JP6921700B2 - Antistatic resin composition - Google Patents

Description

The present invention relates to an antistatic resin composition. More specifically, the present invention relates to an antistatic resin composition containing a cyclic polyether ester and a thermoplastic resin.

The molded body of the thermoplastic resin is used for housings of home appliances and electronic devices. In these molded bodies, it is desired to prevent static electricity, and a method of kneading a polymer-type antistatic agent is known as a method of imparting antistatic properties to a thermoplastic resin. However, it is necessary that the polymer-type antistatic agent and the thermoplastic resin are incompatible with each other. Therefore, the antistatic agent tends to be unevenly distributed on the resin surface, the antistatic agent bleeds out in the process of using the molded product, and the antistatic agent is gradually lost, so that sufficient durability cannot be obtained. was there. Further, in order to obtain a sufficient antistatic effect, a large amount of antistatic agent must be added, which causes a problem that the resin physical characteristics and appearance of the molded product are deteriorated.

A specific polyether / polyolefin block polymer as an antistatic resin composition that can impart excellent antistatic properties with excellent durability by adding a smaller amount than before so as not to affect the resin physical properties and appearance of the molded product. (See Patent Document 1) and the like are known.
However, the resin compositions described in Patent Document 1 and the like also do not have sufficient antistatic properties and their sustainability, and resin compositions having further excellent antistatic properties and their sustainability are desired.

Japanese Unexamined Patent Publication No. 2012-97239

An object of the present invention is to provide an antistatic resin composition having excellent antistatic properties and its durability.

The present inventors have arrived at the present invention as a result of studies for achieving the above object. That is, the present invention is an antistatic resin composition containing a cyclic polyether ester (A) represented by the general formula (1) and a thermoplastic resin (B) , wherein the thermoplastic resin (B) is polypropylene. And / or an antistatic resin composition containing a block polymer (C) containing a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b), including polypropylene.

In the general formula (1), R ¹ is a linear or branched alkylene group having 3 to 16 carbon atoms. R ² is an alkylene group having 2 to 4 carbon atoms. m is an integer of 1 to 3, n is an integer of 1 - 2000, m pieces is ^{R 1} may be different even in the same, m × n pieces is ^{R 2} is also the same It may be different.

The antistatic resin composition of the present invention is excellent in antistatic property and its durability.

The antistatic resin composition of the present invention contains a cyclic polyether ester represented by the above general formula (1) and a thermoplastic resin.

In the general formula (1), R ¹ is a hydrocarbon group having 2 to 21 carbon atoms. At ^{least one hydrogen atom of R 1} may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group.

Examples of the hydrocarbon group having 2 to 21 carbon atoms include an alkylene group having 2 to 21 carbon atoms, an alkenylene group having 2 to 21 carbon atoms, an arylene group having 6 to 21 carbon atoms, and an aralkylene group having 7 to 21 carbon atoms. Be done.

Examples of the alkylene group having 2 to 21 carbon atoms include a linear alkylene group having 2 to 21 carbon atoms (ethylene group, trimethylene group, tetramethylene group, pentamethylene group and n-henicosanylene group) and a branched alkylene group having 3 to 21 carbon atoms. Groups (1-methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethyltrimethylene group, 1 -N-Butyl trimethylene group, 1-n-hexyl trimethylene group, 1-n-propyl trimethylene group, 1-n-heptilt methylene group, 1-n-octyl methylene group, 1-n-heptyl tetramethylene group Methylene group and 1-n-octylethylene group, etc.) and cycloalkylene group having 4 to 21 carbon atoms (cyclobutylene group, cyclopentylene group, 2-methylcyclopentylene group, cyclohexylene group, 1,3-dimethylcyclohexyl) Silen group, cycloheptylene group, 1-ethylcyclopentylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cycloundecylene group, cyclododecylene group, cyclotriderene group, cyclotetradecylene group, cyclopentadecylene group, cyclohexyl Sadecylene group, cycloheptadecylene group, cyclooctadecylene group, cyclononadesilene group, cycloeicocilene group, norbornylene group, dicyclopentylene group, isopropyridene dicyclohexylene group, cyclohexanedimethylene group, etc.) Can be mentioned.

Examples of the alkenylene group having 2 to 21 carbon atoms include a linear alkenylene group having 2 to 21 carbon atoms (etenylene group, propenylene group, henicosenylene group, etc.) and a branched alkenylene group having 3 to 21 carbon atoms (1-ethylethenylene group, 1, 2-Dimethyl ethenylene group, 1-butyl ethenylene group, 1-hexyl ethenylene group, 1-octyl ethenylene group, etc.) and the like can be mentioned.

Examples of the arylene group having 6 to 21 carbon atoms include an o-, p- or m-phenylene group, a 2,4-naphthylene group, a biphenylene group, a terphenylene group, an anthylene group, a phenylenelene group, a fluorenylene group, a pyrenylene group and a group. Can be mentioned.

Examples of the aralkylene group having 7 to 21 carbon atoms include a phenylmethylene group, a diphenylmethine group, a 1-phenylethylene group, an o-phenylene ethyl group and a naphthylmethylene group.

Examples of the group in which at least one of the hydrogen atoms of these groups is substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group include a 1-bromo-trimethylene group, a 1-acetyl-trimethylene group and a 1-methoxy-trimethylene group. And 1-phenoxy-trimethylene group and the like.

Of these, R ¹ is preferably a linear or branched alkylene group having 3 to 16 carbon atoms, and is an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a tetradecamethylene group, a methylethylene group, 1 -N-propyl trimethylene group, 1-n-heptilt methylene group, 1-n-octyl methylene group, 1-n-heptyl tetramethylene group, 1-n-hexyl trimethylene group, 1-n-hexyl tetramethylene group More preferably, a methylene group, a 1-n-undecyl trimethylene group and a 1-n-undecyltetramethylene group.

In the general formula (1), R ² is a divalent hydrocarbon group having 2 to 8 carbon atoms. Among the divalent hydrocarbon groups having 2 to 8 carbon atoms, preferred ones include a phenylethylene group and an alkylene group having 2 to 4 carbon atoms, and more preferably a linear alkylene group having 2 to 4 carbon atoms (ethylene). Groups, propylene groups, butylene groups, etc.) and branched alkylene groups having 3 or 4 carbon atoms (methylethylene group, ethylethylene group, methylpropylene group, 2-methylpropylene, etc.) are mentioned, and particularly preferably 2 to 4 carbon atoms. Is a linear alkylene group and a branched alkylene group having 3 to 4 carbon atoms, most preferably an ethylene group and a propylene group.

In the above general formula (1), m means the number of repetitions of the unit represented by ^{[R 1} CO (OR ² ) _n O], and n is the number of added moles of the oxyalkylene group represented by ^{(OR 2).} Means.

m is an integer of 1 to 3, preferably 1. n is an integer of 1 to 2000, and the number of added moles (n) of the oxyalkylene group of the cyclic polyether ester (A) is from the viewpoint of improving compatibility with the thermoplastic resin and improving antistatic property. It is preferably 5 to 1000, more preferably 5 to 500, and particularly preferably an integer of 5 to 100.
Incidentally, when m is 2 or 3, m pieces is R ¹ may be different even in the same, preferably the same. Further, when m is 2 or 3 and / or n is an integer of 2 or more, m × n R ^2s may be the same or different.

If the m × n is ^{R 2} are different, the composition of the m × n is ^{R 2} is, Polym. Chem. , 2014, 5, 6905. It can be measured and analyzed by time-of-flight mass spectrometry (also referred to as MALDI-TOF MS) by the matrix-assisted laser desorption / ionization method described in 1.

As the cyclic polyether ester (A) contained in the antistatic resin composition of the present invention, if m is 1 to 3, the number of added moles of the oxyalkylene group represented by n in the general formula (1) is A cyclic polyether ester (A) having a specific value may be used, or a plurality of cyclic polyether esters (A) having different values of n may be used in combination.
When a plurality of cyclic polyether esters (A) having different values (n) of the number of added moles of the oxyalkylene group represented by n in the general formula (1) are used in combination, the oxy of the cyclic polyether ester (A) to be used is used. The value and ratio of the number of added moles of the alkylene group can be adjusted according to the type of the thermoplastic resin and the like.

The adjustment of the values of m and n in the general formula (1) and the adjustment of the content of the cyclic polyether ester (A) having n, which is a value in a specific range, are the active hydrogen-containing groups used in the alkenylation reaction described later. It can be carried out by adjusting the ratio of the lactone having no ester and the alkylene oxide having 2 to 8 carbon atoms and changing the method of adding the alkylene oxide. For example, the alkylene oxide reacting with the lactone having no active hydrogen-containing group. The content of the cyclic polyether ester (A) having a specific value n can be increased by reacting stepwise, and the total proportion of the cyclic polyether ester (A) in which n has a value in a certain range is increased. be able to.
The m value and n value of the cyclic polyether ester (A) are described in Polymer. Chem. , 2014, 5, 6905. It can be analyzed and confirmed by the MALDI-TOF MS described in.

The number average molecular weight (hereinafter abbreviated as Mn) of the cyclic polyether ester (A) contained in the antistatic resin composition of the present invention can be adjusted according to the type of the thermoplastic resin and the like, but it is thermally. From the viewpoint of compatibility with the plastic resin, it is preferably 200 to 350,000, more preferably 200 to 10000, and particularly preferably 200 to 6000.
The Mn of the cyclic polyether ester (A) can be set in a preferable range by adjusting the number of moles of oxyalkylene groups added.

The Mn of the cyclic polyether ester (A) can be measured by gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions.
-Device: "Waters Alliance 2695" [manufactured by Waters]
-Column: "Guardcolum SuperH-L" (1), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 connected 1 each" [all manufactured by Tosoh Corporation]
-Sample solution: 0.25 wt% tetrahydrofuran solution-Solution injection amount: 10 μL
・ Flow rate: 0.6 mL / min ・ Measurement temperature: 40 ° C
・ Detection device: Refractive index detector ・ Reference material: Standard polyethylene glycol

As the cyclic polyether ester (A) used in the antistatic resin composition of the present invention, preferably, R ¹ is a tetradecamethylene group, R ² is an ethylene group and a propylene group, and m is 1 to 1. 3. Cyclic polyether ester compositions in which n is 5 to 500 can be mentioned.

The cyclic polyether ester (A) used in the antistatic resin composition of the present invention uses a lactone having no active hydrogen-containing group and an alkylene oxide having 2 to 8 carbon atoms to form the above-mentioned active hydrogen-containing group. It can be obtained by carrying out a reaction (also referred to as an alkoxylation reaction) in which an oxyalkylene group is inserted between the carbonyl of the ester group of the lactone that does not have it and the oxygen atom. The alkoxylation reaction may be carried out by using a lactone having no active hydrogen-containing group and an alkylene oxide having 2 to 8 carbon atoms with a catalyst used for a ring-opening addition reaction of the alkylene oxide, an alkoxylation reaction or the like. good.
The active hydrogen-containing group means a functional group to which an alkylene oxide can be ring-opened and added, and examples thereof include a hydroxyl group, a carboxyl group, a mercapto group and an amino group.

In the alkoxylation reaction, a side reaction in which a cyclic polyether ester represented by the general formula (1) is further inserted and added to the cyclic polyether ester represented by the general formula (1) produced in the alkoxylation reaction. May occur.
Therefore, the cyclic polyether ester (A) obtained by the alkoxylation reaction is not only the cyclic polyether ester in which m = 1 in the general formula (1), but also the [R ¹ CO (OR) in the general formula (1). comprises ²⁾ n _O] cyclic polyether ester having two in one molecule a unit represented by (i.e. m = 2) and / or 3 have a cyclic polyether ester (i.e. m = 3), the reaction product Is a composition containing a cyclic polyether ester having 1 to 3 units represented by ^{[R 1} CO (OR ² ) _n O] in the general formula (1) as a main component.
The composition of the cyclic polyether contained in the reaction product is described in Polymer. Chem. , 2014, 5, 6905. It can be analyzed and confirmed by the MALDI-TOF MS described in.

The cyclic polyether ester (A), which is a reaction product of the alkoxylation reaction, is a mixture, and is further fractionated and purified by a known method such as a gel permeation method or silica gel column chromatography to obtain specific m and n. Cyclic polyether ester (A) having the above can be obtained. The cyclic polyether ester (A) contained in the antistatic resin composition of the present invention was obtained by fractionating and purifying the reaction product even if the reaction product of the alkoxylation reaction was used as it was. Cyclic polyether esters may be used.

The lactone having no active hydrogen-containing group used to obtain the cyclic polyether ester (A) has one hydroxyl group and one carboxyl group, and excludes the above-mentioned one hydroxyl group and one carboxyl group. A cyclic ester obtained by intramolecularly dehydrating a hydroxyl group and a carboxyl group of a monohydroxycarboxylic acid having 4 to 22 carbon atoms and which does not have another active hydrogen-containing group can be used. As a method for synthesizing a lactone by intramolecular dehydration, a method of heat dehydration by a known method, J.A. S. Nimitz, R.M. H. Wollemberg, Terahedron Lett. A known synthetic method can be used as described in 1978, 19, 3523, and a method using an enzyme such as lipase.

As a monohydroxycarboxylic acid having 4 to 22 carbon atoms which does not have another active hydrogen-containing group other than one hydroxyl group and one carboxyl group, a linear hydroxycarboxylic acid having 4 to 22 carbon atoms (3-hydroxy) Propanic acid, 4-hydroxybutyric acid, 5-hydroxypentanoic acid, 6-hydroxyhexanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, 4-hydroxy-2-butenoic acid, etc.) and branches with 3 to 22 carbon atoms. Hydroxycarboxylic acids (3-hydroxybutanoic acid, 5-hydroxytridecanoic acid, 2-methylene-4-hydroxybutyric acid, 4-phenyl-4-hydroxybutyric acid, 2,2-dimethyl-4-hydroxybutyric acid, 4-hexyl- 4-Hydroxybutyric acid, 4-hydroxy-2-methyl-2-butenoic acid, etc.) and the like.

As the lactone having no active hydrogen-containing group, at least one hydrogen atom among the hydrogen atoms bonded to the carbon atom of the hydroxycarboxylic acid having 4 to 22 carbon atoms is a halogeno group, an acetyl group, an alkoxy group or a phenoxy. Lactones having a structure in which the hydroxycarboxylic acid substituted with a group is intramolecularly dehydrated can also be used.
Among the monohydroxycarboxylic acids having 4 to 22 carbon atoms, examples of the hydroxycarboxylic acid in which at least one of the hydrogen atoms bonded to the carbon atom is replaced with a halogeno group include 2-bromo-4-hydroxybutyric acid. Examples of the hydroxycarboxylic acid substituted with an acetyl group include 2-acetyl-4-hydroxybutanoic acid, and examples of the hydroxycarboxylic acid substituted with an alkoxy group include 2-methoxy-4-hydroxybutyric acid. Examples of the hydroxycarboxylic acid substituted with a phenoxy group include 2-phenyl-4-hydroxybutylic acid.

