CN109153778A

CN109153778A - Polyether polymer and composition and formed body containing the polyether polymer

Info

Publication number: CN109153778A
Application number: CN201780031441.XA
Authority: CN
Inventors: 小田实生; 平山大悟; 近田安史; 山崎敦朗
Original assignee: Daiso Co Ltd
Current assignee: Osaka Soda Co Ltd
Priority date: 2016-06-06
Filing date: 2017-06-06
Publication date: 2019-01-04
Also published as: TW201815884A; JP7031582B2; JPWO2017213140A1; WO2017213140A1; KR20190016490A

Abstract

The present invention provide sheet resistance value be suppressed to it is certain hereinafter, and the good polyether polymer of shape stability and composition and formed body containing the polyether polymer.The polyether polymer, which is characterized in that at least meet following one: the water absorption rate at 23 DEG C, 50%RH is 1.5 weight % hereinafter, and sheet resistance value is 1.0 × 10¹²(Ω/sq.) below；It and in the sheet resistance value under 10 DEG C, 15%RH and the sheet resistance value at 35 DEG C, 85%RH is 1.0 × 10⁸~1.0 × 10¹²(Ω/sq.)。

Description

Polyether polymer and composition and formed body containing the polyether polymer

Technical field

Of the invention (hereinafter also referred to the application) be related to polyether polymer and composition containing the polyether polymer and Formed body.Particularly, the present invention relates to sheet resistance value under the defined conditions in a certain range while, it is suppressed that appearance Variation, the i.e. good polyether polymer of shape stability and composition and formed body containing the polyether polymer.Such as this That invents the OA equipment rubber roll material and antistatic material for being related to being suitable as duplicator etc. shows good surface electricity Resistance value, and with the good single polyether polymer (hereinafter also referred to " copolyether ") of the equilibrium response of water absorption rate.This Outside, the copolyether that above-mentioned " single polyether polymer " refers to single kind, it is various with aftermentioned patent document 1 The mixture of multiple copolyethers distinguishes.Moreover, it relates in low temperature, low-moisture conditions and high temperature, high humility Under the conditions of the polyether polymer with stable sheet resistance value, and used the antistatic material of polyether polymer.

Background technique

Copolyether with ionic conductivity, other than being widely used in OA equipment rubber roll material, also with tree Rouge and other rubber mix are utilized as the antistatic material for playing semipermanent and continuing function.In general, resin and rubber etc. High molecular material due to being easy electrification, there is a problem of attracting dust and dirt, damage it is beautiful.Additionally, it is known that due to electrostatic The maloperation for leading to electronic equipment etc., especially for prevent maloperation need by the sheet resistance value of rubber and plastics control exist 1.0×10¹⁰~1.0 × 10¹²(Ω/Sq.) below (non-patent literature 1).

In addition, the previous polyether material as antistatic material, uses the homopolymer and ethylene oxide and ring of ethylene oxide The copolymer (patent document 1) of Ethylene Oxide.Specifically, in patent document 1, as the balance two for making surface resistance and water imbibition Vertical method proposes the method for mixing the homopolymer of propylene oxide low to ethylene oxide copolymer mixing water absorption rate.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 8-183901 bulletin

Non-patent literature

Non-patent literature 1: forming Vol.17No.12, p805,2005

Summary of the invention

The polyether material of copolyether etc. exists simultaneously the big problem of water imbibition, ruler although ionic conductivity is good Very little stability is insufficient, there is the problem of causing the tone variations of gonorrhoea etc. along with water suction.In addition, mixed as antistatic material The composition of conjunction and formed body is obtained using the composition also produce same problem.

As polyether material, the material of above patent document 1 can be enumerated.However, due in this method in addition to need 2 kinds it is poly- Except ether polymer, the polymer for mixing different characteristics is also requirement, bad due to dispersing, and may be occurred in same material Sheet resistance value and water absorption rate it is uneven.

Additionally, there are the classes in low temperature, low-moisture conditions and high temperature, high humidity following table surface resistance large change Topic, it is desirable to which the polyethers obtained under low temperature, low-moisture conditions and high temperature, high humidity with stable sheet resistance value is poly- Close object.

The present invention studies regarding to the issue above, it is intended that providing under conditions of 23 DEG C, 50%RH；And Under conditions of 10 DEG C, 15%RH and 35 DEG C, 85%RH；At least one of meet as defined in sheet resistance value (below also will The characteristic is known as " semiconduction is good ") while, inhibit cosmetic variation, i.e. shape stability is good (below also by the characteristic Referred to as " dimensional stability is good ") polyether polymer, and the composition containing the polyether polymer, and, using described poly- Ether polymer or the formed body of composition production.More specifically, the purpose of the application is to provide and is suitable as such as OA and sets Spare rubber rollers, the semiconduction of antistatic material and antistatic material monomer and the good single polyethers of dimensional stability Polymer and its cross-linking agent, and the low temperature, low-moisture conditions and the high temperature that use in antistatic material etc., high humidity are provided Under, the polyether polymer with stable sheet resistance value, and the antistatic material containing the polyether polymer.

The present inventor in order to solve the above problems, has carried out in-depth study repeatedly, as a result, it has been found that, pass through one Kind polyether polymer, and then its cross-linking agent solves above-mentioned project, which is characterized in that, at least meets following One of: the water absorption rate at 23 DEG C, 50%RH is 1.5 weight % hereinafter, and sheet resistance value is 1.0 × 10¹²(Ω/sq.) Below；And the sheet resistance value under 10 DEG C, 15%RH and the sheet resistance value at 35 DEG C, 85%RH be 1.0 × 10⁸~1.0 × 10¹²(Ω/sq.)。

That is, can be described below about the present invention.

1 a kind of polyether polymer of item, which is characterized in that it at least meets following one: the water suction at 23 DEG C, 50%RH Rate is 1.5 weight % hereinafter, and sheet resistance value is 1.0 × 10¹²(Ω/sq.) below；And at 10 DEG C, 15%RH Sheet resistance value and the sheet resistance value at 35 DEG C, 85%RH are 1.0 × 10⁸~1.0 × 10¹²(Ω/sq.)。

2 polyether polymers according to item 1 of item, which is characterized in that it contains the structural unit from (A) ethylene oxide 65-99 molar percentage, 35-1 moles hundred of structural unit from (B) oxirane monomers constituted with 4 or more carbon atom number Divide ratio, come from the structural unit 0-10 molar percentage that (C) has the oxirane monomers of cross-linking functional group.

3 polyether polymers according to item 1 or 2 of item, which is characterized in that it contains the structure from (A) ethylene oxide Unit 65-90 molar percentage comes from (B) with 30-5 moles of structural unit of the carbon atom number 4-10 oxirane monomers constituted Percentage comes from the structural unit 1-8 molar percentage that (C) has the oxirane monomers of cross-linking functional group.

4 polyether polymers according to item 2 of item, which is characterized in that the ring that (B) is constituted with 4 or more carbon atom number Oxidative ethane monomer is the oxirane monomers with alkyl or alkoxy.

5 polyether polymers according to any one of item 2-4 of item, which is characterized in that (C) has bridging property official The oxirane monomers that can be rolled into a ball are glycidyl methacrylate, allyl glycidyl ether.

A kind of 6 compositions of item, contain polyether polymer described in any one of 1-5 or its cross-linking agent；And choosing At least one of self-conductance electrical property imparting agent, rubber, resin and solvent.

A kind of 7 formed bodies of item, are made using polyether polymer or composition described in any one of item 1-6 Formed body.

In addition, 1a- 5a of following item can be recorded as about the present invention.

A kind of polyether polymer of 1a, which is characterized in that the water absorption rate at 23 DEG C, 50%RH be 1.5 weight % hereinafter, And sheet resistance value is 1.0 × 10¹²(Ω/sq.) below.

Item 2a polyether polymer according to item 1a, which is characterized in that it contains the structure list from (A) ethylene oxide First 65-99 moles of % (molar percentage), the structural unit from (B) oxirane monomers constituted with 4 or more carbon atom number 35-1 moles of %, 0-10 moles of % of structural unit that (C) has the oxirane monomers of cross-linking functional group is come from.

Item 3a polyether polymer according to item 2a, which is characterized in that the ethylene oxide constituted with 4 or more carbon atom number Monomer is the oxirane monomers with alkyl or alkoxy.

Item 4a polyether polymer according to item 2a or 3a, which is characterized in that the epoxy second with cross-linking functional group Alkane monomer is glycidyl methacrylate, allyl glycidyl ether.

A kind of item cross-linking agent of 5a, polyether polymer described in any one of item 1a-4a is crosslinked.

In addition, 1b- 5b of following item can be recorded as about the present invention.

A kind of polyether polymer of 1b, which is characterized in that sheet resistance value at 10 DEG C, 15%RH and 35 DEG C, Sheet resistance value under 85%RH is 1.0 × 10⁸~1.0 × 10¹²(Ω/sq.)。

A kind of item antistatic material of 2b, contains polyether polymer described in a 1b.

Item 3b antistatic material according to item 2b, which is characterized in that it is to contain the structure for coming from (A) ethylene oxide 65-90 moles of % of unit, the structural unit 30-5 from (B) alkylene oxide (oxirane monomers) constituted with carbon atom number 4-10 Mole %, have from (C) cross-linking functional group oxirane monomers 1-8 moles of % of structural unit polyether polymer.

Item 4b antistatic material according to item 3b, which is characterized in that (C) has ethylene oxide of cross-linking functional group Monomer is glycidyl methacrylate, allyl glycidyl ether.

A kind of item composition containing antistatic material of 5b, contains antistatic material described in a 2b-4b and resin.

A kind of item composition containing antistatic material of 6b, contains antistatic material described in a 2b-4b and rubber.

A kind of item composition containing antistatic material of 7b, contains antistatic material described in a 2b-4b, rubber and tree Rouge.

