it has a high water absorption rate and is extremely inferior in terms of appearance change in a high temperature and high humidity environment. The polyether copolymer of Comparative Example 3 has a high surface resistance, and is inferior to the polyether copolymers of Examples 1 to 3 in the balance between semiconductivity and water absorption.

In Table 2, the polyether copolymers of Examples 2 to 3 are 1.0 × 10 ⁸ to 1.0 × 10 ¹² (Ω / sq.) Under low temperature / low humidity conditions and high temperature / high humidity conditions. The polyether copolymer of Comparative Examples 1 and 2 has a wide range of surface resistance values under low temperature / low humidity conditions and high temperature / high humidity conditions. Therefore, it was an unfavorable result in applications such as antistatic materials.

<Example of molded body>
Example 4
The polyether copolymer obtained in Example 3 was dissolved in tetrahydrofuran to a solid concentration of 15% by weight, and then the photopolymerization initiator Irgacure 907 (2-methyl-1- (4-methylthiophenyl) -2- A uniform solution was prepared by adding 1.5 parts by weight of morpholinopropan-1-one) to 100 parts by weight of the polyether copolymer. After dropping a certain amount of solution on the PET film, it was coated with an applicator and the tetrahydrofuran was evaporated to form a uniform film having a thickness of 100 μm. A UV irradiation machine using a high-pressure mercury lamp as a light source was irradiated with 1 J / cm ² to obtain a crosslinked film (molded product).

<Drying the molded body>
The molded body of Example 4 was conditioned for 48 hours in a dry bath adjusted to a dew point of −50 ° C.

<Measurement of surface resistance value>
The dried molded body of Example 4 was conditioned for 48 hours in a constant temperature and humidity chamber adjusted to a temperature of 10 ° C. and a humidity of 15% RH (low temperature and low humidity conditions). The surface resistance value of was measured.
The dried molded body of Example 4 was conditioned for 48 hours in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and a humidity of 50% RH, and the surface resistance value of the molded body in the constant temperature and humidity chamber was adjusted. Measurements were made.
In addition, the dried molded body of Example 4 was conditioned for 48 hours in a constant temperature and humidity chamber adjusted to a temperature of 35 ° C. and a humidity of 85% RH (high temperature and high humidity conditions). The surface resistance value of the molded body was measured.
For the measurement, an insulation resistance meter (manufactured by Mitsubishi Chemical Corporation, Hiresta UX MCP-HT800) was used to apply a voltage of 100 volts, and the resistance value after 1 minute was read to calculate the surface resistance value. The measurement results are shown in Table 3.

<Environmental change assessment>
23 ° C. × 15% RH environment, 23 ° C. × 50% RH environment, 35 ° C. × 85% RH environment, and 35 ° C. × 85% RH environment. The environmental variation value of the surface resistance value with respect to 50% RH (standard environment) was determined. The results are shown in Table 3. The smaller the change in the surface resistance value with respect to the standard environment, the smaller the environmental dependency.
The environmental fluctuation value of the surface resistance value is the difference between the common logarithm of the surface resistance value in the environment of 10 ° C. × 15% RH and the common logarithm of the surface resistance value in the environment of 23 ° C. × 50% RH, and 23 ° C. × It is calculated from the difference between the two values: the common logarithm of the surface resistance value in a 50% RH environment and the common logarithm of the surface resistance value in a 35 ° C. × 85% RH environment. More specifically, it is calculated by the following calculation formula.
Environmental variation value of surface resistance value = [log ₁₀ (surface resistance value at 10 ° C. × 15% RH) −log ₁₀ (surface resistance value at 23 ° C. × 50% RH)] − [log ₁₀ (23 ° C. × 35 Surface resistance value at% RH) −log ₁₀ (surface resistance value at 35 ° C. × 85% RH)]

Next, Examples 5 and 6 and Example 7 below are shown as examples to which a conductivity imparting agent is added.

(Example 5)
The polyether copolymer obtained in Example 3 was dissolved in tetrahydrofuran to a solid concentration of 15% by weight, and then the photopolymerization initiator Irgacure 907 (2-methyl-1- (4-methylthiophenyl) -2- 1.5 parts by weight of morpholinopropan-1-one) per 100 parts by weight of the polyether copolymer, and sodium salt (sodium trifluoromethanesulfonate, manufactured by Tokyo Chemical Industry Co., Ltd.) A uniform solution was prepared by adding 5 parts by weight to 100 parts by weight. After dropping a certain amount of solution on the PET film, it was coated with an applicator and the tetrahydrofuran was evaporated to form a uniform film having a thickness of 100 μm. A UV irradiation machine using a high-pressure mercury lamp as a light source was irradiated with 1 J / cm ² to obtain a crosslinked film (molded product).

(Example 6)
The polyether copolymer obtained in Example 3 was dissolved in tetrahydrofuran to a solid concentration of 15% by weight, and then the photopolymerization initiator Irgacure 907 (2-methyl-1- (4-methylthiophenyl) -2- 1.5 parts by weight of morpholinopropan-1-one) with respect to 100 parts by weight of the polyether copolymer, and potassium salt (potassium trifluoromethanesulfonate, manufactured by Tokyo Chemical Industry Co., Ltd.) A homogeneous solution was prepared by adding 10 parts by weight to 100 parts by weight. After dropping a certain amount of solution on the PET film, it was coated with an applicator and the tetrahydrofuran was evaporated to form a uniform film having a thickness of 100 μm. A UV irradiation machine using a high-pressure mercury lamp as a light source was irradiated with 1 J / cm ² to obtain a crosslinked film (molded product).