As the lactone having no active hydrogen-containing group, β-lactone (β-propiolactone, β-butyrolactone, etc.), γ-lactone (γ-butyrolactone, etc.), δ-lactone (δ-valerolactone, etc.) are preferable. Etc.), ε-lactone (ε-caprolactone, etc.), lactone having a long-chain alkyl group (γ-enant lactone, γ-undecanolactone, γ-dodecalactone, δ-dodecanolactone, etc.), large cyclic lactone (15) -Pentadecanolactone), aromatic lactone (3,4-dihydrocmarin) and the like. These lactones may be used alone or in combination of two or more.

Examples of the alkylene oxide having 2 to 8 carbon atoms used in the alkoxylation reaction (hereinafter, may be abbreviated as AO) include ethylene oxide, 1,2-propylene oxide, oxetane, 1,2-, 1,3-1, 1. , 4- or 2,3-butylene oxide, styrene oxide and the like, preferably alkylene oxides having 2 to 3 carbon atoms (ethylene oxide, 1,2-propylene oxide and oxetane), ethylene oxide and 1,2-propylene oxide. Oxides are more preferred.
The alkylene oxide may be used alone or in combination of two or more. When two or more types are used in combination, the binding form may be random, block, or both, but the antistatic improver is efficiently supplemented and the functional deterioration due to cleaning is suppressed. It is preferable to use it alone or in a block.
When two or more kinds as alkylene oxides, resulting circular polyetherester (A) are the compounds of formula (1) as the n is R ^2, different types of R ² corresponding to the type of alkylene oxide used It is a cyclic polyether ester having.

The alkoxylation reaction is preferably carried out in the presence of a catalyst. As the catalyst used in the reaction step, hydroxides of metals (boron, tin, nickel, zinc, aluminum, etc.), inorganic acids (sulfuric acid, phosphoric acid, etc.), alkali metals (lithium, sodium, potassium, cesium, etc.) are hydroxylated. Two types of metals such as substances, amine compounds (diethylamine, triethylamine, etc.), phosphazene, complex metal cyanide complex catalysts (Japanese Patent Laid-Open No. 2005-53952, JP-A-2016-6203, etc.) (Metal complex catalyst, etc. containing in the molecule), an oxide composite described in JP-A-2000-354763, a composite of aluminum (hereinafter abbreviated as Al) and magnesium (hereinafter abbreviated as Mg). It can be carried out using an oxide (M1), a layered compound hydroxide (M2), a calcined product thereof (M3), or the like.

The layered double hydroxide used in the production method of the present invention is a divalent metal (Mg, Fe, Zn, Ca, Li, Ni, Co, Cu, etc.) and a trivalent metal (Al, Fe, Mn, etc.). It means an inorganic layered compound in which the above hydroxides are combined to form a laminated structure, and the general formula is [M 2 ⁺ _1-h M ^{3 +} _h (OH) ₂ ] [(W ^i- ) _{h / i} · jH. ₂ O] ^{[wherein, M 2+} is a divalent ^{metal, M 3+} is a trivalent ^{metal, W i-i-valent} anion _{^{(HCO 3 -, CO 3 2-}} , PO 4 3-, SO 4 2 ⁻ , Cl ⁻ , NO ₂ ⁻ and NO ₃ ^−, etc.), h, i and j are independent positive numbers. ], And includes hydrotalcite, motuchoreite, manaseito, stichtite, pyroaulite, tacobite, eardrite, meikisenelite and the like. These layered double hydroxides are known as clay minerals and may be contained in naturally occurring minerals or synthetically obtained.

One type of catalyst may be used alone, or two or more types may be used in combination. Of these, from the viewpoint of reaction efficiency, a composite oxide of Al and Mg (M1), hydrotalcite having Al and Mg (M2-1), and a calcined product thereof (M3) are preferable.

The composite oxide (M1) used in the present invention is not particularly limited as long as it is an oxide having Al and Mg, but preferred composite oxides include compounds represented by the following general formula (2) or (3). Can be mentioned.
[AMGO ・ Al ₂ O ₃・ bH ₂ O] (2)
_[Mg s _Al t _{O u]} (3)

In the general formula (2), a and b are independent positive numbers. In the general formula (3), s, t and u are independent positive numbers. From the viewpoint of reactivity, s / t is preferably 0.1 or more and less than 5.
Examples of the composite oxide (M1) include 2.5 MgO, Al ₂ O ₃ , bH ₂ O, Mg _0.7 Al _0.3 O _{1.15, and the} like, respectively, of which are Kyoward 300 [Kyowa Chemical Industry Co., Ltd.] Manufactured by] and Kyoward 2000 [manufactured by Kyowa Chemical Industry Co., Ltd.], etc. can be obtained from the market.

Examples of the hydrotalcite (M2-1) used in the present invention include compounds represented by the following general formula (4).
[Mg _1-c Al _c (OH) ₂ ] ^{c +} [CO _{3c / 2} · dH ₂ O] ^c− (4)

Further, in the general formula (4), c is a number satisfying 0 <c ≦ 0.33, and d is a number satisfying 0 <d ≦ 1.0.

The hydrotalcite _{(M2-1), Mg 6 Al 2} (OH) 16 CO 3 · 4H 2 O and _{Mg 4.5 Al 2 (OH) 13} CO 3 · 3.5H 2 O and the like, respectively It can be obtained from the market as Kyoward 500 [manufactured by Kyowa Chemical Industry Co., Ltd.] and Kyoward 1000 [manufactured by Kyowa Chemical Industry Co., Ltd.].

As the hydrotalcite (M2-1) used in the present invention, in addition to the above compounds, known minerals described in West German Patent Publication No. 1592126 and European Patent Publication No. 0207811 can also be used.

As for (M1) and (M2-1), one type may be used alone, or two or more types may be used in combination.
Among these, preferred in view of reactivity is given to the composite oxide (M1), further preferred is _{2.5MgO · Al 2 O 3 · nH} 2 O (n is a positive number) and _Mg 0.7 Al _{0 .3} O _1.15 .

The calcined product of the composite oxide (M1) of Al and Mg or the calcined product of hydrotalcite (M2-1) having Al and Mg (M3) is the composite oxide (B1) of Al and Mg or Hydrotalcite (M2-1) can be obtained by heat treatment in an air atmosphere, preferably in a nitrogen stream, preferably at 400 to 1500 ° C. (more preferably 600 to 1000 ° C.) for 1 to 4 hours. can.

In the reaction step of alkenylation, the content of the catalyst is not particularly limited, but from the viewpoint of reaction rate and filtration efficiency, 0.001 to 20% by weight is preferable, and more preferably 0.001 to 20% by weight based on the total weight of the lactone and the alkylene oxide. It is 0.01 to 1.0% by weight.

Further, in the alkoxylation reaction step of the lactone, a solvent may be added in addition to the lactone, the alkylene oxide and the catalyst from the viewpoint of handling.
Solvents include toluene, xylene, benzene, dimethyl sulfoxide, diglyme, triglyme, 1,4-dioxane, cyclohexane, hexane, diethyl ether, tetrahydrofuran, dimethylformamide, carbon tetrachloride, N-methylpyrrolidone, 1,2-dimethoxyethane. , 1,2-Dichloroethane, chloroform and the like.
As the solvent, one type may be used alone, or two or more types may be used in combination.
Of these, toluene and xylene are preferable from the viewpoint of miscibility with lactones and alkylene oxides.
The weight of the solvent used in the alkoxylation reaction is preferably 0 to 99% by weight, more preferably 0 to 90% by weight, based on the total weight of the cyclic compound, the cyclic ether and the catalyst from the viewpoint of reaction rate and the like. ..

In the alkoxylation reaction, the temperature of the lactone and the lactone, the alkylene oxide and, if necessary, the mixture of the catalyst and the solvent is preferably 90 to 250 ° C, more preferably 100 to 190 ° C.
The time for setting the above temperature is preferably 1 to 200 hours.

In the alkoxylation reaction, lactone, alkylene oxide, and if necessary, a catalyst and solvent are placed in the reaction apparatus, the inside of the system is replaced and sealed with an inert gas (nitrogen, argon, etc.), and the reaction temperature and reaction time are adjusted. This can be done by stirring and mixing.
As the reaction device, a known reaction device such as a mixing vessel (flask with stirrer, autoclave, etc.) to which a stirring device and a heating device are attached can be used.

In the production method of the present invention, the composition obtained by the ring expansion reaction is further filtered by a known method such as a filtration operation (method described in JP-A-2011-213864), a gel permeation method, silica gel column chromatography and the like. A purification step (hereinafter abbreviated as a purification step) may be included. By the above purification step, a cyclic polyester composition having a specific structure can be extracted.

The manufacturing process of the polyester composition of the present invention may include a catalyst removal operation. A known method can be used as a method for removing the catalyst. Specifically, in addition to the method described in JP-A-2010-6964, diatomaceous earth (Daicalite 6000, Radiolite # 700, etc.), which is a filtering agent, can be used. ), Silica gel (Wakogel, etc.), magnesium silicate (Kyoward 600, Kyoward 700), and the like. In the filtration operation, the filtration agent may be used alone or in combination of two or more, but it is preferable to use a plurality of types from the viewpoint of filtration efficiency.
Further, from the viewpoint of improving the filtration rate, it is preferable to use diatomaceous earth, and in order to improve the removal efficiency of the catalyst, it is preferable to use magnesium silicate.
The filtration operation can be performed by a known method, and examples thereof include a method in which the cyclic polyester composition or a solution thereof is passed through a filter layer in which diatomaceous earth and magnesium silicate are laminated in a layered manner. The solvent used for filtration is not limited as long as it dissolves cyclic polyester, but THF, DMF, ethyl acetate, toluene and the like are preferable from the viewpoint of dissolution efficiency.

Examples of the thermoplastic resin (B) contained in the antistatic resin composition of the present invention include polyolefin {polyethylene [polyethylene [high density polyethylene, low density polyethylene, ultrahigh molecular weight polyethylene, etc.)], polypropylene, polyisobutylene, polybutadiene, and polymethylpentene. , Polycycloolefins and copolymers thereof, and modified polyolefin resins having polar functional groups introduced therein], polyacrylic resins [polymethylmethacrylate, etc.], polystyrene {vinyl group-containing aromatic hydrocarbon homopolymers, etc. Alternatively, a copolymer containing a vinyl group-containing aromatic hydrocarbon and at least one selected from the group consisting of (meth) acrylic acid ester, (meth) acrylonitrile and butadiene as a constituent unit [polystyrene, high impact resistant polystyrene, Styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin) and styrene / methyl methacrylate copolymer (MS resin) ) Etc.}, Polyester [Polyethylene terephthalate, Polybutylene terephthalate, Polycyclohexanedimethylene terephthalate, Polybutylene adipate, Polyethylene adipate, etc.], Polyamide [Nylon 66, Nylon 69, Nylon 612, Nylon 6, Nylon 11, Nylon 12, etc. Nylon 46, Nylon 6/66 and Nylon 6/12, etc.], Polycarbonate [Polycarbonate and Polycarbonate / ABS resin alloy, etc.], Polyether [Polyethylene oxide, Polypropylene oxide, etc.], Block polymers having these skeletons, Biomass-derived resin [ Polylactic acid, polyhydroxybutyrate, polytrimethylene terephthalate, esterified starch, cellulose acetate, etc.], polyacetal (homopolymer of formaldehyde or trioxane, copolymer of formaldehyde or trioxane and alkylene oxide, etc.) and two of these. Examples thereof include the above mixtures.

The thermoplastic resin (B) preferably contains a block polymer (C) having a block of the hydrophobic polymer (a) and a block of the hydrophilic polymer (b).
When the antistatic resin composition of the present invention contains the block polymer (C), the block polymer (C) is phase-separated in the thermoplastic resin to form a conductive path by the block of the hydrophilic polymer (b). It is preferable because it has good antistatic properties.
The hydrophobic polymer (a) ^{means a polymer having a volume resistivity value exceeding 1 × 10 11} Ω · cm, and the hydrophilic polymer (b) is 1 × 10 ⁵ to 1 × 10 ¹¹ Ω. -It means a polymer having a volume resistivity value of cm. The volume specific resistance value of the hydrophilic polymer (b) is preferably 1 × 10 ⁶ to 1 × 10 ⁹ Ω · cm, and more preferably 1 × 10 ⁶ to 1 × 10 ⁸ Ω · cm. This range is preferable from the viewpoint that the antistatic property and the moisture permeability of the film are easily compatible with each other when the antistatic resin composition is formed into a film.
The volume resistivity value in the present invention is a value obtained by measuring in an atmosphere of 23 ° C. and 50% RH in accordance with ASTM D257 (1984).

[Hydrophobic polymer (a)]
Examples of the hydrophobic polymer (a) contained in the block polymer (C) include polyamide (a1), a copolymer of constituent monomers of polyamide (a1), polyolefin (a2), and polyamide-imide (a3). May be used in combination of two or more. Among these hydrophobic polymers (a), polyamide (a1) and polyolefin (a2) are preferable from the viewpoint of moisture permeability and mechanical properties.

Examples of the polyamide (a1) include a polyamide obtained by ring-opening polymerization or polycondensation of an amide-forming monomer (α) and a polycondensate of diamine (β) and a dicarboxylic acid (γ).

Examples of the polyamide (a1) include a polyamide obtained by ring-opening polymerization or polycondensation of an amide-forming monomer (α) and a polyamide obtained by polycondensation of a diamine (β) and a dicarboxylic acid (γ). Further, the copolymerization weight obtained by copolymerizing at least one kind of constituent monomers selected from the group consisting of amide-forming monomers (α), diamines (β) and dicarboxylic acids (γ). Examples of the coalescence include polyamines and polycarboxylic acids in addition to the above-mentioned polyamide (a1).

Examples of the amide-forming monomer (α) include lactam (α1-1) and aminocarboxylic acid (α1-2). Preferred lactams (α1-1) include lactams having 4 to 20 carbon atoms (caprolactam, enantractam, laurolactam, undecanolactam, etc.).
Preferable aminocarboxylic acids (α1-2) are aminocarboxylic acids having 2 to 20 carbon atoms (ω-aminocaproic acid, ω-aminoenant acid, ω-aminocapric acid, ω-aminopelargonic acid, ω-amino). Capric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and mixtures thereof, etc.) and the like.

Preferred diamines (β) are aliphatic diamines having 2 to 20 carbon atoms (ethylenediamine, propylenediamine, hexamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine and 1,20. -Eikosandiamine, etc.), alicyclic diamines with 5 to 20 carbon atoms [1,3- or 1,4-cyclohexanediamine, isophoronediamine, 4,4'-diaminocyclohexylmethane and 2,2-bis (4-) Aminocyclohexyl) propane, etc.], aromatic diamines with 6 to 20 carbon atoms [p-phenylenediamine, 2,4- or 2,6-toluylene diamine and 2,2-bis (4,4'-diaminophenyl) propane , P- or m-xylylene diamine, bis (aminoethyl) benzene, bis (aminopropyl) benzene, bis (aminobutyl) benzene, etc.] and the like.