A kind of item composition containing antistatic material of 8b, contains antistatic material described in a 2b-4b and solvent.

A kind of item formed body of 9b, the composition described in any one of item 5b-8b containing antistatic material is shaped It forms.

In accordance with the invention it is possible to provide sheet resistance value under the defined conditions and be it is a certain range of simultaneously, inhibit outer See variation, the i.e. good polyether polymer of shape stability and composition and formed body containing the polyether polymer.According to The polyether polymer and its cross-linking agent of aforementioned present invention, are preferred for the purposes of antistatic material etc., are specifically preferred for needing Antistatic material, OA equipment rubber rollers of semiconduction etc..

Specific embodiment

Polyether polymer of the invention, which is characterized in that it at least meets following one: the suction at 23 DEG C, 50%RH Water rate is 1.5 weight % hereinafter, and sheet resistance value is 1.0 × 10¹²(Ω/sq.) below；And at 10 DEG C, 15%RH Sheet resistance value and the sheet resistance value at 35 DEG C, 85%RH be 1.0 × 10⁸~1.0 × 10¹²(Ω/sq.)。

It is white from not occurring under high temperature and humidity as the water absorption rate of polyether polymer of the invention at 23 DEG C, 50%RH From the viewpoint of the problem of cosmetic variation of turbid and buckling deformation etc., be 1.5 weight % hereinafter, preferably 1.4 weight % hereinafter, Particularly preferably 1.2 weight % or less.About the lower limit of the water absorption rate at 23 DEG C, 50%RH, there is no particular limitation, can be with For 0.01 weight % or more, or 0.1 weight % or more.From the rising for inhibiting sheet resistance value, it is ensured that a degree of From the viewpoint of water absorption rate, above-mentioned 0.3 weight % of water absorption rate or more, preferably 0.5 weight % or more can be made, more preferably More than 0.7 weight %.

Water absorption rate at 23 DEG C, 50%RH, can be from the weight of polyether polymer in the dry state and with temperature 23 DEG C, the weight of the humidity 50%RH polyether polymer that has carried out status adjustment calculates as follows.

Water absorption rate (weight %) at 23 DEG C, 50%RH=((state tune has been carried out with 23 DEG C of temperature, humidity 50%RH The weight of polyether polymer under weight-drying regime of the polyether polymer of section) polyether polymer under/drying regime weight Amount) × 100

In addition, in the present invention, it is set as 160 DEG C true by the way that polyether polymer to be paved on mold, and with temperature Empty hot press is suppressed 2 minutes, is configured to the polymer sheet of 1mm thickness, using the polymer sheet as test film, test film is existed It is adjusted to carry out the weight of the test film of the drying regime after 48 hours status adjustments in -50 DEG C of dew point of drying box, as dry The weight of polyether polymer under dry state.In addition, the test film of above-mentioned drying regime is being adjusted to 23 DEG C of temperature, humidity The weight that the test film after 48 hours status adjustments is carried out in the constant temperature and humidity cabinet of 50%RH, as with 23 DEG C of temperature, humidity 50%RH has carried out the weight of the polyether polymer of status adjustment.

It is 1.0 × 10 as the sheet resistance value of polyether polymer of the invention at 23 DEG C, 50%RH¹²(Ω/sq.) Hereinafter, preferably 1.0 × 10¹¹(Ω/sq.) is hereinafter, more preferably 7.0 × 10¹⁰(Ω/sq.) below.About in 23 DEG C, 50% The lower limit of sheet resistance value under RH, there is no particular limitation, can be 1.0 × 10⁷More than (Ω/sq.), or 1.0 ×10⁸More than (Ω/sq.).

Sheet resistance value at 23 DEG C, 50%RH acquires as follows.That is, by the way that polyether polymer to be paved on mold, And suppressed 2 minutes with the vacuum hotpressing machine that temperature is set as 160 DEG C, it is configured to the polymer sheet of 1mm thickness, by the polymer sheet Material carries out the drying shape after 48 hours status adjustments as test film, by test film in the drying box for being adjusted to -50 DEG C of dew point The test film of state carries out 48 hours status adjustments in the constant temperature and humidity cabinet for being adjusted to 23 DEG C of temperature, humidity 50%RH, then will The test film, using the insulating-resistance meter of the Hiresta of Mitsubishi chemical Co., Ltd etc., applies in same constant temperature and humidity cabinet 100 volts of voltage, read 1 minute after resistance value and calculate sheet resistance value.

Polyether polymer of the invention meets above-mentioned characteristic, alternatively, sheet resistance value at 10 DEG C, 15%RH and 35 DEG C, the sheet resistance value under 85%RH is all satisfied: lower limit is preferably 1.0 × 10⁸More than (Ω/sq.), more preferably 2.0 × 10⁸More than (Ω/sq.), the upper limit is preferably 1.0 × 10¹²(Ω/sq.) is hereinafter, more preferably 5.0 × 10¹¹(Ω/sq.) below. By making in the sheet resistance value under 10 DEG C, 15%RH and the sheet resistance value at 35 DEG C, 85%RH to be the range, one As temperature and humidity under conditions of, can expect the sheet resistance value for having stable.Meet above-mentioned at 23 DEG C, 50%RH While water absorption rate and sheet resistance value, more preferably meet the above-mentioned sheet resistance value at 10 DEG C, 15%RH and 35 DEG C, Sheet resistance value under 85%RH.

It is acquired as follows in the sheet resistance value under 10 DEG C, 15%RH and the sheet resistance value at 35 DEG C, 85%RH.That is, It suppresses 2 minutes, is configured to by the way that polyether polymer to be paved on mold, and with the vacuum hotpressing machine that temperature is set as 160 DEG C The polymer sheet of 1mm thickness will be carried out using the polymer sheet as test film in the drying box for being adjusted to -50 DEG C of dew point The test film of drying regime after 48 hours status adjustments is being adjusted to 10 DEG C of temperature, humidity 15%RH (low temperature and low humidity condition), Or 48 hours status adjustments are carried out in the constant temperature and humidity cabinet of 35 DEG C of temperature, humidity 85%RH (high temperature and humidity condition), then will The test film, using the insulating-resistance meter of the Hiresta of Mitsubishi chemical Co., Ltd etc., applies in same constant temperature and humidity cabinet 100 volts of voltage, read 1 minute after resistance value and calculate sheet resistance value.

Shown in the comparative example 3 of embodiment as be described hereinafter, in order to improve shape stability, if water absorption rate excessively reduces, surface Resistance value is got higher.In contrast, if above-mentioned, of the invention polyether polymer is in the suction of sheet resistance value and influence shape stability It is showed well in the balance of water rate, can be realized low sheet resistance value and excellent in shape stability two are vertical.

As the polyether polymer for meeting above-mentioned characteristic, preferably comprises the structural unit 65-99 from (A) ethylene oxide and rub That percentage, comes the structural unit 35-1 molar percentage from (B) oxirane monomers constituted with 4 or more carbon atom number There is the structural unit 0-10 molar percentage of the oxirane monomers of cross-linking functional group from (C).

As the polyether polymer for meeting above-mentioned characteristic, the structural unit 65-90 of (A) ethylene oxide is further preferably come from Molar percentage, from (B) with the structural unit 30-5 molar percentage of the carbon atom number 4-10 oxirane monomers constituted, There is the structural unit 1-8 molar percentage of the oxirane monomers of cross-linking functional group from (C).Hereinafter, being directed to each structure list Member is illustrated.

(structural unit for coming from (A) ethylene oxide)

In polyether polymer, as the structural unit for coming from (A) ethylene oxide, preferably there is 65-99 moles of %, it is more excellent Choosing has 65-95 moles of %, particularly preferably has 65-90 moles of %.In particular, shape stability is good same in order to obtain When, it polymerize in above-mentioned low temperature, low-moisture conditions and the polyethers under high temperature, high humidity with stable sheet resistance value Object, as the structural unit for coming from (A) ethylene oxide, lower limit is preferably 65 moles of % or more, more preferably 67 moles of % or more, The upper limit is preferably 99 moles of % hereinafter, more preferably 95 moles of % are hereinafter, further preferably 90 moles of % or less.

(structural units of the oxirane monomers constituted from (B) with 4 or more carbon atom number)

In polyether polymer, as the oxirane monomers (alkylene oxide) constituted from (B) with 4 or more carbon atom number Structural unit, lower limit are preferably 1 mole of % or more, more preferably 5 moles of % or more, further preferably 8 moles of % or more, more Further preferably 10 moles of % or more.The upper limit is preferably 35 moles of % hereinafter, more preferably 30 moles of % or less.Such as conduct The range of above structure unit preferably has 35-1 moles of %, more preferably has 35-5 moles of %, further preferably has 30-5 Mole % still more preferably has 30-10 moles of %.In the range, polyether polymer can obtain sufficiently low surface Resistance value.In addition, in particular, in order to be easy to get in low temperature, low-moisture conditions and in any one of high temperature, high humidity Under the conditions of, the polyether polymer of sheet resistance value in a certain range, the lower limit of above structure unit, preferably 15 moles of % More than, more preferably 20 moles of % or more.

As the oxirane monomers constituted with 4 or more carbon atom number, the ethylene oxide list for providing alkyl may be exemplified Body, the oxirane monomers with alkoxy, the oxirane monomers with epoxy group, the ethylene oxide with aromatic group Monomer, the oxirane monomers with ester group, the oxirane monomers (epoxy alcohol) with hydroxyl, it is however preferred to have the ring of alkyl Oxidative ethane monomer, the oxirane monomers with alkoxy.

