JP2018059077A - Agent for imparting dielectric heating properties to polyolefin resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dielectric heating property imparting agent for polyolefin resin which imparts excellent dielectric heating characteristics to polyolefin resin without impairing mechanical strength and appearance. A block of polymer (a) having a volume resistivity exceeding 1 × 10 11 Ω · cm and a block of polymer (b) having a volume resistivity of 1 × 10 5 to 1 × 10 11 Ω · cm are structural units. Dielectric heating property imparting agent (Z) for polyolefin resin, comprising block polymer (A) contained as [Selection figure] None

Description

The present invention relates to a dielectric heating property imparting agent for polyolefin resin. Specifically, the present invention relates to a dielectric heating property-imparting agent for polyolefin resin that imparts excellent dielectric heating characteristics to the polyolefin resin.
The dielectric heating characteristic in the present invention means a property in which an object is heated due to heat generation due to dielectric loss in a high-frequency electric field, and is evaluated by the weldability after dielectric heating described later. .

  As represented by dielectric welding (high frequency welding) technology, dielectric heating is known as a useful method that can shorten the manufacturing process time and increase the efficiency in the manufacturing industry that joins synthetic resin molded products. Yes. However, synthetic resins to which dielectric heating can be applied are limited to specific resins. Polymers capable of dielectric heating in response to high frequencies include polyvinyl chloride, functionalized polyolefins (such as copolymers of ethylene and vinyl acetate and ethylene-methyl methacrylate copolymers) and thermoplastic polyurethanes. However, these polymers may not have the physical and mechanical properties required for a particular application.

On the other hand, polyolefin is an excellent thermoplastic resin used for various applications such as packaging, automotive interior members, and structural members. Coupled with the increasing movement to replace polyvinyl chloride using polyolefin materials that do not contain chlorine, polyolefin resins such as polyethylene and polypropylene with dielectric heating properties have been strongly demanded. ing.
Conventionally, as a method of having dielectric heating characteristics in polyolefin, there has been a proposal such as a method of blending carbon black with a polyolefin resin (see, for example, Patent Document 1).

Japanese Patent Laid-Open No. 3-218813

However, the method of blending carbon black has a problem that it is difficult to control the heat generation, and if the heat is excessively heated, the polyolefin resin undergoes thermal degradation.
An object of the present invention is to provide a dielectric heating property-imparting agent for polyolefin resin that imparts excellent dielectric heating properties to the polyolefin resin without impairing mechanical strength and appearance.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, the present invention is the specific volume and blocking resistance exceeds 1 × 10 ¹¹ Ω · cm polymer (a), a volume resistivity ^{1 × 10 5 ~1 × 10 11} Ω · cm polymer (b) And a dielectric polymer having a block polymer (A) containing the block as a constituent unit (Z); a dielectric heat resistance imparting agent (Z) for polyolefin resin; a polyolefin resin (Y); A dielectric heating polyolefin resin composition (X) comprising: a dielectric heating molded article obtained by molding the dielectric heating polyolefin resin composition (X); a molded article obtained by dielectric heating the molded article.

The dielectric heating property-imparting agent (Z) for polyolefin resin of the present invention, the polyolefin resin composition (X) for dielectric heating comprising the dielectric heating property-imparting agent (Z), and molded articles thereof have the following effects.
(1) The dielectric heating property-imparting agent (Z) for polyolefins of the present invention imparts excellent dielectric heating properties (dielectric heating properties) to polyolefin resins without impairing the original mechanical strength (mechanical properties).
(2) A molded product of the polyolefin resin composition for dielectric heating (X) containing the dielectric heating property-imparting agent (Z) of the present invention has excellent dielectric heating characteristics and a good appearance.

  The dielectric heatability imparting agent (Z) for polyolefin resin of the present invention contains a block polymer (A) containing a block of the polymer (a) and a block of the polymer (b) as structural units.

<Polymer (a)>
The polymer (a) in the present invention has a volume resistivity value exceeding 1 × 10 ¹¹ Ω · cm. Specific examples of the polymer (a) include polyamide (a1), polyolefin (a2), and polyamideimide (a3), and these may be used in combination of two or more. Among (a), polyamide (a1) and polyolefin (a2) are preferable from the viewpoint of dielectric heating characteristics, and polyolefin (a2) is more preferable.
In addition, the volume resistivity value in this invention is a numerical value obtained by measuring in 23 degreeC and 50% RH atmosphere based on ASTMD257 (1984).

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

Examples of the amide-forming monomer (α) include lactam (α1-1) and aminocarboxylic acid (α1-2).
Examples of the lactam (α1-1) include lactams having 4 to 20 carbon atoms (caprolactam, enantolactam, laurolactam, undecanolactam, and the like).
As the aminocarboxylic acid (α1-2), an aminocarboxylic acid having 2 to 20 carbon atoms (ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and a mixture thereof).