Preferred dicarboxylic acids (γ) are aliphatic dicarboxylic acids having 2 to 20 carbon atoms (succinic acid, glutaric acid, adipic acid, pimelliic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid). , Maleic acid, fumaric acid, itaconic acid, etc.), aromatic dicarboxylic acid with 8 to 20 carbon atoms (phthalic acid, 2,6- or 2,7-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, di Phenoxyetanedicarboxylic acid, tolylene carboxylic acid, xylylene dicarboxylic acid and 5-sulfoisophthalic acid alkali metal salt, etc.), alicyclic dicarboxylic acid having 5 to 20 carbon atoms (cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid) , Cyclohexene dicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid, succinoic acid, etc.) and the like.

Specific examples of the polyamide (a1) include nylon 6,6, nylon 6,9, nylon 6,12, nylon 6, nylon 11, nylon 12, nylon 4,6, and a copolymer of nylon 6 and nylon 6,6. , A copolymer of nylon 6 and nylon 12, a copolymer of nylon 6 and nylon 6, 6 and nylon 12, and the like.

The polyolefin (a2) includes a polyolefin (a2-1) having a carboxyl group at both ends of the polymer, a polyolefin (a2-2) having a hydroxyl group at both ends of the polymer, and a polyolefin (a2) having an amino group at both ends of the polymer. -3), Polyolefin having an isocyanate group at both ends of the polymer (a2-4), Polyolefin having a carboxyl group at one end of the polymer (a2-5), Polyolefin having a hydroxyl group at one end of the polymer (a2-6). , Polyolefin (a2-7) having an amino group at one end of the polymer, polyolefin (a2-8) having an isocyanate group at one end of the polymer, and the like.
Of these, polyolefins having a carboxyl group at the end (a2-1) and polyolefins having a carboxyl group at one end of the polymer (a2-5) are preferable.
The terminal in the present invention means a terminal where the repeating structure of the monomer unit constituting the polymer is interrupted. Further, both ends mean both ends in the main chain of the polymer, and one end means one end in the main chain of the polymer.

The polyolefin (a2-1) having a carboxyl group at both ends of the polymer contains a polyolefin having both ends modifiable as a main component (preferably a content of 50% by weight or more, more preferably 75% by weight or more, and particularly preferably 80). -100% by weight), and examples thereof include polyolefins having carboxyl groups introduced at both ends of the polyolefin (a2-01). Examples of the polyolefin (a2-2) having hydroxyl groups at both ends of the polymer include polyolefins having hydroxyl groups introduced at both ends of the polyolefin (a2-01). Examples of the polyolefin (a2-3) having amino groups at both ends of the polymer include polyolefins having amino groups introduced at both ends of the polyolefin (a2-01). Examples of the polyolefin (a2-4) having an isocyanate group at both ends of the polymer include a polyolefin having an isocyanate group introduced at both ends of the polyolefin (a2-01).

The polyolefin (a2-01) whose main component is a polyolefin whose both ends can be modified includes one or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10). (Co) polymerization of the mixture [(Co) polymerization means polymerization or copolymerization. The same applies below. ] And the modified polyolefin {high molecular weight [preferably number average molecular weight (hereinafter abbreviated as Mn) 50,000 to 150,000] polyolefin is mechanically, thermally or chemically reduced. What can be obtained from} etc. are included.
Of these, a modified polyolefin is preferable from the viewpoint of easy modification and availability when introducing a carboxyl group, a hydroxyl group, an amino group or an isocyanate group, and more preferable is heat. It is a reduced polyolefin. According to the thermal reduction, as described later, a low molecular weight polyolefin having an average number of terminal double bonds per molecule of 1.5 to 2 can be easily obtained, and the low molecular weight polyolefin has a carboxyl group, a hydroxyl group, or an amino group. Alternatively, it is easy to introduce an isocyanate group or the like to modify it.

The Mn of the polymer in the present invention can be measured by gel permeation chromatography (GPC) under the following conditions.
Equipment (example): "HLC-8120" [manufactured by Tosoh Corporation]
Column (example): "TSKgelGMHXL" (2)
"TSKgel Multipore HXL-M" (1)
Sample solution: 0.3 wt% orthodichlorobenzene solution Injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 135 ° C
Detection device: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400 , 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

The heat-decomposed polyolefin is not particularly limited, but is obtained by heating a high-molecular-weight polyolefin in an inert gas (300 to 450 ° C. for 0.5 to 10 hours, for example, JP-A-3-62804). Those obtained by the method described in the publication), and those obtained by heating in air to reduce heat, etc. can be mentioned.

As the high molecular weight polyolefin used for thermal decomposition, a (co) polymer [Mn] of one kind or a mixture of two or more kinds of olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10). Is preferably 12,000 to 100,000, more preferably 15,000 to 70,000. The melt flow rate (hereinafter abbreviated as MFR; the unit is g / 10 min) is preferably 0.5 to 150, more preferably 1 to 100. ] Etc. can be mentioned. Here, MFR is a numerical value representing the melt viscosity of the resin, and the larger the value, the lower the melt viscosity. An extruded plastometer defined by JIS K6760 is used for the measurement of MFR, and the measuring method conforms to the method specified by JIS K7210 (1976). For example, in the case of polypropylene, it is measured under the conditions of 230 ° C. and a load of 2.16 kgf.
Examples of the olefin having 2 to 30 carbon atoms include an α-olefin having 2 to 30 carbon atoms and a diene having 4 to 30 carbon atoms.
Examples of α-olefins having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-icosene and 1-. Tetracosen and the like can be mentioned.
Examples of the diene having 4 to 30 carbon atoms include butadiene, isoprene, cyclopentadiene and 1,11-dodecadien.
Among the olefins having 2 to 30 carbon atoms, ethylene, propylene, α-olefin having 4 to 12 carbon atoms, butadiene, isoprene and a mixture thereof are preferable from the viewpoint of molecular weight control, and ethylene is more preferable. Propylene, α-olefins having 4 to 10 carbon atoms, butadiene and mixtures thereof, particularly preferred are ethylene, propylene, butadiene and mixtures thereof.

The Mn of the polyolefin (a2-01) is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000, from the viewpoint of moisture permeability and mechanical properties. Is.
The number of terminal double bonds in the polyolefin (a2-01) is preferably 1 to 40 per 1,000 carbon atoms, more preferably 2 to 30, and particularly preferably 2 to 30 from the viewpoint of moisture permeability and mechanical properties. Is 4 to 20 pieces.

The average number of terminal double bonds per molecule of polyolefin (a2-01) is preferably 1.1 to 5 from the viewpoint of ease of forming a repeating structure in the molecule, moisture permeability, and mechanical properties. The number is preferably 1.3 to 3, particularly preferably 1.5 to 2.5, and most preferably 1.8 to 2.2.

By using the method for obtaining a low molecular weight polyolefin by heat reduction, it is possible to easily obtain a polyolefin having an average number of terminal double bonds of 1.5 to 2 per molecule in the range of Mn 800 to 6,000. Yes [Katsuhide Murata, Tadahiko Makino, Journal of the Japanese Society of Chemistry, p. 192 (1975)].

As the polyolefins (a2-5) to (a2-8), instead of the polyolefin (a2-01), a polyolefin having a modifiable one end as a main component (preferably a content of 50% by weight or more, more preferably 75). A polyolefin (a2-02) having a weight% or more, particularly preferably 80 to 100% by weight) in which a carboxyl group, a hydroxyl group, an amino group or an isocyanate group is introduced into one end can be used.

A polyolefin (a2-02) containing a polyolefin whose one end can be modified as a main component can be obtained in the same manner as the polyolefin (a2-01), and the Mn of the polyolefin (a2-02) has moisture permeability and mechanical properties. From the viewpoint of the above, it is preferably 2,000 to 50,000, more preferably 2,500 to 30,000, and particularly preferably 3,000 to 20,000.
The number of double bonds per 1,000 carbon atoms of the polyolefin (a2-02) is preferably 0.3 to 20 from the viewpoint of controlling the molecular weight of the block polymer (C), and more preferably 0.5. ~ 15, particularly preferably 0.7-10.

The average number of double bonds per molecule of polyolefin (a2-02) is preferably 0.5 to 1 from the viewpoint of ease of forming a repeating structure in the molecule and the thermoplasticity of the block polymer (C) described later. It is 4, more preferably 0.6 to 1.3, particularly preferably 0.7 to 1.2, and most preferably 0.8 to 1.1.
Among the polyolefins (a2-02), a low molecular weight polyolefin obtained by thermal denaturation is preferable from the viewpoint of easiness of denaturation, and more preferably Mn obtained by thermal denaturation is 3, 000-20,000 polyethylene and / or polypropylene.
When a method for obtaining a low molecular weight polyolefin by heat reduction is used, a polyolefin having an Mn in the range of 6,000 to 30,000 and an average number of terminal double bonds per molecule of 1 to 1.5 can be obtained. Be done.
Since the low molecular weight polyolefin obtained by thermal decomposition has an average number of the terminal double bonds, it is easy to introduce a carboxyl group, a hydroxyl group, an amino group, an isocyanate group, or the like to modify the low molecular weight polyolefin.

The polyolefins (a2-01) and (a2-02) are obtained as a mixture thereof, but the mixture may be used as it is, or may be used after purification and separation. Of these, a mixture is preferable from the viewpoint of manufacturing cost and the like.

Hereinafter, polyolefins (a2-1) to (a2-4) having a carboxyl group, a hydroxyl group, an amino group or an isocyanate group at both ends of the polyolefin (a2-01) will be described, but a piece of the polyolefin (a2-02). Regarding the polyolefins (a2-5) to (a2-8) having these groups at the ends, the polyolefins (a2-1) to (a2-) other than replacing the polyolefin (a2-01) with the polyolefin (a2-02). It can be obtained in the same manner as in 4).

As the polyolefin (a2-1) having a carboxyl group at both ends of the polymer, the terminal of the polyolefin (a2-01) is α, β-unsaturated carboxylic acid (anhydride) [α, β-unsaturated carboxylic acid, the same. It means an alkyl (1 to 4 carbon atoms) ester or an anhydride thereof. The same applies below. ], The polyolefin (a2-1-1) and the polyolefin (a2-1-1) obtained by the second modification with lactam or an aminocarboxylic acid are further modified with the polyolefin (a2-1-2) and the polyolefin (a2-1-2). Polyolefin (a2-1-3) obtained by modifying a2-01) by oxidation or hydroformylation, and polyolefin (a2) obtained by further modifying polyolefin (a2-1-3) with lactam or aminocarboxylic acid. -1--4) and a mixture of two or more of these can be used.

Examples of the α, β-unsaturated carboxylic acid (anhydride) used for obtaining the polyolefin (a2-1-1) include monocarboxylic acid, dicarboxylic acid, alkyl (1 to 4 carbon atoms) ester of mono or dicarboxylic acid, and Anhydrides of mono or dicarboxylic acid can be mentioned, and specifically, (meth) acrylic acid [(meth) acrylic acid means acrylic acid or methacrylic acid. The same applies below. ], Methyl (meth) acrylate, butyl (meth) acrylate, maleic anhydride (anhydride), dimethyl maleate, fumaric acid, itaconic acid (anhydride), diethyl itaconic acid and citraconic acid (anhydride). Be done.
Of these, from the viewpoint of easiness of modification, dicarboxylic acid, an alkyl ester of mono or dicarboxylic acid and an anhydride of mono or dicarboxylic acid are preferable, and maleic acid (anhydride) and fumaric acid are more preferable. , Particularly preferred is maleic acid (anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydrous) used is based on the weight of the polyolefin (a2-01), the ease of forming a repeating structure in the molecule, and the thermoplasticity of the block polymer (C) described later. From the viewpoint, it is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight, and particularly preferably 2 to 20% by weight.
Modification with α, β-unsaturated carboxylic acid (anhydrous) can be performed by, for example, the terminal double bond of (a2-01) by either a solution method or a melting method. It can be carried out by subjecting (anhydrous) to an addition reaction (ene reaction), and the reaction temperature is preferably 170 to 230 ° C.

Polyolefin (a2-1-2) can be obtained by further secondary modification of polyolefin (a2-1-1) with lactam or aminocarboxylic acid.
As the lactam and the aminocarboxylic acid used for the secondary modification, the same ones as those exemplified in the above-mentioned polyamide can be used, and the preferable ones are also the same.

The amount of lactam or aminocarboxylic acid used for the secondary denaturation is preferably based on the weight of the polyolefin (a2-1) from the viewpoint of ease of forming a repeating structure in the molecule and the thermoplasticity of the block polymer (C). Is 0.5 to 200% by weight, more preferably 1 to 150% by weight, and particularly preferably 2 to 100% by weight.

The polyolefin (a2-3) can be obtained by oxidizing the polyolefin (a2-01) with oxygen and / or ozone (oxidation method) or by introducing a carboxyl group by hydroformylation by the oxo method.
The introduction of the carbonyl group by the oxidation method can be carried out by a known method, for example, the method described in US Pat. No. 3,692,877. Introduction of carbonyl groups by hydroformylation can be carried out by a variety of methods, including known methods, such as Macromolecules, VOL. This can be done by the method described on pages 31, 5943.
Polyolefin (a2-4) can be obtained by secondary modification of (a2-3) with lactam or aminocarboxylic acid.
Examples of the lactam and the aminocarboxylic acid include the same as those exemplified as the lactam and the aminocarboxylic acid used for the secondary modification of the polyolefin (a2-1), and the preferable range and the amount used are also the same.

The Mn of the polyolefin (a2-1) is preferably 800 to 25,000, more preferably 1,000 to 20,000, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. Particularly preferably, it is 2,500 to 10,000.
The acid value of the polyolefin (a2-1) is preferably 4 to 280 mgKOH / g, more preferably 4 to 100 mgKOH, from the viewpoint of reactivity with the hydrophilic polymer (b) and thermoplasticity of the block polymer (C). / G, particularly preferably 5 to 50 mgKOH / g.

Examples of the polyolefin (a2-2) having a hydroxyl group at both ends of the polymer include a polyolefin having a hydroxyl group obtained by modifying the polyolefin (a2-1) having a carboxyl group at both ends of the polymer with an amine having a hydroxyl group, and two of these. Mixtures of seeds and above can be used.

Examples of the amine having a hydroxyl group that can be used for modification include an amine having a hydroxyl group having 2 to 10 carbon atoms, and specifically, 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, and 4-amino. Butanol, 5-aminopentanol, 6-aminohexanol and 3-aminomethyl-3,5,5-trimethylcyclohexanol can be mentioned.