When illustrating the oxirane monomers constituted with 4 or more carbon atom number, may be exemplified out epoxy butane, oxepane, The oxirane monomers with alkyl of octylene oxide etc., methyl glycidyl ether, ethyl ether, butyl glycidyl Ether, hexyl glycidyl ether, 2- hexyl glycidyl ether, methoxyethoxyethyl glycidol ether etc. have alkyl The oxirane monomers of oxygroup (also referred to as alkoxy), 1,2- cyclopentane epoxide, 1,2-epoxycyclohexane, 1,2- epoxide ring 12 The oxirane monomers with naphthenic base of alkane etc., styrene oxide, phenyl glycidyl ether etc. with aromatic group Oxirane monomers, the oxirane monomers with ester group of 2,3- epoxy butane propyl propionates etc., 4,5- epoxy -1- amylalcohols, 3, The oxirane monomers etc. with hydroxyl of 4- epoxy-n-butyl alcohol etc., these monomers can also be simultaneously other than being used alone Use two or more.

Wherein, it is however preferred to have the oxirane monomers of alkyl or alkoxy.Wherein, 2- hexyl glycidyl ether, Or the alkylene oxide constituted with carbon atom number 4-10, especially with ethylene oxide be easy copolymerization point on, preferably epoxy butane, Oxepane.Particularly, low temperature, low-moisture conditions and high temperature and high humidity it is any under the conditions of, in order to be easy To sheet resistance value be a certain range of polyether polymer, the alkylene oxide preferably constituted with carbon atom number 4-10, more preferably For the alkylene oxide constituted with carbon atom number 4-8, epoxy butane, 1, the 2- oxepane of further preferably 1,2- epoxy butane etc. Deng oxepane.

(structural unit from (C) with the oxirane monomers of cross-linking functional group)

In polyether polymer, as from (C) have cross-linking functional group oxirane monomers structural unit, under Limit is preferably 0 mole of % or more, and more preferably 1 mole of % or more, further preferably 2 moles of % or more, particularly preferably 3 rub Your % or more as the upper limit is preferably 10 moles of % hereinafter, more preferably 8 moles of % hereinafter, further preferably 6 moles of % with Under, particularly preferably 5 moles of % or less.Such as the range as above structure unit, preferably there is 0-10 moles of %, more preferably With 1-8 moles of %, more preferably there is 1-6 moles of %, particularly preferably there is 1-5 moles of %.

In particular, while shape stability is good in order to obtain, in above-mentioned low temperature, low-moisture conditions and high temperature, height With the polyether polymer of stable sheet resistance value under damp condition, preferably make the ring that there is cross-linking functional group from (C) The structural unit of oxidative ethane monomer is in the range of 1-8 molar percentage.

As the oxirane monomers with cross-linking functional group, can be used can be crosslinked copolyether of the invention Any oxirane monomers, such as halogen plain oxirane monomers can be enumerated.As specific example, epoxy chloropropionate can be enumerated The epihalohydrins class of alkane, epibromohydrin, epiiodohydrin, epichlorhydrin etc., p-chlorostyrene oxide, dibromo phenyl glycidol ether, m-chloro Methyl styrene oxide, p-chloromethyl styrene oxide, chloroethene acid glycidyl ester, glycidic acid chloromethyl ester, tetrafluoro Ethylene oxide, 1, the halogen substituted epoxy ethane other than the epihalohydrins class of 1,2,3,3,3- hexafluoro -1,2- propylene oxide etc., alkene Propyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, crotons acid glycidyl ester, 3,4- ring The ethylene oxide containing ethylenic unsaturated group of oxygen -1- butylene etc., glycidyl methacrylate, glycidyl contracting Water glyceride etc..These oxirane monomers with cross-linking functional group also can be used together 2 kinds in addition to the individual uses More than.From monomer price and from the aspect of obtaining, preferably allyl glycidyl ether, glycidyl methacrylate. Particularly preferably glycidyl methacrylate.

Structural unit as the oxirane monomers constituted from (B) with 4 or more carbon atom number comes from described (C) the preferred combination of the structural unit of the oxirane monomers with cross-linking functional group, can be sweet for 2- ethylhexylglycidylether Oily ether or the alkylene oxide constituted with carbon atom number 4-10, especially epoxy butane, oxepane；With unsaturated group containing ethylene Group ethylene oxide, the especially combination of glycidyl methacrylate, said combination reach present invention provide that table In surface resistance and water absorption rate preferably.

It is poly- particularly as the polyethers of the water absorption rate at 23 DEG C, 50%RH and sheet resistance value with above-mentioned record Close object, may be exemplified out containing from (A) ethylene oxide 65-99 moles of % of structural unit, from (B) with carbon atom number 4 with 35-1 moles of % of structural unit of the oxirane monomers of upper composition, the ethylene oxide list from (C) with cross-linking functional group The polyether polymer of 0-10 moles of % of structural unit of body.

In addition, as above-mentioned record on the sheet resistance value under 10 DEG C, 15%RH and the surface at 35 DEG C, 85%RH Resistance value is 1.0 × 10⁸~1.0 × 10¹²(Ω/sq.) polyether polymer may be exemplified out containing from (A) ethylene oxide 65-99 moles of % of structural unit, the oxirane monomers constituted with 4 or more carbon atom number from (B) structural unit 35-1 Mole %, have from (C) cross-linking functional group oxirane monomers 0-10 moles of % of structural unit polyether polymer.

The polymerization composition of polyether polymer can be passed through by the way that polyether polymer is dissolved in deuterated chloroform¹H-NMR is acquired The integrated value of each unit, and determined and formed by their calculated result.

The weight average molecular weight of polyether polymer, lower limit are preferably 10,000 or more, and more preferably 100,000 or more, further preferably It is 300,000 or more, the upper limit is preferably 5,000,000 hereinafter, more preferably 3,000,000 hereinafter, further preferably 2,000,000 or less.Such as it is poly- The weight average molecular weight of ether polymer is preferably 10,000-500 ten thousand, and more preferably 100,000-300 ten thousand, further preferably 300,000-200 Ten thousand.The lower limit of above-mentioned weight average molecular weight is still more preferably 500,000 or more, particularly preferably 900,000 or more, particularly preferably It is 1,100,000 or more.The weight average molecular weight of polyether polymer is converted using gel permeation chromatography (GPC) by standard polystyren It calculates.

The glass transition temperature of polyether polymer, preferably -35 DEG C are hereinafter, be more preferably -40 DEG C hereinafter, further excellent Be selected as -44 DEG C hereinafter, be still more preferably -49 DEG C hereinafter, be still more preferably -54 DEG C hereinafter, still more preferably for - 59 DEG C hereinafter, particularly preferably -61 DEG C or less.The lower limit of the glass transition temperature of polyether polymer, such as can be -80 DEG C More than.The crystal melting caloric of polyether polymer is preferably 25J/g hereinafter, more preferably 22J/g is hereinafter, further preferably 19J/g hereinafter, particularly preferably 16J/g hereinafter, from reduce environmental turbulence index from the viewpoint of, particularly preferably 8J/g with Under.The lower limit of the crystal melting caloric of polyether polymer, such as can be 0J/g or more.The glass transition temperature of polyether polymer Degree is the value obtained with Differential Scanning Calorimetry measurement (DSC), and crystal melting caloric is the value acquired by melting peakss.

(preparation method of polyether polymer)

Containing from (A) ethylene oxide 65-99 moles of % of structural unit, constituted with 4 or more carbon atom number from (B) 35-1 moles of % of structural unit of oxirane monomers, the structure that (C) has the oxirane monomers of cross-linking functional group is come from The preparation of the polyether polymer of 0-10 moles of % of unit, can be used can be such that the substance of oxirane compound ring-opening polymerisation makees For catalyst, implemented in the range of temperature -20~100 DEG C by solution polymerization process, slurry polymerization process etc..It is urged as such Agent, such as what can be enumerated based on organo-aluminium and make water, the oxygen-containing acid compound of phosphorus and acetylacetone,2,4-pentanedione etc. and react with it are urged Agent class, based on organic zinc and catalyst class, organotin-phosphoric acid ester condensates catalyst class for reacting with it water etc.. Organotin-phosphoric acid the ester condensation recorded in No. 3773694 specification of rice state patent of present invention applicant can be used for example Object catalyst class prepares copolyether of the invention.In addition, being preferably substantially by this when preparation method combined polymerization in this way A little ingredients are copolymerized at random.

In the present invention, other than the state use for polymerizeing polyether polymer, it also can be used and polymerize the polyethers Cross-linking agent made of object crosslinking.

Cross-linking agent made of polyether polymer of the invention is crosslinked, can make polyether polymer cross-linking reaction itself and obtain It arrives, can also heat and be crosslinked together with the crosslinking agent of suitable cross-linking functional group, suitable cross-linking functional group also can be used Thermal polymerization, photoinitiator (also referred to as Photoepolymerizationinitiater initiater) crosslinking obtain.The crosslinking, in addition to heating, It can be carried out by the active energy beam of irradiation ultraviolet light etc..In addition, can be used together with crosslinking agent in the present invention known Crosslinking accelerator, crosslinking accelerating auxiliaries, crosslinking delay agent, the present invention in can be together with thermal polymerization, photoinitiator Use well known cross-linking aid.