  Examples of the diamine (β) include aliphatic diamines having 2 to 20 carbon atoms (ethylenediamine, propylenediamine, hexamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, and 1,20-eicosane. Diamines, etc.), alicyclic diamines having 5 to 20 carbon atoms [1,3- or 1,4-cyclohexanediamine, isophoronediamine, 4,4′-diaminocyclohexylmethane and 2,2-bis (4-aminocyclohexyl) Propane and the like], aromatic diamines having 6 to 20 carbon atoms [p-phenylenediamine, 2,4- or 2,6-toluylenediamine and 2,2-bis (4,4′-diaminophenyl) propane, p- Or m-xylylenediamine, bis (aminoethyl) benzene, bis (aminopropyl) ben Emissions and bis (aminobutyl) benzene, etc.] and the like.

  Examples of the dicarboxylic acid (γ) include aliphatic dicarboxylic acids having 2 to 20 carbon atoms (succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid. , Fumaric acid and itaconic acid), aromatic dicarboxylic acids having 8 to 20 carbon atoms (phthalic acid, 2,6- or 2,7-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid) Acid, tolylene dicarboxylic acid, xylylene dicarboxylic acid, 5-sulfoisophthalic acid alkali metal salt, etc.), alicyclic dicarboxylic acid having 5 to 20 carbon atoms (cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid) Acid, dicyclohexyl-4,4′-dicarboxylic acid, camphoric acid, etc.) .

  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. And a copolymer of nylon 6 and nylon 12 and a copolymer of nylon 6, nylon 6, 6 and nylon 12.

Examples of the polyolefin (a2) include a polyolefin (a2-1) having carboxyl groups at both ends of the polymer, a polyolefin (a2-2) having hydroxyl groups at both ends of the polymer, and a polyolefin (a2) having amino groups at both ends of the polymer. -3) and polyolefin (a2-4) having an isocyanate group at both ends of the polymer, polyolefin (a2-5) having a carboxyl group at one end of the polymer, and polyolefin (a2-6) having a hydroxyl group at one end of the polymer And polyolefin (a2-7) having an amino group at one end of the polymer and polyolefin (a2-8) having an isocyanate group at one end of the polymer.
Of these, (a2-1) and (a2-5) having a carboxyl group at the terminal are preferable from the viewpoint of ease of modification and suppression of coloring after resin mixing.
In addition, the terminal in this invention means the terminal part which the repeating structure of the monomer unit which comprises a polymer interrupts. Moreover, both ends mean both ends in the main chain of the polymer, and one end means any one end in the main chain of the polymer.

  As (a2-1), a polyolefin (a2) whose main component (preferably the content is 50% by weight or more, more preferably 75% by weight or more, and particularly preferably 80 to 100% by weight) is a polyolefin that can be modified at both ends. -01) having carboxyl groups introduced at both ends thereof; (a2-2) having (a2-01) having hydroxyl groups introduced at both ends; (a2-3) having (a2-01) As for (a2-4), those obtained by introducing isocyanate groups at both ends of (a2-01) can be used.

  As (a2-5) to (a2-8), in place of the polyolefin (a2-01), a polyolefin whose one end can be modified is a main component (preferably a content of 50% by weight or more, more preferably 75% by weight). As mentioned above, what introduce | transduced respectively the carboxyl group, a hydroxyl group, an amino group, or an isocyanate group can be used for the one end of the polyolefin (a2-02) made into 80 weight% especially preferably.

In the polyolefin (a2-01) whose main component is a polyolefin whose both ends can be modified, one or two or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10 carbon atoms) are used. (Co) polymerization of the mixture [(co) polymerization means polymerization or copolymerization. The same applies below. ] Obtained by (polymerization method) and degraded polyolefin {high molecular weight [preferably number average molecular weight (hereinafter abbreviated as Mn) 50,000 to 150,000] polyolefin, mechanical, thermal or chemical (Degraded method)} is included.
Among these, a degraded polyolefin (degraded polyolefin) is preferable from the viewpoint of ease of modification and availability when introducing a carboxyl group, a hydroxyl group, an amino group, or an isocyanate group. Further preferred is a heat-degraded polyolefin (heat-degraded polyolefin).
According to the thermal degradation, as described later, a low molecular weight polyolefin having an average number of terminal double bonds of 1.5 to 2 per molecule is easily obtained, and the low molecular weight polyolefin is a carboxyl group, a hydroxyl group, or an amino group. Alternatively, it is easy to modify by introducing an isocyanate group or the like.

Mn of the polymer in the present invention can be measured under the following conditions using gel permeation chromatography (GPC).
Apparatus (example): “HLC-8120” [manufactured by Tosoh Corporation]
Column (example): “TSKgelGMHXL” (2 pieces)
"TSKgelMultiporeHXL-M" (1 pc.)
Sample solution: 0.3 wt% orthodichlorobenzene solution Solution injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 135 ° C
Detector: 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-degraded polyolefin is not particularly limited, and is obtained by heating a high molecular weight polyolefin in an inert gas (at 300 to 450 ° C. for 0.5 to 10 hours, for example, JP-A-3-62804). Obtained by the method described in the gazette), and heat-degraded by heating in air.