The molded products obtained in Example 5 and Example 6 were measured for surface resistance and evaluated for environmental variation in the same manner as in Example 4 above. The results are shown in Table 4 below.

(Example 7)
20 parts by weight of the polyether copolymer obtained in Example 3, 5 parts by weight of potassium salt (potassium trifluoromethanesulfonate, manufactured by Tokyo Kasei Kogyo Co., Ltd.), 75 weights of ABS resin (EX-18A, manufactured by UMGABS) After blending, the resin composition was melt-kneaded with a vented twin-screw extruder to obtain a resin composition. The resin composition was molded using an injection molding machine (model number “SE18DUZ”, manufactured by Sumitomo Heavy Industries, Ltd.) under conditions of a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. to obtain a molded product. A test piece (40 mm square, 1 mm thickness) was cut out from the molded product. About this test piece, it carried out similarly to the said Example 4, and performed the measurement of surface resistance value, and environmental fluctuation evaluation. The results are shown in Table 5 below.

Next, the characteristics of the molded product obtained using the polyether copolymer of the present invention (Example 8) and the molded product obtained using a polyether copolymer other than the present invention (Comparative Example 3) are compared. did.

(Example 8)
After blending 20 parts by weight of the polyether copolymer obtained in Example 3 and 80 parts by weight of ABS resin (EX-18A, UMGABS Co., Ltd.), the mixture was melt-kneaded in a twin-screw extruder with a vent. A resin composition was obtained. The resin composition was molded using an injection molding machine (model number “SE18DUZ”, manufactured by Sumitomo Heavy Industries, Ltd.) under conditions of a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. to obtain a molded product. A test piece (40 mm square, 1 mm thickness) was cut out from the molded product.
(Comparative Example 3)
Except that 20 parts by weight of the polyether copolymer obtained in Example 3 was changed to 20 parts by weight of the polyether copolymer obtained in Comparative Example 2, the same operation as in Example 8 was performed, and a test piece was obtained. Obtained.

For each of the above test pieces, the surface resistance value was measured and the environmental variation was evaluated in the same manner as in Example 4. The results are shown in Table 6 below.

<Appearance evaluation>
The test piece was immersed in water at 23 ° C. for 7 days, and the appearance was evaluated based on whether or not blistering occurred on the surface as described below. The results are shown in Table 6 below.
No blistering (appearance is good): ○
Blister occurred (exterior appearance): ×

From the results of Examples 4 to 8 and Comparative Example 3 described above, the polyether copolymer of the present invention was used for the production of a molded product, and was obtained even when the mixture with the polyether copolymer was various. It can be seen that environmental fluctuation of the surface resistance value of the molded product can be suppressed.

The polyether polymer of the present invention is configured as described above, and has a surface resistance value of 23 ° C. and 50% RH; and 10 ° C., 15% RH and 35 ° C., and 85% RH. In at least one of the above, exhibiting excellent semiconductivity, excellent balance characteristics with water absorption, and excellent shape stability. In particular, it has a stable surface resistance value under the low temperature / low humidity conditions and high temperature / high humidity conditions of the present invention. Polyether copolymers are mixed with resins and rubbers and used as antistatic materials, but in the future, they are also expected to be used as single antistatic materials that have elasticity, chemical resistance, heat resistance, etc. as rubber. .

Claims (7)

1. The water absorption at 23 ° C. and 50% RH is 1.5% by weight or less and the surface resistance value is 1.0 × 10 ¹² (Ω / sq.) Or less;
   The surface resistance value at 10 ° C. and 15% RH and the surface resistance value at 35 ° C. and 85% RH are both 1.0 × 10 ⁸ to 1.0 × 10 ¹² (Ω / sq.); A polyether polymer characterized by satisfying at least one of them.
2. (A) 65 to 99 mole percent of structural units derived from ethylene oxide, (B) 35 to 1 mole percent of structural units derived from an oxirane monomer composed of 4 or more carbon atoms, (C) an oxirane unit having a crosslinkable functional group The polyether polymer according to claim 1, comprising 0 to 10 mole percent of a structural unit derived from a monomer.
3. (A) 65 to 90 mole percent of structural units derived from ethylene oxide, (B) 30 to 5 mole percent of structural units derived from an oxirane monomer composed of 4 to 10 carbon atoms, and (C) an oxirane having a crosslinkable functional group The polyether polymer according to claim 1 or 2, which contains 1 to 8 mole percent of structural units derived from monomers.
4. The polyether polymer according to claim 2, wherein the (B) oxirane monomer having 4 or more carbon atoms is an oxirane monomer having an alkyl group or an alkoxy group.
5. 5. The polyether polymer according to claim 2, wherein the (C) oxirane monomer having a crosslinkable functional group is glycidyl methacrylate or allyl glycidyl ether.
6. A composition comprising the polyether polymer according to any one of claims 1 to 5 or a crosslinked product thereof; and at least one selected from a conductivity-imparting agent, rubber, resin and solvent.
7. A molded article produced using the polyether polymer or composition according to any one of claims 1 to 6.