Following substances can be used as above-mentioned crosslinking agent.Firstly, there is bridging property as (C) in polyether polymer The oxirane monomers of functional group, using halogen-containing oxirane monomers, especially with epihalohydrins class or the epihalohydrins class When the ethylene oxide that halogen in addition replaces, as the crosslinking agent that can be used, can enumerate ethylenediamine, hexamethylene diamine, Diethylenetriamine, three second tetramines, hexa, p-phenylenediamine, isopropyl phenylenediamine, N, N'- dicinnamylidene -1,6- oneself two The polyamines crosslinking agent of amine, ethylenediamine carbamate, hexamethylene diamine carbamate etc., ethylene thiourea, 1,3- diethyl The Thiourea crosslinking agent of base thiocarbamide, 1,3- dibutyl thiourea, trimethyl thiourea etc., 2,5- dimercapto-1,3,4-thiadiazoles, 2- mercapto Base -1,3, the thiadiazole crosslinking agent of 4- thiadiazoles -5- Thiobenzoate etc., 2,4,6- tri-thiols -1,3,5-triazines, 2- first Oxygroup -4,6- dimercapto triazine, 2- hexylamino -4,6- dimercapto triazine, 2- diethylamino -4,6- dimercapto triazine, 2- Hexamethylene alkylamino -4,6- dimercapto triazine, 2- dibutylamino -4,6- dimercapto triazine, 2- anilino- -4,6- dimercapto three The mercapto-triazine class crosslinking agent of piperazine, 2- anilino- -4,6- dimercapto triazine etc., pyrazine -2,3- dithiocarbonates, 5- methyl - 2,3- dimercapto pyrazines, 5- ethyl pyrazine -2,3- dithiocarbonates, 5,6- dimethyl -2,3- dimercapto pyrazines, 5,6- diformazans The Pyrazine crosslinking agent of base pyrazine -2,3- dithiocarbonates etc., quinoxaline -2,3- dithiocarbonates, 6- methyl-quinoxaline - 2,3- dithiocarbonates, 6- ethyl -2,3- dimercapto quinoxaline, 6- isopropyl quinoxaline -2,3- dithiocarbonates, 5,8- The quinoxaline crosslinking agent of dimethylquinoxalin -2,3- dithiocarbonates etc., 4,4'- dihydroxydiphenyl sulfoxides, 4,4'- bis- Hydroxy diphenyl sulfone (bisphenol S), 1,1- cyclohexylene-bis- (4- hydroxy benzenes), the chloro- 1,4- cyclohexylene-of 2- bis- (4- hydroxy benzenes), 2,2- isopropylidene-bis- (4- hydroxy benzenes) (bisphenol-A), hexafluoroisopropylidenyl-bis- (4- hydroxy benzenes) (bisphenol AFs) and the fluoro- 1,4- of 2- The bisphenols crosslinking agent etc. of phenylene-bis- (4- hydroxy benzenes) etc..

There are the oxirane monomers of cross-linking functional group as (C) in polyether polymer, it is sweet using allyl glycidyl When the ethylene oxide containing ethylenic unsaturated group of oily ether, glycidyl methacrylate etc., as crosslinking agent, Ke Yishi The crosslinking agent used in usual alkadiene rubber, such as sulphur, tetramethylthiuram disulfide, five Asia of tetra-sulfurized pair can be enumerated The sulphur class crosslinking agent of methyl thiuram, morpholine disulfide etc., the quininie dioxime class crosslinking of parabenzoquinone dioxime, benzoyl quinone dioxime etc. Agent, the resinae crosslinking agent of poly- hydroxymethylphenol, alkyl phenolic resin, bromo alkyl phenolic resin etc..

It is preferably 0.1-10 parts by weight relative to 100 parts by weight of polyether polymer, more preferably as the amount of crosslinking agent 0.1-5 parts by weight.

For using the condition of the crosslinking of crosslinking agent, heating temperature is 100-200 DEG C, heating time according to temperature without Together, 0.5-300 minutes time is usually carried out.As heating means, it can be used with dies compress molding, injection moulding, steam Vapour passes through the arbitrary methods such as infrared or microwave heating.

As the thermal polymerization that can be used in the present invention, can enumerate selected from organic peroxide initiator, Radical initiator in azo compound type initiator etc..

As organic peroxide initiator, ketone peroxide, peroxy ketal, hydroperoxides, dialkyl group mistake are used The initiator usually used in crosslinking purposes such as oxide, diacyl peroxide, peroxyester can enumerate the bis- (uncles of 1,1- Butyl peroxy) -3,3,5- trimethyl-cyclohexane, di-tert-butyl peroxide, tert-butyl cumyl peroxide, peroxidating two be withered Base, 2,5- dimethyl -2,5- two (t-butyl peroxy) hexane, benzoyl peroxide, t-butyl peroxy -2 ethyl hexanoic acid ester etc..

As azo compound type initiator, azonitrile compound, azo amide compound, azo amidification can be used and close Azo-compound used in object etc., usual crosslinking purposes can enumerate 2,2'- azodiisobutyronitrile, (the 2- first of 2,2'- azo two Base butyronitrile), 2,2'- azo two (4- methoxyl group -2,4- methyl pentane nitrile), 2,2- azo two (the third amidine of 2- Methyl-N-phenyl) two Hydrochloride, 2,2'- azo two [2- (2- imidazoline -2- base) propane], [2- methyl-N- (2- ethoxy) propionyl of 2,2'- azo two Amine], 2,2'- azo two (2- methylpropane), 2,2'- azo two [2- (methylol) propionitrile] etc..

Other than these compounds are used alone, also it may be two kinds or more.It is preferable to use organic peroxides Class initiator.

As active energy beam, ultraviolet light, visible light, electron beam etc. can be used.Especially from the price of equipment, control From the point of view of the easiness of system, preferably ultraviolet light.

As the photoinitiator that can be used in the present invention, alkylbenzene ketone initiator can be enumerated, benzophenone draws Hair agent, acylphosphine oxide class initiator, titanocenes class initiator, triazines initiator, double imidazoles initiators, oxime esters are drawn Send out agent etc..It is preferable to use alkylbenzene ketone initiator, benzophenone initiator, acylphosphine oxide class initiator it is light-initiated Agent.Other than aforesaid compound in addition to that will be used as photoinitiator is used alone, also two or more kinds may be used.

As the specific example of alkylbenzene ketone initiator, 2,2- dimethoxy -1,2- diphenylethane -1- can be enumerated Ketone, 1- hydroxy-cyclohexyl-phenyl ketone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 1- [4- (2- hydroxyl-oxethyl)-benzene Base] -2- hydroxy-2-methyl -1- propane -1- ketone, 2- hydroxyl -1- [4- [4- (2- hydroxy-2-methyl-propiono)-benzyl] benzene Base]-2- methyl-propan-1- ketone, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinopropane-1- ketone etc..Preferably 2,2- bis- Methoxyl group -1,2- diphenylethane -1- ketone, 1- hydroxy-cyclohexyl-phenyl ketone, 2- hydroxy-2-methyl -1- phenyl-propan -1- Ketone, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinopropane-1- ketone.

The specific example of benzophenone initiator can enumerate benzophenone, 2- chlorobenzophenone, the bis- (diethyl of 4,4'- Amino) benzophenone, bis- (dimethylamino) benzophenone of 4,4'-, 2- benzoyl methyl benzoate etc..Preferably hexichol first Bis- (diethylamino) benzophenone of ketone, 4,4'-, bis- (dimethylamino) benzophenone of 4,4'-.

As the specific example of acylphosphine oxide class initiator, 2,4,6- trimethylbenzoy-diphenies-can be enumerated Phosphine oxide, bis- (2,4,6- trimethylbenzoyl) phenyl phosphine oxides etc..Preferably bis- (2,4,6- trimethylbenzoyl) benzene Base phosphine oxide.

In the case that cross-linking reaction is using heat, it can be heated 10 minutes by the temperature setting with room temperature to 200 DEG C or so It was carried out by 24 hours or so.

In the case where using ultraviolet light, xenon lamp, mercury vapor lamp, high-pressure sodium lamp and metal halide lamp can be used, for example, can By using high-pressure sodium lamp as the UV irradiating machine of light source with accumulated exposure amount 1-10000mJ/cm²Irradiation carries out.

The amount of thermal polymerization used in cross-linking reaction, relative to 100 parts by weight of polyether polymer, lower limit is preferably It is more than 0.01 parts by weight, it is more than more preferably 0.1 parts by weight, the upper limit be preferably 10 parts by weight hereinafter, more preferably 4 parts by weight with Under.

The amount of photoinitiator used in cross-linking reaction, relative to 100 parts by weight of polyether polymer, lower limit is preferably 0.01 More than parts by weight, more than more preferably 0.1 parts by weight, the upper limit is preferably 6 parts by weight hereinafter, below more preferably 4 parts by weight.