Of these, amines having a hydroxyl group having 2 to 6 carbon atoms (2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-amino) are preferable from the viewpoint of ease of modification. Hexanol, etc.), more preferred are 2-aminoethanol and 4-aminobutanol, and particularly preferred are 2-aminoethanol.

The amount of the amine having a hydroxyl group used for the modification is based on the weight of the polyolefin (a2-1) to be modified, from the viewpoint of the ease of forming a repeating structure in the molecule and the mechanical properties of the moisture-permeable waterproof film described later. It is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight, and particularly preferably 2 to 30% by weight.
The Mn of the polyolefin (a2-2) is preferably 800 to 25,000, more preferably 1,000 to 20,000, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. Particularly preferably, it is 2,500 to 10,000.
The hydroxyl value of the polyolefin (a2-2) is preferably 4 to 280 mgKOH / g, more preferably 4 to 100 mgKOH, from the viewpoint of reactivity with the hydrophilic polymer (b) and thermoplasticity of the block polymer (C). / G, particularly preferably 5 to 50 mgKOH / g.

Examples of the polyolefin (a2-3) having an amino group at both ends of the polymer include a polyolefin having an amino group obtained by modifying the polyolefin (a2-1) having a carboxyl group at both ends of the polymer with a diamine (q1). Two or more mixtures of the above can be used.
As the diamine (q1), a diamine having 2 to 12 carbon atoms can be used, and specific examples thereof include ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine and decamethylenediamine.
Of these, diamines having 2 to 8 carbon atoms (ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, etc.) are preferable from the viewpoint of ease of modification, and ethylenediamine and hexamethylenediamine are more preferable. Particularly preferred is ethylenediamine.

The amount of diamine (q1) used for modifying the polyolefin (a2-1) is preferably based on the weight of the polyolefin (a2-1) from the viewpoint of ease of forming a repeating structure in the molecule and mechanical properties of the film. It is 0.5 to 50% by weight, more preferably 1 to 40% by weight, and particularly preferably 2 to 30% by weight. The modification of the polyolefin (a2-1) with the diamine (q1) is preferably 0.5 to 1,000 weight based on the weight of the polyolefin (a2-1) from the viewpoint of preventing the formation of the polyamide (imide). %, More preferably 1 to 500% by weight, particularly preferably 2 to 300% by weight of the diamine (q1), and then the unreacted diamine (q1) is removed under reduced pressure at 120 to 230 ° C. ..

The Mn of the polyolefin (a2-3) is preferably 800 to 25,000, more preferably 1,000 to 20,000, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. Particularly preferably, it is 2,500 to 10,000.
The amine value of the polyolefin (a2-3) is preferably 4 to 280 mgKOH / g, more preferably 4 to 100 mgKOH, from the viewpoint of reactivity with the hydrophilic polymer (b) and thermoplasticity of the block polymer (C). / G, particularly preferably 5 to 50 mgKOH / g.

Examples of the polyolefin (a2-4) having an isocyanate group at both ends include a polyolefin having an isocyanate group in which (a2-2) is modified with poly (2 to 3 or more) isocyanate (hereinafter abbreviated as polyisocyanate). Examples include a mixture of two or more of these.
As the polyisocyanate, an aromatic polyisocyanate having 6 to 20 carbon atoms (excluding carbon atoms in the NCO group, the same applies hereinafter), an aliphatic polyisocyanate having 2 to 18 carbon atoms, and an alicyclic type having 4 to 15 carbon atoms. Includes polyisocyanates, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms, modified versions of these polyisocyanates, and mixtures of two or more of these.

Aromatic polyisocyanates include 1,3- or 1,4-phenylenediocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'-or 4,4'-diphenylmethane. Diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane and 1 , 5-Naftylene diisocyanate and the like.

Examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanatomethyl caproate. Examples thereof include bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanatoethyl). ) -4-Cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornene diisocyanate and the like.

Examples of the aromatic aliphatic polyisocyanate include m- or p-xylene diisocyanate (XDI) and α, α, α', α'-tetramethylxylene diisocyanate (TMXDI).

Examples of the modified polyisocyanate include urethane modified products, urea modified products, carbodiimide modified products and uretdione modified products.
Of the polyisocyanates, TDI, MDI and HDI are preferable, and HDI is more preferable.

The reaction between the polyisocyanate and the polyolefin (a2-2) can be carried out in the same manner as the known urethanization reaction.
The molar equivalent ratio (NCO / OH) of the polyisocyanate to the polyolefin (a2-2) is preferably 1.8 / 1-3 / 1, and more preferably 2/1.
If necessary, a known catalyst used in the urethanization reaction may be used to promote the urethanization reaction. Examples of the catalyst include metal catalysts {tin catalysts [dibutyltin dilaurate and stanas octoate, etc.], lead catalysts [lead 2-ethylhexanoate, lead octenoate, etc.], and other metal catalysts [metal salts of naphthenate (cobalt naphthenate, etc.). Etc.) and phenylmercury propionate, etc.]}; amine catalysts {triethylenediamine, diazabicycloalkene [1,8-diazabicyclo [5,4,0] undecene-7, etc.], dialkylaminoalkylamines (dimethylaminoethylamine and Dimethylaminooctylamine, etc.), heterocyclic aminoalkylamine [2- (1-aziridinyl) ethylamine, 4- (1-piperidinyl) -2-hexylamine, etc.] carbonate or organic acid (gilic acid, etc.) salt, N -Methyl or ethylmorpholine, triethylamine and diethyl- or dimethylethanolamine, etc.}; and a combination system of two or more of these.
The amount of the catalyst used is preferably 3% by weight or less, preferably 0.001 to 2% by weight, based on the total weight of the polyisocyanate and the polyolefin (a2-2).

The Mn of the polyolefin (a2-4) is preferably 800 to 25,000, more preferably 1,000 to 20,000, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. Particularly preferably, it is 2,500 to 10,000.

As the polyamide imide (a3), a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring selected from the amide-forming monomer (α) and the amide-forming monomer (α). Alternatively, a polymer having its anhydride (δ) [hereinafter referred to as polycarboxylic acid (anhydride) (δ)] as a constituent monomer, and a mixture thereof are included.

Examples of the polycarboxylic acid (anhydrous) (δ) include trivalent carboxylic acids [monocyclic trivalent carboxylic acids (trimeric acid, etc.), polycyclic trivalent carboxylic acids (1,2,5- or 2,6,7). -Naphthalene tricarboxylic acid, 3,3', 4-biphenyltricarboxylic acid, benzophenone-3,3', 4-tricarboxylic acid, diphenylsulfone-3,3', 4-tricarboxylic acid and diphenyl ether-3,3', 4- Tricarboxylic acids, etc.) and their anhydrides] and tetravalent carboxylic acids [monocyclic tetravalent carboxylic acids (pyromellitic acids, etc.), polycyclic tetravalent carboxylic acids (biphenyl-2,2', 3,3'-tetracarboxylic acids, etc.) Acids, benzophenone-2,2', 3,3'-tetracarboxylic acid, diphenylsulfone-2,2', 3,3'-tetracarboxylic acid and diphenyl ether-2,2', 3,3'-tetracarboxylic acid Etc.), and these anhydrides].

As a method for producing the polyamide-imide (a3), as in the case of the polyamide (a1), one or more selected from the diamine (β) and the dicarboxylic acid (γ) are used as the molecular weight adjuster. Then, a method of ring-opening polymerization or polycondensation of the amide-imide-forming monomer in the presence thereof can be mentioned.
The amount of the molecular weight adjusting agent used is preferably 2 to 80% by weight, more preferably 4 to 75% by weight, based on the total weight of the amidimide-forming monomer and the molecular weight adjusting agent, from the viewpoint of moisture permeability and mechanical properties of the film. Weight%.

The Mn of the polyamide-imide (a3) is preferably 200 to 5,000, more preferably 500 to 4,000, from the viewpoint of moldability and manufacturing of the moisture permeable waterproof material.

The Mn of the hydrophobic polymer (a) is preferably 200 to 25,000, more preferably 500 to 20,000, and particularly preferably 1 from the viewpoint of the dispersibility of the block polymer (C) and the mechanical properties of the film. It is between 000 and 15,000.

[Hydrophilic polymer (b)]
Examples of the hydrophilic polymer (b) include the hydrophilic polymer described in Patent No. 3488163, specifically, a polyether (b1), a polyether-containing hydrophilic polymer (b2), and a cationic polymer (b3). And anionic polymer (b4) and the like.

Examples of the polyether (b1) include a polyether diol (b1-1), a polyether diamine (b1-2) and a modified product thereof (b1-3). Examples of the polyether diol (b1-1) include those obtained by subjecting the diol (b0) to a cycloaddition reaction of an alkylene oxide having 2 to 4 carbon atoms (hereinafter abbreviated as AO).

Examples of the diol (b0) include an aliphatic dihydric alcohol having 2 to 12 carbon atoms, an alicyclic dihydric alcohol having 5 to 12 carbon atoms, an aromatic dihydric alcohol having 6 to 18 carbon atoms, and a tertiary amino group-containing diol. And so on.
Examples of the aliphatic dihydric alcohol having 2 to 12 carbon atoms include ethylene glycol (hereinafter abbreviated as EG), 1,2-propylene glycol (hereinafter abbreviated as PG), and 1,4-butanediol (hereinafter 1,1). Examples thereof include 4-BD (abbreviated as 4-BD), 1,6-hexanediol (hereinafter abbreviated as 1,6-HD), neopentyl glycol (hereinafter abbreviated as NPG) and 1,12-dodecanediol.
Examples of the alicyclic dihydric alcohol having 5 to 12 carbon atoms include 1,4-di (hydroxymethyl) cyclohexane and 1,5-di (hydroxymethyl) cycloheptane.
Examples of the aromatic dihydric alcohol having 6 to 18 carbon atoms include monocyclic aromatic dihydric alcohols (xylylenediol, hydroquinone, catechol, resorcin, ursiol, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxy. Diphenyl-2,2-butane and dihydroxybiphenyl, etc.) and polycyclic aromatic dihydric alcohols (dihydroxynaphthalene, binaphthol, etc.) and the like.
Examples of the tertiary amino group-containing diol include aliphatic or alicyclic primary amines having 1 to 12 carbon atoms (methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, pentylamine, isopentylamine). , Cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine, dodecylamine, etc.) and aromatic primary amines (aniline, benzylamine, etc.) with 6 to 12 carbon atoms. Bishydroxyalkylated products can be mentioned.
Of these, from the viewpoint of reactivity with the bishydroxyalkylated product, an aliphatic dihydric alcohol having 2 to 12 carbon atoms and an aromatic dihydric alcohol having 6 to 18 carbon atoms are preferable, and EG is more preferable. And bisphenol A.

Examples of AO include ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3-propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,3-, 1,4-, Examples thereof include 2,3- or butylene oxide (hereinafter abbreviated as BO), and a mixture of two or more of these.
If necessary, other AOs [α-olefin oxide having 5 to 12 carbon atoms, styrene oxide, epichlorohydrin, etc.] should be used in combination in a small proportion (30% by weight or less based on the total weight of AO). You can also.
When two or more types of AO are used in combination, the binding form may be either random binding or block binding. Preferable AOs are EO alone and EO in combination with other AOs.

The ring-opening addition reaction of AO can be carried out by a known method, for example, in the presence of an alkaline catalyst at a temperature of 100 to 200 ° C.
The content of AO based on the weight of the polyether diol (b1-1) is preferably 5 to 99.8% by weight, more preferably 8 to 99.6% by weight, and particularly preferably 10 to 98% by weight. Is.
When ethylene oxide is contained as AO, the content of oxyethylene groups based on the total weight of AO contained in the polyether diol (b1-1) is preferably 5 to 100% by weight, more preferably 10 to 100% by weight. %, Especially preferably 50 to 100% by weight, most preferably 60 to 100% by weight.

Examples of the polyether diamine (b1-2) include a polyether diamine in which all the hydroxyl groups of the polyether diol (b1-1) are converted into amino groups, and examples thereof include the polyether diol (b1-1). It can be produced by reacting with acrylonitrile and hydrogenating the obtained cyanoethylated product.

Examples of the modified product (b1-3) include an aminocarboxylic acid modified product (terminal amino group) of a polyether diol (b1-1) or a polyether diamine (b1-2), an isocyanate modified product (terminal isocyanate group), and an epoxy modification. Things (terminal epoxy group) and the like can be mentioned.
The modified aminocarboxylic acid can be obtained by reacting a polyether diol (b1-1) or a polyether diamine (b1-2) with an aminocarboxylic acid or a lactam.
The isocyanate-modified product can be obtained by reacting a polyether diol (b1-1) or a polyether diamine (b1-2) with a polyisocyanate, or by reacting a polyether diamine (b1-2) with a phosgene. Can be done.
Epoxy modified products include polyether diols (b1-1) or polyether diamines (b1-2), and epoxydos (epoxy resins such as diglycidyl ether, diglycidyl ester, and alicyclic diepoxy: epoxy equivalents 85-600). Or by reacting a polyether diol (b1-1) with an epihalohydrin (epichlorohydrin or the like).

The Mn of the polyether (b1) is preferably 150 to 20,000, more preferably 300 to 18,000, and particularly preferably 1, from the viewpoint of heat resistance and reactivity with the hydrophobic polymer (a). It is 000 to 15,000, most preferably 1,200 to 8,000.

Examples of the polyether-containing hydrophilic polymer (b2) include a polyether ester amide (b2-1) having a segment of a polyether diol (b1-1) and a polyether amide imide having a segment of a polyether diol (b1-1). (B2-2), a polyether ester (b2-3) having a segment of (b1-1), a polyether amide (b2-4) having a segment of a polyether diamine (b1-2), and a polyether diol (b1). -1) or polyether urethane (b2-5) having a segment of polyether diamine (b1-2) can be mentioned.

The polyether ester amide (b2-1) is composed of a polyamide (a1) having a carboxyl group at both ends (a1') and a polyether diol (b1-1).
Examples of the polyamide (a1') having a carboxyl group at both ends include the ring-opening polymer of the lactam (α1-1), the polycondensate of the aminocarboxylic acid (α1-2), and the diamine (β) and the dicarboxylic acid. Examples thereof include polyamide with an acid (γ).
Among the polyamides (a1') having carboxyl groups at both ends, the ring-opening polymer of caprolactam, the polycondensate of 12-aminododecanoic acid, and adipic acid are preferable from the viewpoint of moisture permeability and mechanical properties of the film. A polyamide with hexamethylenediamine, more preferably a ring-opening polymer of caprolactam.

The polyether amide imide (b2-2) is composed of a polyamide-imide (a3) having at least one imide ring and a polyether diol (b1-1).
Examples of the polyamide imide (a3) having at least one imide ring include aminocarboxylic acid (α1-2), which is a polymer composed of lactam (α1-1) and the polycarboxylic acid (anhydrous) (δ). Examples thereof include a polymer composed of the polycarboxylic acid (anhydrous) (δ), a polymer composed of polyamide (a1') and the polycarboxylic acid (anhydrous) (δ), and a mixture thereof.

Examples of the polyether ester (b2-3) include those composed of polyester (Q) and polyether diol (b1-1).
Examples of the polyester (Q) include a polyester containing a dicarboxylic acid (γ) and a diol (b0).
Examples of the polyether amide (b2-4) include those composed of a polyamide (a1) and a polyether diamine (a212).
As the polyether urethane (b2-5), the diisocyanate among the polyisocyanates, the polyether diol (b1-1) or the polyether diamine (b1-2), and if necessary, the chain extender [the diol (b0) and Diamine (β), etc.]

The content of the polyether (b1) segment in the polyether-containing hydrophilic polymer (b2) is preferably 30 to 80% by weight based on the weight of the polyether-containing hydrophilic polymer (b2) from the viewpoint of moldability. , More preferably 40 to 70% by weight.
The content of the oxyethylene group in the polyether-containing hydrophilic polymer (b2) is preferably 30 to 80% by weight based on the weight of the polyether-containing hydrophilic polymer (b2) from the viewpoint of moisture permeability and moldability. , More preferably 40 to 70% by weight.
The lower limit of Mn of the polyether-containing hydrophilic polymer (b2) is preferably 800, more preferably 1,000, from the viewpoint of heat resistance. The upper limit of Mn of the polyether-containing hydrophilic polymer (b2) is preferably 50,000, more preferably 30,000, from the viewpoint of reactivity with the hydrophobic polymer (a).

Examples of the cationic polymer (b3) include polymers having a cationic group separated by a nonionic molecular chain in the molecule.
The nonionic molecular chain is a group consisting of a divalent hydrocarbon group, an ether bond, a thioether bond, a carbonyl bond, an ester bond, an imino bond, an amide bond, an imide bond, a urethane bond, a urea bond, a carbonate bond and a syroxy bond. Examples thereof include a divalent hydrocarbon group having one or more groups selected from the above, a hydrocarbon group having a heterocyclic structure having a nitrogen atom or an oxygen atom, and the like. Of the nonionic molecular chains, a divalent hydrocarbon group and a divalent hydrocarbon group having an ether bond are preferable. Examples of the cationic group include a group having a quaternary ammonium salt or a phosphonium salt. Examples of the counter anion forming the quaternary ammonium salt or the phosphonium salt include superacid anions and other anions. Examples of the superacid anion include an anion of a superacid (boric acid tetrafluoride, phosphoric acid hexafluoride, etc.) derived from a combination of a protonic acid and a Lewis acid, and an anion such as trifluoromethanesulfonic acid. Other anions include halogen ions (F ⁻ , Cl ⁻ , Br ⁻ and I ^−, etc.), OH ⁻ , PO ₄ ⁻ , CH ₃ OSO ₄ ⁻ , C ₂ H ₅ OSO ₄ ⁻ , and ClO ₄ ^−. Can be mentioned. Examples of Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride and tantalum pentafluoride. The number of cationic groups in one molecule of the cationic polymer (b3) is preferably 2 to 80, more preferably 3 to 60.

Specific examples of the cationic polymer (b3) include the cationic polymer described in JP-A-2001-278985.

The Mn of the cationic polymer (b3) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly preferably 1,000 to 15,000, from the viewpoint of moisture permeability and reactivity with the hydrophobic polymer (a). Is 1,200 to 8,000.

The anionic polymer (b4) contains a dicarboxylic acid (γ') having a sulfonyl group and a diol (b0) [preferably polyether (b1)] as essential constituent units, and 2 to 80 in the molecule, preferably. Is a polymer having 3 to 60 sulfonyl groups.
Examples of the dicarboxylic acid (γ') having a sulfonyl group include those obtained by introducing a sulfonyl group into the dicarboxylic acid (γ), and include an aromatic dicarboxylic acid having a sulfonyl group, an aliphatic dicarboxylic acid having a sulfonyl group, and a sulfonyl. Examples thereof include aromatic dicarboxylic acids and aliphatic dicarboxylic acids having a sulfonyl group in which only the group is a salt.

Examples of the aromatic dicarboxylic acid having a sulfonyl group include 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid, and ester-forming derivatives thereof [alkyl. (1 to 4 carbon atoms) esters (methyl esters, ethyl esters, etc.), acid anhydrides, etc.] can be mentioned.
Examples of the aliphatic dicarboxylic acid having a sulfonyl group include sulfosuccinic acid and its ester-forming derivative [alkyl (1 to 4 carbon atoms) ester (methyl ester, ethyl ester, etc.), acid anhydride, etc.].
Examples of the salt forming an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid having a sulfonyl group in which only the sulfonyl group is a salt include alkali metal (lithium, sodium and potassium, etc.) salts and alkaline earth metals (magnesium, calcium, etc.). Amine salts such as salts, ammonium salts, mono, di or triamines having hydroxyalkyl (2-4 carbon atoms) groups (mono, di or triethylamine, mono, di or triethanolamine, diethylethanolamine, etc.) and the amines. Quaternary ammonium salt and the like can be mentioned.
Of these, aromatic dicarboxylic acids having a sulfonyl group are preferred, more preferred are 5-sulfoisophthalic acid salts, and particularly preferred are 5-sulfoisophthalic acid sodium salts and 5-sulfoisophthalic acid potassium salts. ..

Of the diols (b0) constituting the anionic polymer (b4), the preferred one is the polyether (b1), which is an alkane diol having 2 to 10 carbon atoms, EG, and polyethylene glycol (hereinafter abbreviated as PEG) (polymerization). Degrees 2 to 20), EO adducts of bisphenol (bisphenol A, etc.) (number of moles added: 2 to 60 mols) and mixtures of two or more of these.
As a method for producing the anionic polymer (b4), a known method for producing polyester can be applied as it is. The polyesterification reaction is carried out under reduced pressure in a temperature range of 150 to 240 ° C., and the reaction time is preferably 0.5 to 20 hours. Further, if necessary, a known catalyst used for the esterification reaction may be used. Examples of the esterification catalyst include antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin oxide, dibutyltin oxide, etc.), titanium catalysts (tetrabutyl titanate, etc.), zirconium catalysts (tetrabutylzirconate, etc.) and metal acetates. Examples include catalysts (zinc acetate, etc.).

The Mn of the anionic polymer (b4) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly preferably 1,000 to 15,000, from the viewpoint of moisture permeability and reactivity with the hydrophobic polymer (a). Is 1,200 to 8,000.

Among the block polymers (C), the block of the hydrophobic polymer (a) possessed by the block polymer (C) is a block of the polyamide (a1) or the polyolefin (a2) from the viewpoint of moisture permeability of the molded product and the like. The block of the hydrophilic polymer (b) contained in the block polymer (C) is a block made of the polyether (b1), and the block of the hydrophobic polymer (a) and the block of the hydrophilic polymer (b) are esters. It is preferably a block polymer bonded via at least one bond selected from the group consisting of a bond, an amide bond, an ether bond, an imide bond and a urethane bond.
The polyamide (a1) contained in the block of the hydrophilic polymer (b) includes a polyamide having 4 to 20 carbon atoms as a constituent monomer, and a polyamide having 2 to 20 carbon atoms as a constituent monomer. It is preferable that the polyamide (β) having 2 to 20 carbon atoms and the dicarboxylic acid (γ) having 2 to 20 carbon atoms are constituent monomers, or a copolymer of these constituent monomers.

The weight ratio of the block of the hydrophobic polymer (a) constituting the block polymer (C) to the block of the hydrophilic polymer (b) is preferably 10/90 to 80 / from the viewpoint of moisture permeability and mechanical properties of the film. It is 20, more preferably 20/80 to 75/25.

The structure in which the block of the hydrophobic polymer (a) constituting the block polymer (C) and the block of the hydrophilic polymer (b) are bonded is a type (a)-(b), (a)-(b). -(A) type, (b)-(a)-(b) type and [(a)-(b)] n type (n represents the average number of repetitions) are included.
As for the structure of the block polymer (C), from the viewpoint of moisture permeability and mechanical properties of the molded product, the block of the hydrophobic polymer (a) and the block of the hydrophilic polymer (b) are repeatedly and alternately bonded [(a). )-(B)] n-type is preferable.
[(A)-(b)] n in the n-type structure is preferably 2 to 50, more preferably 2.3 to 30, and particularly preferably 2 from the viewpoint of moisture permeability and mechanical properties of the molded product. .7 to 20, most preferably 3 to 10. ^{n can be determined by Mn and 1 1} H-NMR analysis of the block polymer (C).

The Mn of the block polymer (C) is preferably 2,000 to 1,000,000, more preferably 4,000 to 500,000, and particularly preferably 6,000 to 100, from the viewpoint of the mechanical properties of the film. It is 000.

A block polymer having a structure in which a block of the hydrophobic polymer (a) and a hydrophilic polymer (b) are bonded via an ester bond, an amide bond, an ether bond or an imide bond can be produced by the following method. can.
The block of the hydrophobic polymer (a) and the hydrophilic polymer (b) are put into a reaction vessel, and the amidation reaction and the esterification reaction are carried out under stirring at a reaction temperature of 100 to 250 ° C. and a pressure of 0.003 to 0.1 MPa. Alternatively, a method of reacting for 1 to 50 hours while removing the water produced by the imidization reaction (hereinafter abbreviated as produced water) from the reaction system can be mentioned. The weight ratio of the block of the hydrophobic polymer (a) to the hydrophilic polymer (b) is 10/90 to 80/20, more preferably 20/80 to 75/20, from the viewpoint of water permeability and mechanical properties of the film. 25.

When the reaction in the above-mentioned production method is an esterification reaction, 0.05 to 0. It is preferable to use 5% by weight of the catalyst. As catalysts, inorganic acids (sulfuric acid, hydrochloric acid, etc.), organic sulfonic acids (methanesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid, etc.) and organic metal compounds (dibutyltin oxide, tetraisopropoxytitanate, bistri). Ethanolamine titanate, potassium titanate oxalate, etc.) and the like can be mentioned. When a catalyst is used, after the esterification reaction is completed, the catalyst can be neutralized if necessary and treated with an adsorbent to remove and purify the catalyst. Examples of the method for removing the produced water from the reaction system include the following methods.
(1) A method in which an organic solvent incompatible with water (for example, toluene, xylene, cyclohexane, etc.) is used to azeotrope the organic solvent and the produced water under reflux, and only the produced water is removed from the reaction system. ..
(2) A method in which a carrier gas (for example, air, nitrogen, helium, argon, carbon dioxide, etc.) is blown into the reaction system, and the generated water is removed from the reaction system together with the carrier gas.
(3) A method in which the inside of the reaction system is depressurized and the generated water is removed from the reaction system.

A block polymer having a structure in which a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) are bonded via a urethane bond or a urea bond can be produced by the following method.
Examples thereof include a method in which the hydrophobic polymer (a) is charged into a reaction vessel, heated to 30 to 100 ° C. with stirring, and then the hydrophilic polymer (b) is charged and reacted at the same temperature for 1 to 20 hours. The weight ratio of the block of the hydrophobic polymer (a) to the block of the hydrophilic polymer (b) is 10/90 to 80/20, more preferably 20/80, from the viewpoint of moisture permeability and mechanical properties of the film. ~ 75/25.
To accelerate the reaction, 0.001-5 wt% organic metal compounds (dibutyltin dilaurate, dioctyltin dilaurate, based on the total weight of the block of hydrophobic polymer (a) and block of hydrophilic polymer (b), Lead octanoate, bismuth octanoate, etc.), tertiary amines {triethylenediamine, trialkylamines having an alkyl group having 1 to 8 carbon atoms (trimethylamine, tributylamine, trioctylamine, etc.) and diazabicycloalkenes [1] , 8-diazabicyclo [5,4,0] undecene-7], etc.} and the like are preferably used.

The antistatic resin composition of the present invention contains 0.1 to 20% by weight of the cyclic polyether ester (A) based on the total weight of the antistatic resin composition from the viewpoint of sustainability of antistatic properties. It is preferable, and it is more preferable to contain 0.1 to 10% by weight.

When the thermoplastic resin (B) contains the block polymer (C), the weight ratio of the block polymer (C) contained in the thermoplastic resin (B) is the total of the thermoplastic resins (B) from the viewpoint of antistatic property. Based on weight, 5-100% is preferred.

The antistatic resin composition of the present invention can further contain the antistatic property improver (D) as long as the effects of the present invention are not impaired.
Examples of the antistatic property improving agent (D) include alkali metal or alkaline earth metal salt (D1), quaternary ammonium salt (D2), surfactant (D3) and ionic liquid (D4).

Examples of the alkali metal or alkaline earth metal salt (D1) include alkali metals (lithium, natriu, potassium, etc.) or alkaline earth metals (magnesium, calcium, etc.)] and organic acids [mono or dicarboxylic having 1 to 7 carbon atoms. Salts with acids (firic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.), sulfonic acids having 1 to 7 carbon atoms (methanesulfonic acid, p-toluenesulfonic acid, etc.) and thiocyanic acid], and the organic acid. Examples thereof include salts of inorganic acids [hydrochloric acid halides (hydrochloric acid, hydrobromic acid, etc.), perchloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.).

Examples of the quaternary ammonium salt (D2) include amidinium (1-ethyl-3-methylimidazolium, etc.) or guanidium (2-dimethylamino-1,3,4-trimethylimidazolinium, etc.) and the organic acid or inorganic acid. Examples include salts with acids.

Examples of the surfactant (D3) include known nonionic surfactants and anionic surfactants described in JP-A-2014-122331, JP-A-2016-37525, JP-A-2014-9197, and the like. , Cationic surfactants, amphoteric surfactants and the like.

The ionic liquid (D4) is a compound excluding the above (D1) to (D3), has a melting point of 25 ° C. or lower, and at least one of the constituent cations or anions is an organic ion, and has an initial conductivity. A molten salt having a value of 1 to 200 ms / cm (preferably 10 to 200 ms / cm) can be mentioned, and specific examples thereof include the molten salt exemplified in WO95 / 15572.

When the antistatic resin composition of the present invention contains an alkali metal or an alkaline earth metal salt (D1), the amount used is 0.01 to 3% by weight based on the total weight of the antistatic resin composition. It is preferably 0.05 to 2% by weight, and more preferably 0.05 to 2% by weight. When the amount of the alkali metal or the alkaline earth metal salt (D1) is in this range, it is preferable that the antistatic property and the appearance of the resin can be compatible with each other.

The antistatic resin composition of the present invention may contain another known additive (E) as long as the effect of the present invention is not impaired. Examples of the additive (E) include a colorant (E1), a mold release agent (E2), an antioxidant (E3), a flame retardant (E4), an ultraviolet absorber (E5), an antibacterial agent (E6), and a compatibilizer. (E7), filler (E8) and the like can be mentioned.