In the present invention, cross-linking aid and photoinitiator can be used in combination.Cross-linking aid is usually multi-functional compounds (for example, containing CH₂=CH-, CH₂=CH-CH₂-、CF₂The compound of at least two in=CF-, HS-).Cross-linking aid it is specific Example, can be triallyl trimerization cyanurate, iso-cyanuric acid triallyl ester, 1,3,5- triacryl hexahydro -1, 3,5- triazine (トリア Network リ Le ホルマー Le), trimellitic acid triallyl, N are N'- meta-phenylene bismaleimide, right Phthalic acid dipropyl, diallyl phthalate, tetraallyl terephthalamide, triallyl phosphate, hexafluoro triolefin Propyl isocyanuric acid ester, N- methyl tetrafluoro diallyl isocyanuric acid ester, trimethylol-propane trimethacrylate, three hydroxyl first Base propane triacrylate, two mercaptan of methane, 1,2- dimercaptoethylsulfide, 1,2- propanedithiol, 1,3- propanedithiol, 1,4- Butanediethiol, 1,6- hexanedithiol, two mercaptan of 1,7- heptane, 1,8- octanedithiol, two mercaptan of 1,9- nonane, 1,10- Decanedithiol, two mercaptan of 1,12- dodecane, 2,2- dimethyl -1,3- propanedithiol, 3- methyl-1,5- pentanedithiol, 2- methyl-1, bis- (mercapto methyl) hexamethylenes of 8- octanedithiol, two mercaptan of 1,4- hexamethylene, 1,4-, two sulphur of 1,1- hexamethylene Alcohol, two mercaptan of 1,2- hexamethylene, bicyclic bis- mercaptan of [2,2,1] hept- exo-cis-2,3-, bis- (mercapto methyl) hexamethylenes of 1,1-, Two mercaptan chemical combination of bis- (2- mercaptoethyl) ethers, ethylene glycol bis- (2- mercaptoacetates), ethylene glycol bis- (3-thiopropionates) etc. Object；1,1,1- tri- (mercapto methyl) ethane, 2- ethyl -2- mercapto methyl -1,3- propanedithiol, three mercaptan of 1,2,3- propane, Trimethylolpropane tris (2- mercaptoacetate), trimethylolpropane tris (3-thiopropionate), three ((mercaptopropionyl oxygroups)- Ethyl) isocyanuric acid ester etc. three mercaptan compounds；Pentaerythrite four (2- mercaptoacetate), (the 3- sulfydryl third of pentaerythrite four Acid esters), pentaerythrite four (3- mercaptobutylate), six -3-thiopropionate of dipentaerythritol etc. with 4 or more SH bases Aliphatic poly mercaptan compound, 1,2- thioresorcin, 1,3- thioresorcin, the 1,4- thioresorcin, 1,2- of mercaptan compound etc. Bis- (mercapto methyl) benzene of bis- (mercapto methyl) benzene, 1,3-, bis- (mercapto methyl) benzene of 1,4-, 1,2- bis- (2- mercaptoethyl) benzene, 1, Bis- (2- mercaptoethyl) benzene of 3-, bis- (2- mercaptoethyl) benzene of 1,4-, bis- (the 2- sulfydryl ethyoxyl) benzene of 1,2-, bis- (the 2- sulfydryls of 1,3- Ethyoxyl) benzene, bis- (the 2- sulfydryl ethyleneoxy) benzene of 1,4-, 1,2,3- tri-thiol benzene, 1,2,4- tri-thiol benzene, 1,3,5- tri-thiol Benzene, 1,2,3- tri- (mercapto methyl) benzene, 1,2,4- tri- (mercapto methyl) benzene, 1,3,5- tri- (mercapto methyl) benzene, tri- (2- of 1,2,3- Mercaptoethyl) benzene, 1,2,4- tri- (2- mercaptoethyl) benzene, 1,3,5- tri- (2- mercaptoethyl) benzene, (the 2- sulfydryl ethoxy of 1,2,3- tri- Base) benzene, 1,2,4- tri- (2- sulfydryl ethyoxyl) benzene, 1,3,5- tri- (2- sulfydryl ethyoxyl) benzene, tetra- sulfydryl benzene of 1,2,3,4-, 1,2, Tetra- sulfydryl benzene of 3,5-, tetra- sulfydryl benzene of 1,2,4,5-, 1,2,3,4- tetra- (mercapto methyl) benzene, 1,2,3,5- tetra- (mercapto methyl) benzene, 1,2,4,5- tetra- (mercapto methyl) benzene, 1,2,3,4- tetra- (2- mercaptoethyl) benzene, 1,2,3,5- tetra- (2- mercaptoethyl) benzene, 1,2, 4,5- tetra- (2- mercaptoethyl) benzene, 1,2,3,4- tetra- (2- sulfydryl ethyoxyl) benzene, 1,2,3,5- tetra- (2- sulfydryl ethyleneoxy) benzene, 1,2,4,5- tetra- (2- sulfydryl ethyleneoxy) benzene, 2,2'- dimercapto biphenyl, 4,4'- thiobis-benzenethiol, 4,4'- dimercapto connection Benzene, 4,4'- dimercapto bibenzyl, 2,5- first dimercaptobenzene, 3,4- first dimercaptobenzene, 1,4- naphthyl disulfide alcohol, 1,5- naphthyl disulfide alcohol, 2, 6- naphthyl disulfide alcohol, 2,7- naphthyl disulfide alcohol, two mercaptan of 2,4- dimethyl benzene -1,3-, two mercaptan of 4,5- dimethyl benzene -1,3-, 9,10- Bis- (the 2- sulfydryl ethylmercapto group) benzene of anthracene diformazan alkanethiol, 1,3-, bis- (the 2- sulfydryl ethylmercapto group) benzene of 1,4-, bis- (the 2- sulfydryl second sulphur of 1,2- Ylmethyl) benzene, bis- (the 2- sulfydryl Ethylsulfanylmethyl) benzene of 1,3-, bis- (the 2- sulfydryl Ethylsulfanylmethyl) benzene of 1,4-, (the 2- mercapto of 1,2,3- tri- Base ethylmercapto group) benzene, 1,2,4- tri- (2- sulfydryl ethylmercapto group) benzene, 1,3,5- tri- (2- sulfydryl ethylmercapto group) benzene, (the 2- mercapto of 1,2,3,4- tetra- Base ethylmercapto group) benzene, 1,2,3,5- tetra- (2- sulfydryl ethylmercapto group) benzene, 1,2,4,5- tetra- (2- sulfydryl ethylmercapto group) benzene etc. fragrant adoption Mercaptan etc..Other than these compounds are used alone, also it may be two kinds or more.

The shape of polyether polymer of the invention or its cross-linking agent does not limit, such as other than bulk, can enumerate fibre Dimension, film, sheet material, particle, powder.

Polyether polymer of the invention or its cross-linking agent, can be used for requiring the field of antistatic property, such as automobile component, OA equipment, household appliance components, Electrical and Electronic field, or in its keeping and containing box, pipe etc. with using on the way.This hair Bright polyether polymer or its cross-linking agent, in above-mentioned field, can be used as antistatic material it is preferable to use.Hereinafter, as with Way is illustrated by taking antistatic material as an example.

The polyether polymer or its cross-linking agent can be used as substrate (base material) use.At this point, in addition to poly- using only polyethers Except the case where closing object or its cross-linking agent, following additives can also be contained in polyether polymer or its cross-linking agent.

It i.e. in the present invention, within the scope of the effect of the invention, can be in the present invention according to purpose or needs Polyether polymer, blend using the common additive blended in general rubber composition in its cross-linking agent, such as fill out Material, plasticizer, sour accepting agent, softening agent, age resister, colorant, stabilizer, adhesion auxiliary agent, release agent, is led at processing aid Hot imparting agent, surface non-adhesive agent, adhesion imparting agent, softness-conferring agent, improved heat resistance agent, fire retardant, ultraviolet light are inhaled Receive the various additives of agent, oil resistivity modifier, foaming agent, antiscorching agent, lubricant etc..

As antistatic material, the antistatic material containing the polyether polymer can be, can be only by described Polyether polymer constitute antistatic material, can also be with spheroidizing, powder.

It in the present invention, can be using the polyether polymer or its cross-linking agent as selected from conductivity-imparting agent, rubber, tree The additive of at least one of rouge and solvent come using.I.e. the present invention also includes containing the polyether polymer or its crosslinking Object, and the composition selected from least one of conductivity-imparting agent, rubber, resin and solvent.

Such as the antistatic material can be made by using simultaneously with conductivity-imparting agent, resin, rubber, solvent It is used for the composition containing antistatic material.

As conductivity-imparting agent used in the composition such as the composition containing antistatic material of the invention, Organic sulfonic acid alkali metal salt can be exemplified.

As the type for the alkali metal for constituting organic sulfonic acid alkali metal salt, the alkali gold of lithium, sodium, potassium, rubidium, caesium etc. can be enumerated Belong to, wherein preferably sodium, potassium, caesium, particularly preferably sodium and potassium.

As organic sulfonic acid alkali metal salt, it is preferably selected from alkali metal salt, the three (fluothane of bis- (oroalkane sulfonyl base) imines Base sulfonyl) salt in the alkali metal salt of methide and the alkali metal salt of trifluoroalkyl sulfonic acid.

When particular instantiation organic sulfonic acid alkali metal sulfonate, it may be exemplified out bis- (trimethyl fluoride sulfonyl) imine lithium Li (CF₃SO₂)₂N, bis- (trimethyl fluoride sulfonyl) imines potassium K (CF₃SO₂)₂N, bis- (trimethyl fluoride sulfonyl) imines sodium Na (CF₃SO₂)₂N、 Three (trimethyl fluoride sulfonyl) lithium methide Li (CF₃SO₂)₃C, three (trimethyl fluoride sulfonyl) methylpotassium K (CF₃SO₂)₃C, three (fluoroform Base sulphonyl) sodium methide Na (CF₃SO₂)₃C, trifluoromethanesulfonic acid lithium Li (CF₃SO₃), trifluoromethanesulfonic acid potassium K (CF₃SO₃), trifluoro methylsulphur Sour sodium Na (CF₃SO₃).Other than these compounds are used alone, also it may be two kinds or more.

There is no particular limitation for the content of conductivity-imparting agent, relative to 100 parts by weight of polyether polymer, for 0.1-30 weight Part is measured, more than preferably 0.5 parts by weight, more than more preferably 1.0 parts by weight, more than further preferably 1.5 parts by weight, especially More than preferably 2.0 parts by weight, additionally, it is preferred that for 25 parts by weight hereinafter, more preferably 20 parts by weight are hereinafter, further preferably Below 15 parts by weight

It is preferably hot as resin used in the composition such as the composition containing antistatic material of the invention Polyethylene terephthalate, poly- terephthaldehyde can be used as thermoplastic resin in plastic resin or thermoplastic elastomer (TPE) The polyester resin of sour butanediol ester etc., polystyrene resin, ABS resin, AS resin, polyamide, gathers polycarbonate resin Phenylene ether resins, polyvinyl resin, acrylic resin, polyvinyl chloride resin, acetal resin, acrylic resin etc..As Styrene analog thermoplastic elastomer, polyamide-type thermoplastic elastomer, polyolefins thermoplastic can be used in thermoplastic elastomer (TPE) Elastomer, polyester-type thermoplastic elastomer, polyvinyl chloride analog thermoplastic elastomer, polyurethane-type thermoplastic elastomer etc..They It may be used alone, can also be two or more kinds in combination.