Coloring agents (E1) include inorganic pigments (white pigments, cobalt compounds, iron compounds, sulfides, etc.), organic pigments (azo pigments, polycyclic pigments, etc.) and dyes (azo-based, indigoid-based, sulfide-based, alizarin). System, aclysine system, thiazole system, nitro system, aniline system, etc.) and the like.

The release agent (E2) includes an alkyl (1 to 4 carbon atoms) ester of a fatty acid having 12 to 18 carbon atoms (butyl stearate, etc.) and a glycol (2 to 8 carbon atoms) ester of a fatty acid having 2 to 18 carbon atoms. Examples thereof include (ethylene glycol monostearate, etc.), polyvalent (trivalent or higher) alcohol esters of fatty acids having 2 to 18 carbon atoms (hardened castor oil, etc.), liquid paraffins, and the like.

Examples of the antioxidant (E3) include phenol compounds [monocyclic phenol (2,6-di-t-butyl-p-cresol, etc.)) and bisphenol [2,2'-methylenebis (4-methyl-6-t-butylphenol). ) Etc.] and polycyclic phenol [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, etc.], etc.], sulfur compounds (dilauryl- 3,3'-thiodipropionate, etc.), phosphorus compounds (triphenylphosphite, etc.), amine compounds (octylated diphenylamine, etc.) and the like.

Examples of the flame retardant (E4) include a halogen-containing flame retardant, a nitrogen-containing flame retardant, a sulfur-containing flame retardant, a silicon-containing flame retardant, and a phosphorus-containing flame retardant.

Examples of the ultraviolet absorber (E5) include benzotriazole [2- (2'-hydroxy-5'-methylphenyl) benzotriazole, etc.], benzophenone (2-hydroxy-4-methoxybenzophenone, etc.), salicylate (phenylsalicylate, etc.). Etc.) and acrylates (2-ethylhexyl-2-cyano-3, 3'1-diphenylacrylate, etc.) and the like.

Examples of the antibacterial agent (E6) include benzoic acid, sorbic acid, phenol halide, organic iodine, nitrile (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylenebisthianocyanate, etc.), N- Examples thereof include haloalkylthioimides, copper agents (8-oxyquinolin copper, etc.), benzimidazoles, benzthiazoles, trihaloallyl, triazoles, organic nitrogen-sulfur compounds (suraoff 39, etc.), quaternary ammonium compounds, and pyridine compounds.

As the compatibilizer (E7), a modified vinyl polymer having one or more functional groups (polar groups) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group (for example, Polymers described in JP-A-3-258850, modified vinyl polymers having a sulfonic acid group described in JP-A-6-345927, block polymers having a polyolefin moiety and an aromatic vinyl polymer moiety, etc.) And so on.

Examples of the filler (E8) include inorganic fillers (calcium carbonate, talc, clay, etc.) and organic fillers (urea, calcium stearate, etc.) and the like.

When the antistatic resin composition of the present invention contains the additive (E), the total content of the additive (E) with respect to the total weight of the antistatic resin composition is preferably from the viewpoint of mechanical properties of the molded product. Is 45% by weight or less, more preferably 0.001 to 40% by weight, and particularly preferably 0.01 to 35% by weight.
Among them, the content of the colorant (E1) based on the total weight of the antistatic resin composition is preferably 0.1 to 3% by weight, more preferably 0. The contents of the mold release agent (E2), the antioxidant (E3) and the ultraviolet absorber (E5) based on the total weight of the antistatic resin composition are 2 to 2% by weight, and the mechanical properties of the molded product are respectively. From the viewpoint of the above, it is preferably 0.01 to 3% by weight, more preferably 0.05 to 1% by weight, and is a flame retardant (E4) and an antibacterial agent (E6) based on the total weight of the antistatic resin composition. ) Is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, respectively, from the viewpoint of mechanical properties of the molded product, and is based on the total weight of the antistatic resin composition. The contents of the compatibilizer (E7) and the filler (E8) are preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, respectively, from the viewpoint of the mechanical properties of the molded product.

The antistatic resin composition of the present invention can be obtained by melt-mixing a cyclic polyether ester (A) and a thermoplastic resin, and an antistatic agent (D) and an additive (E) to be used if necessary. can. As a method of melt-mixing, generally, pellet-shaped or powder-shaped components are mixed by an appropriate mixer [Hensiel mixer (registered trademark), etc.], and then melt-mixed by an extruder to be pelletized. The method of conversion can be applied.

The order of addition of each component at the time of melt mixing is not particularly limited, and for example, the methods described in the following [1] and [2] can be used.
[1] A method in which a thermoplastic resin (B) is melted, and then a cyclic polyether ester (A) and, if necessary, an antistatic agent (D) and an additive (E) are collectively added and melt-mixed.
[2] A high-concentration composition (masterbatch) is prepared by melting and mixing a part of the thermoplastic resin (B) and the cyclic polyether ester (A) in advance, and then the remaining thermoplastic resin and, if necessary, charged. A method of melt-mixing the preventive agent (D) and the additive (E) (master batch method or master pellet method).
When the method of [2] is used, the concentration of the cyclic polyether ester (A) in the masterbatch is preferably 40 to 80% by weight, more preferably 50 to 70% by weight.
Of the methods [1] and [2], the method [2] is preferable from the viewpoint that the cyclic polyether ester (A) can be easily dispersed in the thermoplastic resin.

The antistatic resin composition of the present invention can be obtained as it is or mixed with another thermoplastic resin and then heat-molded to obtain an antistatic resin molded product. Examples of the molding method include injection molding, compression molding, calender molding, slush molding, rotary molding, extrusion molding, blow molding, film molding (cast method, tenter method, inflation method, etc.), and a single layer depending on the purpose. It can be molded by any method incorporating means such as molding, multi-layer molding or foam molding.

The molded product containing the antistatic resin composition of the present invention has excellent mechanical and permanent antistatic properties, and also has good paintability and printability, and the molded product is painted and / or printed. To obtain a molded article.
Examples of the method for coating the molded product include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, immersion coating, roller coating, and brush coating.
As the paint, a paint generally used for painting plastics can be used, and specific examples thereof include polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint and acrylic urethane resin paint.
The coating film thickness (dry film thickness) can be appropriately selected depending on the intended purpose, but is preferably 10 to 50 μm.

As a method of printing on a molded product or a painted surface of the molded product, any printing method generally used for printing plastic can be used, and gravure printing, flexo printing, screen printing, pad printing can be used. , Dry offset printing, offset printing and the like.
As the printing ink, known printing inks used for printing plastics can be used, and examples thereof include gravure ink, flexo ink, screen ink, pad ink, dry offset ink, and offset ink.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto. In addition, the part in an Example shows a part by weight.
In addition, Examples 1 to 4 and 29 to 36 are Reference Examples 1 to 4 and 29 to 36.

<Production Example 1: Cyclic polyether ester (A1)>
In a stainless steel autoclave with a stirrer and temperature control function, 240 parts (1 mol) of 15-pentadecanolactone, "Kyoward 500" [Kyowa Kagaku Kogyo Co., Ltd .: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · _4H 2 O] after sealing putting 24.2 parts of aluminum perchlorate nonahydrate 1 part by heating for 3 hours at 160 ° C. under reduced pressure and dehydrated. Then, the temperature was raised to 180 ° C., and 88 parts of ethylene oxide (hereinafter abbreviated as EO) was introduced into the autoclave while adjusting the gauge pressure to be in the range of 0.1 to 0.5 MPa at 180 ° C. After introducing the total amount of EO, stirring was continued until the pressure reached 0.01 MPa. Then, 0.3 part of potassium hydroxide was added, and 176 parts of EO was further introduced at 180 ° C. so that the gauge pressure was 0.1 to 0.5 MPa. After introducing the total amount of EO, stirring was continued until the pressure reached 0.01 MPa, and the reaction between 15-pentadecanolactone and EO was carried out. The total time required for the EO addition reaction was 8 hours. Then, the catalyst was filtered off from the reaction mixture obtained by the addition reaction of EO to obtain a cyclic polyether ester composition (A1).
The obtained cyclic polyether ester composition (A1) was analyzed by MALDI-TOF MS.
The cyclic polyether ester composition (A1) contains 90% by weight of the cyclic polyether ester (A1) represented by the general formula (1) in which m is 1 to 3 and n is 1 to 30. It is a mixture of cyclic polyether esters, and the average value of n of the cyclic polyether ester (A1) (that is, the average number of added moles of EO) is 6, and among the cyclic polyether esters (A1), n is 5 to 10. The total weight of the cyclic polyether ester (A1) was 85% by weight based on the total weight of the cyclic polyether ester (A1).

<Production Example 2: Cyclic polyether ester (A2)>
240 parts of 15-pentadecanolactone, 24.2 parts of "Kyoward 500", and 1 part of aluminum perchlorate hexahydrate were placed in a stainless steel autoclave equipped with a stirrer and temperature control function and sealed. Then, it was heated at 160 ° C. for 3 hours under reduced pressure to dehydrate it. Next, the temperature was adjusted to 150 ° C., and 61 parts of propylene oxide (hereinafter abbreviated as PO) was introduced into the autoclave while adjusting the gauge pressure to 0.1 to 0.3 MPa at 150 ° C. After introducing the total amount of PO, stirring was continued until the pressure reached 0.01 MPa, and the reaction between 15-pentadecanolactone and PO was carried out. The time required for the addition reaction of PO was 12 hours. Next, the temperature was adjusted to 180 ° C., and 220 parts of EO was introduced into the autoclave while adjusting the ^{gauge pressure to 1 to 3 kgf / cm 2 at 180 ° C.} After introducing the total amount of EO, stirring was continued until the pressure became 0.01 MPa, and the EO reaction was carried out. The time required for the EO addition reaction was 7 hours. The catalyst was filtered off from the reaction mixture obtained after completing the EO addition reaction to obtain a cyclic polyether ester composition (A2).
The obtained cyclic polyether ester composition (A1) was analyzed by MALDI-TOF MS.

In the cyclic polyether ester composition (A2), 90 is a total of the cyclic polyether esters (A2) represented by the above general formula (1) in which m is 1 to 3 and n is 1 to 30, respectively. It is a mixture containing% by weight, and the average value of n of the cyclic polyether ester (A2) contained in the cyclic polyether ester composition (A2) is 6, of which the average number of moles of PO added is 1, and the average number of moles of PO added is 1. The average number of moles added is 5, and among the cyclic polyether esters (A2), the total weight of the cyclic polyether esters represented by the general formula (1) in which n is 5 to 10 is the cyclic polyether ester (A2). ) Was 90% by weight.

<Production Example 3: Cyclic polyether ester (A3)>
In a stainless steel autoclave with a stirrer and temperature control function, 240 parts of 15-pentadecanolactone and "Kyoward 500" [Kyowa Kagaku Kogyo Co., Ltd .: Mg ₆ Al ₂ (OH) ₁₆ CO _3. 4H ₂ O] 24.2 parts were added and sealed, and then heated at 160 ° C. for 3 hours under reduced pressure to dehydrate. Then, the temperature was adjusted to 180 ° C., and 264 parts of EO was introduced into the autoclave while adjusting the gauge pressure to be within the range of 0.1 to 0.5 MPa at 180 ° C. After adding the entire amount of EO, stirring was continued until the pressure reached 0.01 MPa, and the reaction between 15-pentadecanolactone and EO was carried out. The time required for the EO addition reaction was 10 hours. Then, the catalyst was filtered off from the reaction mixture obtained by the addition reaction of EO to obtain a cyclic polyether ester composition (A3).
The obtained cyclic polyether ester composition (A3) was analyzed by MALDI-TOF MS.
In the cyclic polyether ester composition (A3), the cyclic polyether ester (A3) represented by the general formula (1), wherein m is 1 to 3 and n is 1 to 30, respectively, is 85 in total. It is a mixture containing% by weight, and the average value of n of the cyclic polyether ester (A3) (that is, the average number of moles of EO added) is 6, and n of the cyclic polyether ester (A3) is 5 to 10. The total weight of the cyclic polyether ester was 28% by weight based on the total weight of the cyclic polyether ester (A3).

<Production Example 4: Cyclic Polyether Ester (A4)>
In with stainless steel autoclave a stirring device and temperature control, 15-penta decanoate lactone 240 parts "Kyowaad 500" [manufactured by Kyowa Chemical Industry Co., _{Ltd.: Mg 6 Al 2 (OH)} 16 CO 3 · 4H ₂ O] 24.2 parts and 1 part of aluminum perchlorate hexahydrate were added and sealed, and then heated at 160 ° C. for 3 hours under reduced pressure for dehydration treatment. Next, the temperature was raised to 180 ° C., and 88 parts (2 mol) of ethylene oxide (hereinafter abbreviated as EO) was placed in the autoclave while adjusting the gauge pressure to be within the range of 0.1 to 0.5 MPa at 180 ° C. Introduced. After introducing the total amount of EO, stirring was continued until the pressure reached 0.01 MPa. Then, 0.3 part of potassium hydroxide was added, and 352 parts of EO was further introduced at 180 ° C. so that the gauge pressure was 0.1 to 0.5 MPa. After introducing the total amount of EO, stirring was continued until the pressure reached 0.01 MPa, and the reaction between 15-pentadecanolactone and EO was carried out. The total time required for the EO addition reaction was 8 hours. Then, the catalyst was filtered off from the reaction mixture obtained by the addition reaction of EO to obtain a cyclic polyether ester composition (A4). The obtained cyclic polyether ester composition (A4) was analyzed by MALDI-TOF MS.
The cyclic polyether ester composition (A4) contains 90% by weight of the cyclic polyether ester (A4) represented by the general formula (1) in which m is 1 to 3 and n is 1 to 30. It is a mixture of cyclic polyether esters, and the average value of n of the cyclic polyether ester (A4) (that is, the average number of added moles of EO) is 10, and among the cyclic polyether esters (A4), n is 8 to 13. The total weight of the cyclic polyether ester (A4) was 85% by weight based on the total weight of the cyclic polyether ester (A4).