As the composition such as the composition containing antistatic material of the invention, resin and polyether polymer are mixed There is no particular limitation for resultant, relative to the blended amount of 100 parts by weight of resin, polyether polymer preferably be blended with 0.01 parts by weight with On, more preferably blend 0.05 parts by weight more than, further preferably blend 1 parts by weight more than, preferably be blended with 900 parts by weight hereinafter, More preferably 600 parts by weight are blended hereinafter, further preferably blending 400 parts by weight or less.There is no particular limitation for blending procedure, can To use commonly used approach, roller, extruder, kneader etc. may be exemplified out.

As rubber used in the composition such as the composition containing antistatic material of the invention, may be exemplified Butadiene rubber (BR), SBR styrene butadiene rubbers (SBR), acrylonitrile-butadiene rubber (NBR), acrylic rubber out, with And their mixed rubber of more than two kinds.

As the composition such as the composition containing antistatic material of the invention, rubber and polyether polymer are mixed There is no particular limitation for resultant, relative to the blended amount of 100 parts by weight of rubber, polyether polymer preferably be blended with 0.01 parts by weight with On, 0.05 parts by weight or more are more preferably blended, 1 parts by weight or more is further preferably blended, preferably is blended with 30 parts by weight hereinafter, more 20 parts by weight preferably are blended with hereinafter, further preferably blending 15 parts by weight or less.There is no particular limitation for blending procedure, can make With commonly used approach, roller, extruder, kneader etc. may be exemplified out.

As the solvent used in the composition such as the composition containing antistatic material of the invention, can enumerate Methanol, ethyl alcohol, isopropanol, methyl ethyl ketone, acetone, toluene, tetrahydrofuran, ethyl acetate, chloroform, methylene chloride etc..These solvents It can be used alone or two or more kinds may be used.

As the composition such as the composition containing antistatic material of the invention, solvent and polyether polymer are mixed There is no particular limitation for resultant, relative to the blended amount of 100 parts by weight of solvent, polyether polymer preferably be blended with 0.01 parts by weight with On, 0.05 parts by weight or more are more preferably blended, 1 parts by weight or more is further preferably blended, preferably is blended with 80 parts by weight hereinafter, more 60 parts by weight preferably are blended with hereinafter, further preferably blending 50 parts by weight or less.

As the composition such as the composition containing antistatic material of the invention, in the case where using solvent, contain There is the composition of composition of antistatic material etc., can be the liquid by polyether polymer dissolution in a solvent, at this point, as after It states and can be used as coating liquid use.

As the composition such as the composition containing antistatic material of the invention, can further blend anti-oxidant Agent, stabilizer, ultraviolet absorbing agent, present invention provide that antistatic material in addition, lubricant, plasticizer, colorant, foaming Agent, filler, pigment, fragrance, fire retardant, thermal polymerization as be described hereinafter, photoinitiator, cross-linking aid etc..Wherein, preferably Use thermal polymerization, photoinitiator, cross-linking aid, antioxidant or lubricant.

(formed body)

Also include the polyether polymer and its cross-linking agent in the present invention, or uses the group for containing the polyether polymer Close the formed body of object production.For example, can enumerate, polyether polymer of the invention or its cross-linking agent is independent or addition is above-mentioned After additive, it is configured to such as fiber, film, sheet material, particle, powder.

In addition, composition of the invention can be used by illustrated below be formed as formed body.As forming Body, can enumerate fiber, film, sheet material, particle, powder, for film of substrate etc..These formed bodies can be to show elasticity Formed body (elastic forming body), or do not show elasticity hard formed body.As the elastic forming body, can lift Resilient roller etc. out.

Using the composition of the solvent and polyether polymer, such as uses solvent and gather as the polyethers of antistatic material The composition containing antistatic material for closing object can be used as coating liquid use.As coating method, rolling method, recessed can be enumerated Version rubbing method, dip coating, spray coating method etc..By these methods, the resin, such as poly terephthalic acid second two can will be contained The polyester resin of alcohol ester etc., polycarbonate resin, polystyrene resin, ABS resin, AS resin, polyamide, polyphenylene oxide tree Rouge, polyvinyl resin, acrylic resin, polyvinyl chloride resin, acetal resin, acrylic resin or in them 2 Kind or more hybrid resin and polyether polymer composition, coated in becoming formed body as film on substrate.

In addition, making to contain thermal polymerization, photoinitiator, crosslinking in the composition of the invention containing antistatic material Auxiliary agent can be allowed to cross-linking reaction in forming or after shaping and obtain formed body.Crosslinking can be by heating or irradiating ultraviolet light Deng active energy beam and be crosslinked.

In the case where using ultraviolet light, it is able to use xenon lamp, mercury vapor lamp, high-pressure sodium lamp and metal halide lamp, such as can By using high-pressure sodium lamp as the UV irradiating machine of light source with accumulated exposure amount 1-10000mJ/cm²Irradiation carries out.

As the thermal polymerization that can be used in the present invention, can enumerate selected from organic peroxide initiator, The radical initiator of azo compound type initiator etc..

It is preferable to use organic peroxide initiators.Other than these compounds are used alone, it also can be used together 2 Kind or more.

As the photoinitiator that can be used in the present invention, alkylbenzene ketone initiator can be enumerated, benzophenone draws Hair agent, acylphosphine oxide class initiator, titanocenes class initiator, triazines initiator, double imidazoles initiators, oxime esters are drawn Send out agent etc..It is preferable to use alkylbenzene ketone initiator, benzophenone initiator, acylphosphine oxide class initiator it is light-initiated Agent.As photoinitiator, other than aforesaid compound is used alone, also two or more kinds may be used.

As the specific example of alkylbenzene ketone initiator, 2,2- dimethoxy -1,2- diphenylethane -1- can be enumerated Ketone, 1- hydroxy-cyclohexyl-phenyl ketone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 1- [4- (2- hydroxyl-oxethyl)-benzene Base] -2- hydroxy-2-methyl -1- propane -1- ketone, 2- hydroxyl -1- [4- [4- (2- hydroxy-2-methyl-propiono)-benzyl] benzene Base]-2- methyl-propan-1- ketone, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinopropane-1- ketone etc..Preferably 2,2- bis- Methoxyl group -1,2- diphenyl-ethyl -1- ketone, 1- hydroxy-cyclohexyl-phenyl ketone, 2- hydroxy-2-methyl -1- phenyl-propan -1- Ketone, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinopropane-1- ketone.

It has been observed that formed body of the invention other than fiber, film, sheet material, particle, powder, can also be for base The shape of the film of material etc..Formed body of the invention can be used for requiring the field of antistatic property, example as various formed products Such as automobile component, OA equipment, household appliance components, Electrical and Electronic field, or the purposes in its keeping and containing box, pipe etc. Middle use.In particular, with stable sheet resistance value under the low temperature, low-moisture conditions and high temperature, high humidity Polyether polymer is used preferably as antistatic material.

This application claims Japanese patent application filed on June 6th, 2016 the 2016-112994th and October 17 in 2016 The interests of priority based on Japanese patent application the 2016-203895th filed in day.Day filed on June 6th, 2016 Japanese patent application the 2016-203895th filed in present patent application the 2016-112994th and on October 17th, 2016 The full content of specification is introduced into the present invention as reference.

Embodiment

Hereinafter, carrying out more specific description to the present invention by embodiment, comparative example.As long as but insurmountability of the invention its master Purport is then not limited to following embodiment.

The analysis > of < polymer

The copolymerization of polyether polymer obtained in embodiment, comparative example forms, deuterated by the way that polyether polymer to be dissolved in In chloroform, use¹H-NMR acquires the integrated value of each unit, and acquires ratio of components by their calculated result.Device uses Japan's electricity The JNM GSX-270 type of sub- Co. Ltd. system.

The weight average molecular weight of polyether polymer obtained in embodiment, comparative example, by gel permeation chromatography (GPC) to Under method acquire.

Device: Shimadzu Scisakusho Ltd's GPC system

Pillar: Showa Denko K. K Shodex KD-807, KD-806M, KD-806, KD-803

Detector: differential refractometer

Solvent: dimethylformamide (lithium bromide 1mmol/L)

Flow velocity: 1mL/min

Column temperature: 60 DEG C

Molecular weight standard substance: Showa Denko K. K's standard polystyren

(glass transition temperature (Tg), the measurement of crystal melting caloric (Δ Hc))

Embodiment, comparative example obtained polyether polymer glass transition temperature (Tg) and crystal melting caloric (Δ Hc it) is measured as follows.That is, using the differential scanning calorimetry (DSC) " DSC6220 " of SII technology corporation, by sample 10mg is put into measurement aluminium dish, is warming up to 180 DEG C with 10 DEG C/min of heating speed, is kept for 3 minutes at the same temperature Afterwards, -100 DEG C are cooled to 10 DEG C/min of cooling velocity, after being kept for 3 minutes at the same temperature, again with 10 DEG C/min 180 DEG C are warming up to, glass transition temperature (Tg) is acquired by thermogram at this time.Crystal melting caloric (Δ Hc) passes through the 2nd It is acquired in secondary temperature-rise period along with the fever peak area of melting.

The preparation > of < catalyst for polymerization

Tributyl chlorine is put into the three-necked flask for preparing blender, thermometer and condenser with catalyst for polymerization Change tin 10g and tributyl phosphate 35g, stirred on one side under stream of nitrogen gas, heats 20 minutes on one side and evaporate distillate for 250 DEG C, The condensation product of solid-like at room temperature is obtained as residue.Next it is used as catalyst for polymerization (following to record For condensation product catalyst.).