<Production Example 5: Cyclic polyether ester (A5)>
In with stainless steel autoclave a stirring device and temperature control, 15-penta decanoate lactone 240 parts "Kyowaad 500" [manufactured by Kyowa Chemical Industry Co., _{Ltd.: Mg 6 Al 2 (OH)} 16 CO 3 · 4H ₂ O] 24.2 parts and 1 part of aluminum perchlorate hexahydrate were added and sealed, and then heated at 160 ° C. for 3 hours under reduced pressure for dehydration treatment. Then, the temperature was raised to 180 ° C., and 88 parts of ethylene oxide (hereinafter abbreviated as EO) was introduced into the autoclave while adjusting the gauge pressure to be in the range of 0.1 to 0.5 MPa at 180 ° C. After introducing the total amount of EO, stirring was continued until the pressure became 0.1 to 0.5 MPa. Then, 0.3 part of potassium hydroxide was added, and 1232 parts of EO was further introduced at 180 ° C. so that the gauge pressure was 0.1 to 0.5 MPa. After introducing the total amount of EO, stirring was continued until the pressure reached 0.01 MPa, and the reaction between 15-pentadecanolactone and EO was carried out. The total time required for the EO addition reaction was 8 hours. Then, the catalyst was filtered off from the reaction mixture obtained by the addition reaction of EO to obtain a cyclic polyether ester composition (A5).
The obtained cyclic polyether ester composition (A5) was analyzed by MALDI-TOF MS.
The cyclic polyether ester composition (A5) contains 90% by weight of the cyclic polyether ester (A5) represented by the general formula (1) in which m is 1 to 3 and n is 1 to 30. It is a mixture of cyclic polyether esters, and the average value of n of the cyclic polyether ester (A5) (that is, the average number of added moles of EO) is 30, and among the cyclic polyether esters (A5), n is 28 to 33. The total weight of the cyclic polyether ester (A5) was 85% by weight based on the total weight of the cyclic polyether ester (A5).

<Manufacturing example 6>
"KYOWAAD 300" [Chemical _{Formula: 2.5MgO · Al 2 O 3 ·} nH 2 O (n is a positive number), Kyowa Chemical Industry Co., Ltd.] 24 hours of heat treatment under a nitrogen stream 900 ° C. in an electric furnace And the fired product was adjusted.

<Manufacturing example 7>
30 parts of 15-pentadecanolactone [manufactured by Tokyo Chemical Industry Co., Ltd.] and 1 part of the fired product obtained in Production Example 1 were put into a stainless steel autoclave equipped with a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 27.5 parts of ethylene oxide was press-fitted at 150 ° C. over 10 hours. Then, it was aged for 10 hours to obtain a mixture (PA6) containing the cyclic polyether ester compound (A).
The obtained mixture (PA6) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Kagaku Kogyo Co., Ltd.], which is a filtration aid, and Kyo. Ward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A6).
The obtained cyclic polyether ester compound (A6) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound (A6) was analyzed. ) Is the cyclic polyether ester compound of the present invention in which ^{R 1} is a tetradecamethylene group, R ² is an ethylene group, and n = 5, in the general formula (1), and ^{[R 1} CO (OR). ² ) It was a mixture containing a cyclic polyether ester compound having two repeating units represented by [nO] and a cyclic polyether ester compound having three.

<Manufacturing example 8>
In a stainless steel autoclave equipped with a stirrer and a temperature control function, 5 parts of the cyclic polyether ester compound (A6) obtained in Production Example 7, 2 parts of the calcined product obtained in Production Example 1, and 25 parts of xylene were placed. I put it in. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 45.4 parts of ethylene oxide was press-fitted at 150 ° C. over 10 hours. Then, it was aged for 10 hours to obtain a mixture (PA7-1) containing the cyclic polyether ester compounds (A6) and (A).
The obtained mixture (PA7-1) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A7).
The obtained cyclic polyether ester compound (A7) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound (A7) was analyzed. ^{) Is the cyclic compound of the present invention in which R 1} is a tetradecamethylene group, R ² is an ethylene group, and n = 100 in the general formula (1), and ^{[R 1} CO (OR ² ) nO. ], It was a mixture containing a cyclic compound having two repeating units and a cyclic polyether ester compound (A6) having three repeating units.

<Manufacturing example 9>
10 parts of the cyclic polyether ester compound (A7) obtained in Production Example 8, 2 parts of the calcined product obtained in Production Example 1, and 20 parts of xylene were placed in a stainless steel autoclave equipped with a stirrer and a temperature control function. I put it in. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 14.2 parts of ethylene oxide was press-fitted at 150 ° C. over 3 hours. Then, it was aged for 10 hours to obtain a mixture (PA8-1) containing a cyclic polyether ester compound.
Next, 31.2 parts of propylene oxide was press-fitted over 10 hours and further aged for 10 hours to obtain a mixture (PA8-2) containing a cyclic polyether ester compound.
The obtained mixture (PA8-2) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A8).
The obtained cyclic polyether ester compound (A8) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound (A8) was analyzed. ^{) Is a cyclic compound of the present invention in which R 1} is a tetradecamethylene group, R ² is an ethylene group and a methyl ethylene group, and n = 500 (EO: PO = 250: 250) in the general formula (1). It was a mixture containing a polyether ester compound, a cyclic polyether ester compound having two repeating units represented by [R ¹ CO (OR ^{2) nO], and a cyclic compound having three.}

<Manufacturing example 10>
Twenty parts of 15-pentadecanolactone [manufactured by Tokyo Chemical Industry Co., Ltd.] and two parts of the fired product obtained in Production Example 1 were put into a stainless steel autoclave equipped with a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 48.3 parts of propylene oxide was press-fitted at 150 ° C. over 10 hours and then aged for 5 hours to obtain a mixture (PA9-1) containing a cyclic polyether ester compound. The obtained mixture (PA9-1) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (PA9-2).
20 parts of the cyclic polyether ester compound (PA9-2) and 2 parts of the fired product obtained in Production Example 1 were put into a stainless steel autoclave equipped with a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 42.9 parts of ethylene oxide was press-fitted at 150 ° C. over 10 hours and then aged for 5 hours to obtain a mixture (PA9-2) containing a cyclic polyether ester compound. The obtained mixture (PA9-1) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A9).
The obtained cyclic polyether ester compound (A9) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound (A9) was analyzed. ^{) Is a cyclic polyether of the present invention in which R 1} is a tetradecamethylene group, R ² is an ethylene group and a methyl ethylene group, and n = 50 (EO 40 mol, PO 10 mol) in the general formula (1). It was a mixture containing an ester compound, a cyclic polyether ester compound having two repeating units represented by [R ¹ CO (OR ^{2) nO], and a cyclic polyether ester compound having three.}

<Manufacturing example 11>
Twenty parts of 15-pentadecanolactone [manufactured by Tokyo Chemical Industry Co., Ltd.] and three parts of the fired product obtained in Production Example 1 were put into a stainless steel autoclave equipped with a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 39 parts of the ethylene oxide / propylene oxide (molar ratio 4/1) mixture was press-fitted at 150 ° C. for 10 hours and then aged for 10 hours. Next, 41.0 parts of the reaction mixture was withdrawn from the autoclave, 52.9 parts of the ethylene oxide / propylene oxide (molar ratio 4/1) mixture was press-fitted over 10 hours, and then aged for 10 hours to contain the cyclic polyether ester compound. The mixture (PA10-1) was obtained.
The obtained mixture (PA10-1) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A10).
The obtained cyclic polyether ester compound (A10) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound (A10) was analyzed. ^{) Is a cyclic polyether of the present invention in which R 1} is a tetradecamethylene group, R ² is an ethylene group and a methyl ethylene group, and n = 50 (EO 40 mol, PO 10 mol) in the general formula (1). It was a mixture containing an ester compound, a cyclic polyether ester compound having two repeating units represented by [R ¹ CO (OR ^{2) nO], and a cyclic polyether ester compound having three.}

<Manufacturing example 12>
20 parts of the cyclic polyether ester compound (A7) obtained in Production Example 8, 2 parts of the calcined product obtained in Production Example 1, and 30 parts of xylene were placed in a stainless steel autoclave equipped with a stirrer and a temperature control function. I put it in. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 20.0 parts of ethylene oxide was press-fitted at 150 ° C. over 5 hours. Then, it was aged for 10 hours to obtain a mixture (PA11-1) containing a cyclic polyether ester compound. After extracting 54 parts of the mixture (PA11-1) from the autoclave, 2 parts of the fired product obtained in Production Example 1 and 30 parts of xylene were added. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 37.7 parts of ethylene oxide was press-fitted at 150 ° C. over 6 hours. Then, it was aged for 10 hours to obtain a mixture (PA11-2) containing a cyclic polyether ester compound. Xylene was distilled off under reduced pressure from the obtained mixture (PA11-2), cooled to 60 ° C., 200 parts of ethanol was added to adjust the temperature to 60 ° C., and then the filtration aid Radiolite # 700 [Showa Chemical Co., Ltd.] 5 parts of Kyoward 600 [manufactured by Kyowa Chemical Industry Co., Ltd.] and 5 parts of Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A11).
The obtained cyclic polyether ester compound (A11) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound (A11) was analyzed. ) Is the cyclic polyether ester compound of the present invention in which ^{R 1} is a tetradecamethylene group, R ² is an ethylene group, and n = 1000 in the general formula (1), ^{and further [R 1} CO (OR). ² ) It was a mixture containing a cyclic polyether ester compound having two repeating units represented by [nO] and a cyclic polyether ester compound having three.

<Manufacturing example 13>
20 parts of the cyclic polyether ester compound (A11) obtained in Production Example 12, 2 parts of the calcined product obtained in Production Example 1, and 40 parts of xylene were placed in a stainless steel autoclave equipped with a stirrer and a temperature control function. I put it in. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 19.9 parts of ethylene oxide was press-fitted at 150 ° C. over 3 hours. Then, it was aged for 5 hours to obtain a mixture (PA12-1) containing a cyclic polyether ester compound. Xylene was distilled off under reduced pressure from the obtained mixture (PA12-1), cooled to 60 ° C., 200 parts of ethanol was added to adjust the temperature to 60 ° C., and then the filtration aid Radiolite # 700 [Showa Chemical Industry Co., Ltd.] 5 parts of Kyoward 600 [manufactured by Kyowa Chemical Industry Co., Ltd.] and 5 parts of Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A12).
The obtained cyclic polyether ester compound (A12) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound (A12) was analyzed. ) Is the cyclic polyether ester compound of the present invention in which ^{R 1} is a tetradecamethylene group, R ² is an ethylene group, and n = 1500 in the general formula (1), ^{and further [R 1} CO (OR). ² ) It was a mixture containing a cyclic polyether ester compound having two repeating units represented by [nO] and a cyclic polyether ester compound having three.

<Manufacturing example 14>
20 parts of the cyclic polyether ester compound (A12) obtained in Production Example 13, 2 parts of the calcined product obtained in Production Example 1, and 40 parts of xylene were placed in a stainless steel autoclave equipped with a stirrer and a temperature control function. I put it in. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 6.6 parts of ethylene oxide was press-fitted at 150 ° C. over 1 hour. Then, it was aged for 5 hours to obtain a mixture (PA13-1) containing a cyclic polyether ester compound. Xylene was distilled off under reduced pressure from the obtained mixture (PA13-1), cooled to 60 ° C., 200 parts of ethanol was added to adjust the temperature to 60 ° C., and then the filtration aid Radiolite # 700 [Showa Chemical Industry Co., Ltd.] 5 parts of Kyoward 600 [manufactured by Kyowa Chemical Industry Co., Ltd.] and 5 parts of Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A13).
The obtained cyclic polyether ester compound (A13) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound (A13) was analyzed. ) Is the cyclic polyether ester compound of the present invention in which ^{R 1} is a tetradecamethylene group, R ² is an ethylene group, and n = 2000 in the general formula (1), ^{and further [R 1} CO (OR). ² ) It was a mixture containing a cyclic polyether ester compound having two repeating units represented by [nO] and a cyclic polyether ester compound having three.

<Comparative manufacturing example 1>
Dissolve 5 parts of the polyether ester compound (A6) obtained in Production Example 7 in 100 parts of methanol, add 0.1 part of sodium methoxide [manufactured by Wako Pure Chemical Industries, Ltd.], and use a magnetic stirrer at 50 ° C. The mixture was stirred for 5 hours. Next, the solution was passed through a chromatographic tube filled with DOWEXTM 50WX8 (100-200 mesh) [manufactured by The Dow Chemical Company], and then dried under reduced pressure to obtain a chain polyether ester compound (A'6). ..

<Comparative manufacturing example 2>
In Comparative Production Example 1, the chain was the same as in Comparative Production Example 1 except that the polyether ester compound (A7) obtained in Production Example 8 was changed to the polyether ester compound (A7) obtained in Production Example 8. A state polyether ester compound (A'7) was obtained.

<Manufacturing Example 15: Manufacture of Polyamide>
173 parts of ε-caprolactam, 33.2 parts of terephthalic acid, antioxidant ["Irganox 1010", Ciba Made by Specialty Chemicals Co., Ltd.] 0.4 part and 10 parts of water were added, and after nitrogen replacement, the temperature was raised to 220 ° C with stirring under sealing, and the same temperature (pressure: 0.2 to 0.3 MPa). The mixture was stirred for 4 hours to obtain a polyamide (a1-1) having a carboxyl group at both ends. The acid value of the polyamide (a1-1) was 111, and the Mn was 1,000.

<Production Example 16: Modified Low Molecular Weight Polypropylene>
[Manufacture of polyolefin (a2-1-1α) having carboxyl groups at both ends]
In a pressure-resistant reaction vessel similar to that of Production Example 15, low molecular weight polypropylene [polypropylene (MFR: 10 g / 10 min) obtained by the thermal decomposition method was placed at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Obtained by heat reduction. Mn: 3,400, number of double bonds per 1,000 carbon atoms: 7.0, average number of double bonds per molecule: 1.8, content of polyolefins that can be modified at both ends: 90 weight %] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were added, mixed uniformly, replaced with nitrogen, heated to 200 ° C. with stirring under sealing, melted, and reacted at the same temperature for 10 hours. I let you. Next, excess maleic anhydride and xylene were distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to form a polyolefin (a2-1-1α) 95 having carboxyl groups at both ends of the polymer. I got a part. The acid value of (a2-1-1α) was 27.5, and Mn was 3,600.

<Manufacturing example 17>
[Production of Polyolefin (a2-1-2) obtained by secondary modification of polyolefin (a2-1-1α)]
88 parts of the polyolefin (a2-1-1α) and 12 parts of 12-aminododecanoic acid obtained in Production Example 16 were put into the same pressure-resistant reaction vessel as in Production Example 15, mixed uniformly, and then in a nitrogen gas atmosphere. The temperature is raised to 200 ° C. with stirring, and the reaction is carried out at the same temperature under reduced pressure (0.013 MPa or less) for 3 hours to secondarily denature the polyolefin (a2-1-1α) and then secondarily denature with 12-aminododecanoic acid. 96 parts of the polyolefin (a2-1-2) obtained was obtained. The acid value of the polyolefin (a2-1-2) was 24.8 and the Mn was 4,000.