(embodiment 1)

The inside of the stainless steel reactor of the jacketed of capacity 10L is replaced with nitrogen, above-mentioned condensation product catalysis is added Agent 10g, 2- hexyl glycidyl ether is also recorded as (EHGE) 443g, glycidyl methacrylate (is also recorded as GMA) the 70g and n-hexane 4126g as solvent, on one side with the polymerization of gas-chromatography tracking 2- hexyl glycidyl ether Rate gradually adds ethylene oxide (being also recorded as EO) 355g on one side.Methanol 16g is added after 28 DEG C maintain 8 hours in reaction temperature Stop polymerization reaction.After taking out granular polymer by decantation, under reduced pressure, polyethers copolymerization is obtained within dry 8 hours at 40 DEG C Object 251g.The copolymerization group of obtained copolyether becomes, and 86 moles of % of structural unit from ethylene oxide, comes from 2- ethyl 11 moles of % of hexyl glycidyl ether structural unit, 3 moles of % of structural unit from glycidyl methacrylate.It obtains Copolyether copolymerization composition and weight average molecular weight it is as shown in table 1.

(embodiment 2)

By feeding intake when polymerizeing and its measure be set as condensation product catalyst 10g, 1,2- oxepane (being also recorded as EH) 580g, The amount of ethylene oxide is set as 399g by glycidyl methacrylate 110g and n-hexane 3750g, in addition to this with reality It applies the identical step of example 1 and obtains copolyether 517g.The copolymerization group of obtained copolyether becomes, from ethylene oxide 74 moles of % of structural unit, 22 moles of % of structural unit from 1,2- oxepane, glycidyl methacrylate is come from 4 moles of % of structural unit.The copolymerization composition and weight average molecular weight of obtained copolyether are as shown in table 1.

(embodiment 3)

By feeding intake when polymerizeing and its measure be set as condensation product catalyst 10g, 1,2- epoxy butane (being also recorded as EB) 480g, The amount of ethylene oxide is set as 644g by glycidyl methacrylate 126g and n-hexane 3750g, in addition to this with reality It applies the identical step of example 1 and obtains copolyether 806g.In addition, on one side with the polymerization of gas-chromatography tracking 1,2- epoxy butane Rate gradually adds ethylene oxide on one side.The copolymerization group of obtained copolyether becomes, the structural unit 68 from ethylene oxide Mole %, 28 moles of % of structural unit, the structural unit 4 from glycidyl methacrylate from 1,2- epoxy butane Mole %.The copolymerization composition and weight average molecular weight of obtained copolyether are as shown in table 1.

(comparative example 1)

The inside of the stainless steel reactor of the jacketed of capacity 10L is replaced with nitrogen, above-mentioned condensation product catalysis is added Agent 10g, propylene oxide (being also recorded as PO) 144g and the n-hexane 3750g as solvent track epoxy with gas-chromatography on one side The aggregate rate of propane gradually adds ethylene oxide 1106g on one side.Methanol 16g is added after 28 DEG C maintain 8 hours in reaction temperature Stop polymerization reaction.After taking out granular polymer by decantation, under reduced pressure, polyethers copolymerization is obtained within dry 8 hours at 40 DEG C Object 1086g.The copolymerization group of obtained copolyether becomes, and 9 moles of % of structural unit from propylene oxide, comes from epoxy second 91 moles of % of structural unit of alkane.The copolymerization composition and weight average molecular weight of obtained copolyether are as shown in table 1.

(comparative example 2)

By feeding intake when polymerizeing and its measures and be set as condensation product catalyst 10g, propylene oxide 59g, allyl glycidyl ether The amount of ethylene oxide is set as 1015g by (being also recorded as AGE) 175g and n-hexane 3750g, in addition to this with comparative example 1 Identical step obtains copolyether 1007g.In addition, on one side with gas-chromatography tracking propylene oxide aggregate rate, on one side by Secondary addition ethylene oxide.The copolymerization group of obtained copolyether becomes, and 4 moles of % of structural unit from propylene oxide, comes From the structural unit mole 90% of ethylene oxide, 6 moles of % of structural unit of allyl glycidyl ether.Obtained polyethers copolymerization The copolymerization composition and weight average molecular weight of object are as shown in table 1.

(comparative example 3)

By feeding intake when polymerizeing and its measures and be set as condensation product catalyst 10g, phenyl glycidyl ether (being also recorded as PhGE) The amount of ethylene oxide is set as 346g by 536g, glycidyl methacrylate 68g and n-hexane 4050g, in addition to this with Step same as Example 1 obtains copolyether 881g.The copolymerization group of obtained copolyether becomes, and comes from epoxy second 66 moles of % of structural unit of alkane, 30 moles of % of structural unit from phenyl glycidyl ether, Glycidyl methacrylate is come from 4 moles of % of structural unit of glyceride.The copolymerization composition and weight average molecular weight of obtained copolyether are as shown in table 1.

In order to measure as be described hereinafter the copolyether that above-described embodiment 1-3 and comparative example 1-3 are obtained sheet resistance value and Water absorption rate, such as following production test films.

The production > of < test film

The copolyether of the copolyether of embodiment 1-3 and comparative example 1-3 is paved on mold respectively, and with temperature The vacuum hotpressing machine that degree is set as 160 DEG C is suppressed 2 minutes, the polymer sheet of 1mm thickness is configured to, as embodiment 1-3 and ratio Compared with the test film of example 1-3.

The drying > of < test film

For each test film of embodiment 1-3 and comparative example 1-3,48 are carried out in the drying box for being adjusted to -50 DEG C of dew point After hour status adjustment, the weight of measurement test piece.Using the weight as the weight under drying regime.

The measurement > of sheet resistance value of the < at 23 DEG C, 50%RH, water absorption rate

For each test film of dry embodiment 1-3 and comparative example 1-3,23 DEG C of temperature are being adjusted to, humidity 50%RH 48 hours status adjustments of progress in the constant temperature and humidity cabinet of (being also shown as " 23 DEG C × 50%RH " or " 23 DEG C 50% " below), and The measurement of sheet resistance value is carried out in same constant temperature and humidity cabinet.Measurement using insulating-resistance meter (Mitsubishi chemical Co., Ltd's system, Hiresta UX MCP-HT800), apply 100 volts of voltage, the resistance value after reading 1 minute calculates sheet resistance value.Measurement As a result it is recorded in table 1.

In addition, measurement has carried out 48 hours state tune in the constant temperature and humidity cabinet for being adjusted to 23 DEG C of temperature, humidity 50%RH The weight of the test film of section is calculated by the following formula by the increment rate of the weight of the test film under drying regime, as 23 DEG C, the water absorption rate under 50%RH, merging is recorded in table 1.

Measurement > of the < in the sheet resistance value under 10 DEG C, 15%RH and the sheet resistance value at 35 DEG C, 85%RH

In addition, the surface electricity for the embodiment 2,3 of table 1 and each test film of Comparative Examples 1 and 2, at 10 DEG C, 15%RH Resistance value and the sheet resistance value at 35 DEG C, 85%RH are measured as following.

That is, being adjusted to 10 DEG C of temperature, humidity for each test film of dry embodiment 2-3 and comparative example 1-2 (low temperature and low humidity condition also is indicated as " 10 DEG C × 15%RH " or " 10 DEG C 15% " to 15%RH below.) constant temperature and humidity cabinet in into 48 hours status adjustments of row, and carry out in same constant temperature and humidity cabinet the measurement of the sheet resistance value of each example.

For each test film of dry embodiment 2-3 and comparative example 1-2, it is being adjusted to 35 DEG C of temperature, humidity 85%RH It is small that 48 are carried out in the constant temperature and humidity cabinet of (high temperature and humidity condition also is indicated as " 35 DEG C × 85%RH " or " 35 DEG C 85% " below) When status adjustment, and carry out in same constant temperature and humidity cabinet the measurement of the sheet resistance value of each example.

Measurement uses insulating-resistance meter (Mitsubishi chemical Co., Ltd's system, Hiresta UX MCP-HT800), applies 100 volts Voltage, read 1 minute after resistance value calculate sheet resistance value.Measurement result is recorded in table 2.

< cosmetic variation evaluates >

By each test film of dry embodiment 1-3 and comparative example 1-3 in the perseverance for being adjusted to 35 DEG C of temperature, humidity 85%RH 48 hours status adjustments are carried out in constant temperature and humidity slot, with the cosmetic variation under benchmark visual valuation hot and humid environment below.Its The results are shown in Table 1.

Zero: without buckling deformation

×: there is buckling deformation

[table 1]

[table 2]

The evaluation of each copolyether obtained in embodiment and comparative example is for example following.As can be known from Table 1, water absorption rate is The copolyether of the embodiment 1-3 of 1% front and back is good on the point of the cosmetic variation in hot and humid environment.It can be with epoxy Ethane copolymerization alkyl epoxy ethane among, using the scope of the invention outside the propylene oxide constituted with carbon atom number 3 comparison The copolyether of example 1-2, compared with the copolymer of embodiment 1-3, although sheet resistance value and in no way inferior, water absorption rate Height, it is obvious poor on the point of the cosmetic variation under hot and humid environment.The copolyether sheet resistance value of comparative example 3 is high, On the equilibrium response of semiconduction and water absorption rate, the copolyether than embodiment 1-3 is poor.

In addition, in table 2, the copolyether of embodiment 2-3, in low temperature, low-moisture conditions and high temperature, high humidity Under, for 1.0 × 10⁸~1.0 × 10¹²The polyethers of the polyether polymer of the sheet resistance value of (Ω/sq.), Comparative Examples 1 and 2 is total Polymers is under low temperature, low-moisture conditions and high temperature, high humidity, with the wide sheet resistance value of range, in antistatic material Deng use on the way be undesirable result.

The embodiment > of < formed body

(embodiment 4)

The copolyether that embodiment 3 obtains is dissolved in tetrahydrofuran in a manner of as 15 weight % of solid component concentration In after, relative to 100 parts by weight of copolyether be added Photoepolymerizationinitiater initiater Irgacure907 (2- methyl-1-(4- methyl mercapto Phenyl) -2- morpholinopropane -1- ketone) 1.5 parts by weight, modulate uniform solution.Drip a certain amount of solution in PET film Afterwards, it is coated with application member, makes tetrahydrofuran evaporation that the film of uniform 100 μm of film thickness be made.It is light source using high-pressure sodium lamp UV irradiating machine, 1J/cm²Irradiation obtains crosslinked film (formed body).