<Manufacturing example 18>
[Manufacture of polyolefin (a2-2) having hydroxyl groups at both ends]
In Production Example 16, 90 parts of low molecular weight polypropylene and 10 parts of maleic anhydride obtained by the heat reduction method were used, and 94 parts of low molecular weight ethylene / propylene random copolymer and maleic anhydride 6 obtained by the heat reduction method were used. 98 parts of polyolefin (a2-1-1β) having carboxyl groups at both ends of the polymer was obtained in the same manner as in Production Example 7 except that the parts were changed to parts.
The acid value of the polyolefin (a2-1-1β) was 9.9, and the Mn was 10,200.
The low molecular weight ethylene / propylene random copolymer (Mn: 10,000, number of double bonds per 1,000 carbon atoms: 2.5, 2 per molecule) obtained by the above thermal modification method. The average number of double bonds: 1.8, content of polyolefin that can be modified at both ends: 90% by weight) is 410 for ethylene / propylene random copolymer (ethylene content: 2% by weight, MFR: 10 g / 10 min). It was obtained by heat-polymerizing at ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 14 minutes.
Next, 97 parts of polyolefin (a2-1-1β) and 5 parts of ethanolamine were put into the same pressure-resistant reaction vessel as in Production Example 6, and the temperature was raised to 180 ° C. with stirring under a nitrogen gas atmosphere at the same temperature. It was allowed to react for 2 hours. Further, excess ethanolamine was distilled off under reduced pressure (0.013 MPa or less) at 180 ° C. for 2 hours to obtain a polyolefin (a2-2) having hydroxyl groups at both ends of the polymer. The hydroxyl value of the polyolefin (a2-2) was 9.9, the amine value was 0.01, and Mn was 10,200.

<Manufacturing example 19>
[Production of modified polyolefin (a2-4) having amino groups at both ends]
Except that in Production Example 16, 90 parts of low molecular weight polypropylene and 10 parts of maleic anhydride obtained by the heat reduction method were changed to 80 parts of low molecular weight polypropylene and 20 parts of maleic anhydride obtained by the heat reduction method. In the same manner as in Production Example 7, 92 parts of polyolefin (a2-1-1γ) having carboxyl groups at both ends of the polymer was obtained. The acid value of the polyolefin (a2-1-1γ) was 64.0, and the Mn was 1,700.
The low molecular weight polypropylene (Mn: 1,500, number of double bonds per 1,000 carbon atoms: 17.8, average number of double bonds per molecule:: 1.94, content of polyolefin that can be modified at both ends: 98% by weight) is an ethylene / propylene random copolymer (ethylene content: 3% by weight, MFR: 7 g / 10 min) at 410 ± 0.1 ° C. It was obtained by heat-reducing for 18 minutes.
Next, 90 parts of polyolefin (a2-1-1γ) and 10 parts of bis (2-aminoethyl) ether were put into the same pressure-resistant reaction vessel as in Production Example 15, and the temperature was raised to 200 ° C. with stirring under a nitrogen gas atmosphere. It was warmed and reacted at the same temperature for 2 hours. Further, excess bis (2-aminoethyl) ether was distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 2 hours to obtain a modified polyolefin (a2-4) having amino groups at both ends. The amine value of the modified polyolefin (a2-4) was 64.0, and the Mn was 1,700.

<Manufacturing example 20>
[Manufacturing of cationic polymer (b3α)]
41 parts of N-methyldiethanolamine, 49 parts of adipic acid and 0.3 part of zirconyl acetate were put into the same pressure-resistant reaction vessel as in Production Example 15, and after nitrogen substitution, the temperature was raised to 220 ° C. over 2 hours and 1 hour. The pressure was reduced to 0.013 MPa to carry out the polyesterification reaction. After completion of the reaction, the mixture was cooled to 50 ° C. and 100 parts of methanol was added to dissolve the reaction. Subsequently, the temperature in the reaction vessel was maintained at 120 ° C. with stirring, 31 parts of dimethyl carbonate was added dropwise over 3 hours, and stirring was continued at the same temperature for 6 hours for reaction aging. Then, the mixture was cooled to room temperature, 100 parts of a 60 wt% hexafluorophosphoric acid aqueous solution was added, and the mixture was stirred at room temperature for 1 hour. Next, methanol was distilled off under reduced pressure, and a cationic polymer (b3α) having an average of 12 quaternary ammonium groups (hydroxyl value: 30.1, acid value: 0.5, volume resistivity: 1 × 10 ⁵ Ω · cm). ) Was obtained.

<Manufacturing example 21>
[Manufacturing of anionic polymer (b4α)]
114 parts of diethylene glycol, 268 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 parts of dibutyltin oxide were put into a pressure resistant reaction vessel similar to that of Production Example 15, and the temperature was raised to 190 ° C. under a reduced pressure of 0.067 MPa. The transesterification reaction was carried out by warming and stirring at the same temperature for 6 hours while distilling off methanol, and an anionic polymer (b4α) having an average of 6 sodium sulfonate bases in one molecule (hydroxyl value: 49, acid value 0.6, volume resistivity was obtained ^{3 × 10 8 Ω · cm)} .

<Manufacturing example 22>
[Manufacturing of anionic polymer (b4β)]
67 parts of PEG (Mn: 300), 49 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 part of dibutyltin oxide were put into a pressure resistant reaction vessel similar to that of Production Example 15 under a reduced pressure of 0.067 MPa. The temperature is raised to 190 ° C., and the ester exchange reaction is carried out by stirring at the same temperature for 6 hours while distilling off methanol to carry out a transesterification reaction, which is an anionic polymer (b4β) (hydroxyl group) having an average of 5 sodium sulfonate bases in one molecule. Value: 29.6, acid value: 0.4, volume specific resistance value: 2 × 10 ⁶ Ω · cm) was obtained.

<Manufacturing example 23>
[Manufacturing of block polymer (C1-1)]
199 parts of polyamide (a1-1) and EO adduct of bisphenol A (Mn: 4,000, volume resistivity: 2 × 10 ⁷ Ω · cm) in a reaction vessel equipped with a stirrer, thermometer and heating / cooling device. ) 780 parts and 0.6 parts of zirconyl acetate were added, the temperature was raised to 240 ° C. with stirring, and the condensation reaction was carried out under reduced pressure (0.013 MPa or less) at the same temperature for 6 hours to carry out a condensation reaction, and a viscous block polymer was carried out. (C1-1) was obtained. The Mn of the block polymer (C1-1) was 24,000.

<Manufacturing example 24>
[Manufacturing of block polymer (C1-2)]
In the same pressure-resistant reaction vessel as in Production Example 15, 143 parts of polyamide (a1-1), 320 parts of the anionic polymer (b4α) obtained in Production Example 21, and 0.3 part of the antioxidant "Irganox 1010" were put. Then, the temperature was raised to 240 ° C. with stirring, and the reaction was carried out under reduced pressure (0.013 MPa or less) at the same temperature for 5 hours to obtain a viscous block polymer (C1-2). The Mn of the block polymer (C1-2) was 21,000.

<Manufacturing example 25>
[Manufacturing of block polymer (C2-1)]
67.1 parts of polyolefin (a2-1-1α), polyetherdiamine (b1-2) [α, ω-diaminoPEG (Mn: 2,000, volume resistivity)) in the same pressure-resistant reaction vessel as in Production Example 15. 1 × 10 ⁷ Ω · cm)] 32.9 parts, 0.3 part of the antioxidant “Irganox 1010” and 0.5 part of zirconyl acetate were added, and the temperature was raised to 220 ° C. under reduced pressure with stirring. The reaction was carried out at the same temperature for 3 hours (0.013 MPa or less) to obtain a viscous block polymer (C2-1). The Mn of the block polymer (C2-1) was 50,000.

<Manufacturing example 26>
[Manufacturing of block polymer (C2-2)]
67.1 parts of the polyolefin (a2-1-1α) and 32.9 parts of the polyether diamine (b1-2) obtained in Production Example 16 were added to the polyolefin (a2-1-2) 60 obtained in Production Example 8. .1 part and polyether diol (b1-1α) [PEG (Mn: 3,000, volume resistivity: 1 × 10 ⁷ Ω · cm)] Same as Production Example 25 except that it was changed to 39.9 parts. To obtain a block polymer (B2-2). The Mn of the block polymer (B2-2) was 30,000.

<Manufacturing example 27>
[Manufacturing of block polymer (C2-3)]
67.1 parts of the polyolefin (a2-1-1α) and 32.9 parts of the polyetherdiamine (b1-2) obtained in Production Example 16 were added to the polyolefin (a2-2) 48.0 obtained in Production Example 9. A block polymer (C2-3) was obtained in the same manner as in Production Example 25 except that the parts were changed to 48.0 parts of the cationic polymer (b3α) obtained in Production Example 11 and 4 parts of dodecanedioic acid. The Mn of the block polymer (C2-3) was 100,000.

<Manufacturing example 28>
[Manufacturing of block polymer (C2-4)]
67.1 parts of the polyolefin (a2-1-1α) and 32.9 parts of the polyetherdiamine (b1-2) obtained in Production Example 16 were added to 31.6 parts of the polyolefin (a2-4) obtained in Production Example 10. A block polymer (C2-4) was obtained in the same manner as in Production Example 25 except that the parts were changed to 68.4 parts of the anionic polymer (b4β) and 8 parts of dodecanedioic acid. The Mn of the block polymer (C2-4) was 10,000.

<Manufacturing example 29>
[Manufacturing of block polymer (C2-5)]
67.1 parts of polyolefin (a2-1-1α) and 32.9 parts of polyetherdiamine (b1-2) obtained in Production Example 16 and 71.5 parts of polyolefin (a2-1-2) and polyetherdiol. (B1-1β) [Polytetramethylene glycol (Mn: 1,800, volume resistivity: 1 × 10 ¹¹ Ω · cm) The block polymer (Mn: 1,800, volume resistivity: 1 × 10 11 Ω · cm) was changed to 28.5 parts in the same manner as in Production Example 25. C2-5) was obtained. The Mn of the block polymer (C2-5) was 40,000.

<Manufacturing example 30>
[Manufacturing of block polymer (C2-6)]
67.1 parts of the polyolefin (a2-1-1α) and 32.9 parts of the polyether diamine (b1-2) obtained in Production Example 16 were added to 48.0 parts of the polyolefin (a2-2) and the cationic polymer (b3α). ) 48.0 parts and hexamethylene diisocyanate (HDI) were changed to 3 parts in the same manner as in Production Example 25 to obtain a block polymer (C2-6). The Mn of the block polymer (C2-6) was 100,000.

<Manufacturing example 31>
[Manufacturing of block polymer (C'-1)]
A block polymer (C'-1) was obtained in the same manner as in Compound 2 described in JP2012-97239.

<Examples 1-36, Comparative Examples 1-4>
A mixture of the raw materials constituting the antistatic resin composition dry-blended in the amounts shown in Table 1 is mixed using a twin-screw extruder heated to the temperatures shown in Tables 1 and 2, and has antistatic properties. A resin composition was obtained.
As the thermoplastic resin (B-1) shown in Tables 1 and 2, "PM771M" manufactured by SunAllomer Ltd., which is a polypropylene resin, is used, and as (B-2), PS is used as the polystyrene resin. Impact-resistant polystyrene resin "HIPS433" manufactured by Japan Corporation was used, and a lithium trifluoromethanesulfonic acid salt was used as the antistatic property improver (D1). Further, the block polymer (B'-1) used in Comparative Example 1 includes compound 2 [methoxy (polyethyleneoxy) chain and hydroxy (polyhexadecylethylene) described in Examples of JP2012-97239A. A block polymer composed of an oxy) chain] was prepared and used by the method described in JP2012-97239A. As the cyclic ester (A'1) of the comparative example, 15-pentadecanolactone manufactured by Tokyo Chemical Industry Co., Ltd. was used.

The antistatic resin compositions obtained in Examples 1 to 36 or Comparative Examples 1 to 4 were molded by an injection molding machine (cylinder temperature 240 ° C. and mold temperature 60 ° C.) to prepare test pieces, and tested. The surface specific resistance value and the impact strength of Izot before and after washing the piece with water were evaluated by the following methods, and the results are shown in Tables 1 and 2.

<Performance test>
(1) Surface specific resistance value before washing In accordance with ASTM D257, the test piece (100 x 100 x 2 mm) was subjected to a super-insulation meter "DSM-8103" [manufactured by Toa Radio Co., Ltd.] at 23 ° C. and humidity. It was measured in an atmosphere of 50% RH.
(2) Surface specific resistance value after washing with water A test piece (100 x 100 x 2 mm) is leaned against the surface, washed with running water at 23 ° C. and a flow rate of 100 ml / min with 100 ml of ion-exchanged water, and then a circulation dryer (80 ° C.). ) Was dried for 3 hours. This washing and drying operation was repeated 10 times, and the obtained test piece was measured under the same conditions as in (1).
(3) Izod impact strength Measured according to ASTM D256 Measurement A (notched, 3.2 mm thickness).

The antistatic resin composition of the present invention (Examples 1 to 36) is superior in surface specific resistance value after washing with water and Izod impact strength as compared with Comparative Examples.

The antistatic resin composition of the present invention has both antistatic durability and mechanical properties in a well-balanced manner. Since the above effects are obtained, the antistatic resin composition of the present invention is extremely useful as various molding materials requiring antistatic properties such as housing products for home appliances and OA equipment, various plastic containers, automobile parts, and the like. be.

Claims (4)

An antistatic resin composition containing a cyclic polyether ester (A) represented by the general formula (1) and a thermoplastic resin (B) , wherein the thermoplastic resin (B) contains polypropylene and / or polystyrene. An antistatic resin composition further comprising a block polymer (C) having a block of the hydrophobic polymer (a) and a block of the hydrophilic polymer (b).

[In the formula, R ¹ is a linear or branched alkylene group having 3 to 16 carbon atoms. R ² is an alkylene group having 2 to 4 carbon atoms. m is an integer of 1 to 3 and n is an integer of 1 to 2000. The m R ^1s may be the same or different, and the m × n R ^2s may be the same or different. ] The antistatic resin composition according to claim 1, wherein the cyclic polyether ester (A) is contained in an amount of 0.1 to 20% by weight based on the total weight of the antistatic resin composition. A polyamide having 4 to 20 carbon atoms as a constituent monomer obtained by ring-opening polymerization or polycondensing the amide-forming monomer (α) in the block of the hydrophobic polymer (a) contained in the block polymer (C). , Polymer whose constituent unit is an aminocarboxylic acid having 2 to 20 carbon atoms, Polypolymer obtained by polycondensing diamine (β) having 2 to 20 carbon atoms and dicarboxylic acid (γ) having 2 to 20 carbon atoms, these. The block of the hydrophilic polymer (b) contained in the block polymer (C) is a poly, which is at least one type of block selected from the group consisting of a copolymer of the constituent monomers of polyamide and a polyolefin. A block made of ether, at least one selected from the group consisting of a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond. The antistatic resin composition according to claim 1 or 2 , which is a block polymer bonded via a bond. The invention according to any one of claims 1 to 3, wherein the weight ratio of the block polymer (C) contained in the thermoplastic resin (B) is 5 to 100% by weight based on the total weight of the thermoplastic resin (B). Antistatic resin composition.