The drying > of < formed body

For the formed body of embodiment 4,48 hours status adjustments are carried out in the drying box for being adjusted to -50 DEG C of dew point.

The measurement > of < sheet resistance value

For the formed body of dry embodiment 4, it is being adjusted to 10 DEG C of temperature, humidity 15%RH (low temperature and low humidity condition) 48 hours status adjustments are carried out in constant temperature and humidity cabinet, and the sheet resistance value of above-mentioned formed body is carried out in same constant temperature and humidity cabinet Measurement.

For the formed body of dry embodiment 4, in the constant temperature and humidity cabinet for being adjusted to 23 DEG C of temperature, humidity 50%RH into 48 hours status adjustments of row, and carry out in same constant temperature and humidity cabinet the measurement of the sheet resistance value of above-mentioned formed body.

In addition, being adjusted to 35 DEG C of temperature, humidity 85%RH (high temperature and humidity item for the formed body of dry embodiment 4 Part) constant temperature and humidity cabinet in carry out 48 hours status adjustments, carried out in same constant temperature and humidity cabinet above-mentioned formed body surface electricity The measurement of resistance value.

Measurement uses insulating-resistance meter (Mitsubishi chemical Co., Ltd's system, Hiresta UX MCP-HT800), applies 100 volts Voltage, read 1 minute after resistance value calculate sheet resistance value.Measurement result is recorded in table 3.

< environmental turbulence evaluates >

Be based respectively on that above-mentioned sheet resistance value measures under 10 DEG C × 15%RH environment, 23 DEG C × 50%RH environment Under, the sheet resistance value under 35 DEG C × 85%RH environment, acquire the sheet resistance relative to 23 DEG C × 50%RH (standard environment) The environmental turbulence value of value.The results are shown in Table 3 for it.In addition, the variation of the sheet resistance value relative to standard environment is smaller, environment Interdependence is smaller.

The environmental turbulence value of above-mentioned sheet resistance value is calculated: 10 DEG C × 15%RH environment by the difference of following two numerical value Under sheet resistance value common logarithm and the sheet resistance value under 23 DEG C × 50%RH environment common logarithm difference, and, The common logarithm of sheet resistance value under 23 DEG C × 50%RH environment is normal with the sheet resistance value under 35 DEG C × 85%RH environment With the difference of logarithm.More specifically, being calculated using calculating formula below.

Environmental turbulence value=[log of sheet resistance value₁₀(sheet resistance value under 10 DEG C × 15%RH)-log₁₀(23℃ Sheet resistance value under × 50%RH)]-[log₁₀(sheet resistance value under 23 DEG C × 35%RH)-log₁₀(35 DEG C × 85%RH Under sheet resistance value)]

[table 3]

Next, the embodiment as addition conductivity-imparting agent, shows following embodiment 5,6 and embodiment 7.

(embodiment 5)

Copolyether obtained in embodiment 3 is dissolved in tetrahydro in a manner of becoming 15 weight % of solid component concentration After in furans, (2- methyl-1-(the 4- first of Photoepolymerizationinitiater initiater Irgacure 907 is added relative to 100 parts by weight of copolyether Sulfenyl phenyl) -2- morpholinopropane -1- ketone) 1.5 parts by weight, and sodium salt is added relative to 100 parts by weight of copolyether (trifluoromethanesulfonic acid sodium, Tokyo Chemical Industry Co., Ltd's system) 5 parts by weight, modulate uniform solution.Drip one in PET film It after quantitative solution, is coated with application member, makes tetrahydrofuran evaporation that the film of uniform 100 μm of film thickness be made.Use high-pressure sodium lamp As the UV irradiating machine of light source, 1J/cm²Irradiation obtains crosslinked film (formed body).

(embodiment 6)

Copolyether obtained in embodiment 3 is dissolved in tetrahydro in a manner of becoming 15 weight % of solid component concentration After in furans, (2- methyl-1-(the 4- first of Photoepolymerizationinitiater initiater Irgacure 907 is added relative to 100 parts by weight of copolyether Sulfenyl phenyl) -2- morpholinopropane -1- ketone) 1.5 parts by weight, and sylvite is added relative to 100 parts by weight of copolyether (trifluoromethanesulfonic acid potassium, Tokyo Chemical Industry Co., Ltd's system) 10 parts by weight, modulate uniform solution.It drips in PET film It after a certain amount of solution, is coated with application member, makes tetrahydrofuran evaporation that the film of uniform 100 μm of film thickness be made.Utilize high pressure Mercury lamp is the UV irradiating machine of light source, 1J/cm²Irradiation obtains crosslinked film (formed body).

For formed body obtained in above-described embodiment 5 and embodiment 6, surface electricity is carried out similarly with above-described embodiment 4 The measurement of resistance value and environmental turbulence evaluation.Its result is as described in Table 4.

[table 4]

(embodiment 7)

By 20 parts by weight of copolyether obtained in embodiment 3 and sylvite (trifluoromethanesulfonic acid potassium, Tokyo chemical conversion industry strain Formula commercial firm system) it 5 parts by weight, after the mixing of ABS resin (EX-18A, UMG ABS Ltd.'s system) 75 parts by weight, utilizes and is vented double spiral shells Bar extruder melting mixing, obtains resin combination.By above-mentioned resin combination using injection (mo(u)lding) machine (model " SE18DUZ ", Sumitomo Heavy Industries, Ltd's system), it is shaped with the condition of 250 DEG C of temperature cylinder, 70 DEG C of mold temperature, obtains formed products. Then it is cut out from the formed products and obtains test film (40mm square, 1mm are thick).It is same as above-described embodiment 4 for the test film Ground carries out the measurement and environmental turbulence evaluation of sheet resistance value.Its result is as described in Table 5.

[table 5]

Next, compare the formed products (embodiment 8) obtained using copolyether of the invention, with use the present invention with The characteristic for the formed products (comparative example 3) that outer copolyether obtains.

(embodiment 8)

By 20 parts by weight of copolyether obtained in embodiment 3 and ABS resin (EX-18A, UMG ABS Ltd.'s system) After the mixing of 80 parts by weight, using vented twin screw extruder melting mixing, resin combination is obtained.Above-mentioned resin combination is made With injection (mo(u)lding) machine (model " SE18DUZ ", Sumitomo Heavy Industries, Ltd's system), with 250 DEG C of temperature cylinder, mold temperature 70 DEG C of condition forming, obtains formed products.Then it is cut out from the formed products and obtains test film (40mm square, 1mm are thick).

(comparative example 3)

20 parts by weight of copolyether that embodiment 3 obtains are changed to 20 weight of copolyether that comparative example 2 obtains Part, identical operation is carried out with embodiment 8 in addition to this, obtains test film.

For above-mentioned each test film, the measurement of sheet resistance value is carried out similarly with above-described embodiment 4 and environmental turbulence is commented Valence.Its result is as described in Table 6.

< ocular estimate >

Above-mentioned test film is impregnated 7 days in 23 DEG C of water, it is such as following, whether bubble evaluation appearance is generated according to surface. Its result is as described in Table 6.

It does not generate bubble (appearance is good): zero

It generates bubble (bad order): ×

[table 6]

It is from the result of above-described embodiment 4-8 and comparative example 3 it is found that total using polyethers of the invention in the preparation of formed products When polymers, even if there are various, the sheet resistance values for the formed products that can also inhibit with the blending objects of copolyether Environmental turbulence.

Industrial Availability

Polyether polymer of the invention is as above constituted, and sheet resistance value is under conditions of 23 DEG C, 50%RH；And 10 DEG C, 15%RH and 35 DEG C, under conditions of 85%RH；At least one of within the limits prescribed, good semiconduction is shown While, good with the equilibrium response of water absorption rate, shape stability is good.Especially in low temperature of the invention, low-moisture conditions And under high temperature, high humidity, there is stable sheet resistance value.Although copolyether is blended in resin, makees in rubber For antistatic material utilization, but be also contemplated that from now on as have both elasticity or resistance to chemical reagents as rubber, heat resistance etc. prevent it is quiet The utilization of electric material monomer.

Claims

1. a kind of polyether polymer, which is characterized in that it at least meets following one:

Water absorption rate at 23 DEG C, 50%RH is 1.5 weight % hereinafter, and sheet resistance value is 1.0 × 10¹²(Ω/sq.) with Under；And

It is 1.0 × 10 in the sheet resistance value under 10 DEG C, 15%RH and the sheet resistance value at 35 DEG C, 85%RH⁸~1.0 ×10¹²(Ω/sq.)。

2. polyether polymer according to claim 1, wherein it contains the structural unit 65-99 from (A) ethylene oxide Molar percentage, the oxirane monomers constituted from (B) with 4 or more carbon atom number structural unit 35-1 molar percentage, There is the structural unit 0-10 molar percentage of the oxirane monomers of cross-linking functional group from (C).

3. polyether polymer according to claim 1 or 2, wherein it contains the structural unit from (A) ethylene oxide 65-90 molar percentage comes from (B) with the structural unit 30-5 Mole percent of the carbon atom number 4-10 oxirane monomers constituted Than, from (C) have cross-linking functional group oxirane monomers structural unit 1-8 molar percentage.

4. polyether polymer according to claim 2, wherein the ethylene oxide that (B) is constituted with 4 or more carbon atom number Monomer is the oxirane monomers with alkyl or alkoxy.

5. the polyether polymer according to any one of claim 2-4, wherein (C) has cross-linking functional group Oxirane monomers be glycidyl methacrylate, allyl glycidyl ether.

6. a kind of composition contains polyether polymer or its cross-linking agent described in any one of claim 1-5, Yi Jixuan At least one of self-conductance electrical property imparting agent, rubber, resin and solvent.

7. a kind of formed body is made using polyether polymer described in any one of claim 1-6 or composition Formed body.