The high molecular weight polyolefin used in the thermal degradation method is a (co) polymer of one or a mixture of two or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10 carbon atoms). Mn 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. are mentioned.
Here, MFR is a numerical value representing the melt viscosity of the resin, and the larger the numerical value, the lower the melt viscosity. For the measurement of MFR, an extrusion plastometer defined in JIS K 6760 is used, and the measurement method conforms to the method defined in JIS K 7210 (1976). For example, in the case of polypropylene, it is measured under conditions of 230 ° C. and a load of 2.16 kgf.

Examples of the olefin having 2 to 30 carbon atoms include α-olefins having 2 to 30 carbon atoms and dienes having 4 to 30 carbon atoms.
Examples of the α-olefin having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-icocene and 1-icosene. Tetracocene and the like can be mentioned.
Examples of the diene having 4 to 30 carbon atoms include butadiene, isoprene, cyclopentadiene and 1,11-dodecadiene.
Of the olefins having 2 to 30 carbon atoms, ethylene, propylene, α-olefins having 4 to 12 carbon atoms, butadiene, isoprene and a mixture thereof are preferable from the viewpoint of controlling the molecular weight, and ethylene, Propylene, C 4-10 α-olefin, butadiene and mixtures thereof, particularly preferred are ethylene, propylene, butadiene and mixtures thereof.

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 200 from the viewpoint of dielectric heating property of the molded product described later. 6,000.
The number of terminal double bonds in (a2-01) is preferably 1 to 40 per 1,000 carbon atoms, more preferably 2 to 30 and particularly preferably from the viewpoint of dielectric heating property of the molded product. Is 4-20.

  (A2-01) The average number of terminal double bonds per molecule is preferably from the viewpoint of the ease of taking a repeating structure in the molecule, the dielectric heating property of the molded product, and the thermoplasticity of the block polymer (A) described later. Is 1.1 to 5, more preferably 1.3 to 3, particularly preferably 1.5 to 2.5, and most preferably 1.8 to 2.2.

  When a method for obtaining a low molecular weight polyolefin by a thermal degradation method is used, (a2-01) in which the average number of terminal double bonds per molecule is 1.5 to 2 (a2-01) in the range of 800 to 6,000 Mn. [Katsuhide Murata, Tadahiko Makino, Journal of the Chemical Society of Japan, page 192 (1975)].

Polyolefin (a2-02) whose main component is a polyolefin that can be modified at one end can be obtained in the same manner as (a2-01), and Mn in (a2-02) is the dielectric heating of the molded product described later. From the viewpoint of properties, 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 in (a2-02) is preferably 0.3 to 20 from the viewpoint of the dielectric heating property of the molded product and the molecular weight control of the block polymer (A), More preferably, it is 0.5-15, Most preferably, it is 0.7-10, Most preferably, it is 0.7-7.

(A2-02) The average number of double bonds per molecule is preferably from the viewpoints of easy repetitive structure in the molecule, dielectric heating property of the molded product, and thermoplasticity of the block polymer (A) described later. It is 0.5 to 1.4, more preferably 0.6 to 1.3, particularly preferably 0.7 to 1.2, and most preferably 0.8 to 1.1.
Of the (a2-02), from the viewpoint of ease of modification, a low molecular weight polyolefin obtained by a thermal degradation method is preferred, and a Mn obtained by a thermal degradation method is more preferably 3. , 20,000 to 20,000 polyethylene and / or polypropylene.
When a method for obtaining a low molecular weight polyolefin by a thermal degradation method is used, the average number of terminal double bonds per molecule is 1 to 1.5 (a2−) with Mn in the range of 6,000 to 30,000. 02) is obtained.
Since the low molecular weight polyolefin obtained by the thermal degradation method has the average number of the terminal double bonds, it can be easily modified by introducing a carboxyl group, a hydroxyl group, an amino group or an isocyanate group.

  In addition, (a2-01) and (a2-02) are obtained, for example, as a mixture thereof, but the mixture may be used as it is, or may be used after purification and separation. Among these, a mixture is preferable from the viewpoint of production cost and the like.

  Hereinafter, (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 at one end of the polyolefin (a2-02) (A2-5) to (a2-8) having these groups are the same as (a2-1) to (a2-4), except that (a2-01) is replaced with (a2-02). Can be obtained.

  As the polyolefin (a2-1) having carboxyl groups at both ends of the polymer, the end of (a2-01) is α, β-unsaturated carboxylic acid (anhydride) [α, β-unsaturated carboxylic acid, its alkyl (C1-C4) An ester or its anhydride is meant. The same applies below. ] (A2-1-1), (a2-1-1) having a structure modified with lactam or aminocarboxylic acid (a2-1-2), (a2-01) Polyolefin having a structure modified by oxidation or hydroformylation (a2-1-3), and polyolefin having a structure obtained by secondary modification of (a2-1-3) with lactam or aminocarboxylic acid (a2-1-4) And mixtures of two or more of these can be used.

(A2-1-1) can be obtained by modifying (a2-01) with an α, β-unsaturated carboxylic acid (anhydride).
Examples of α, β-unsaturated carboxylic acids (anhydrides) used for modification include monocarboxylic acids, dicarboxylic acids, mono- or dicarboxylic acid alkyl (C 1-4) esters, and mono- or dicarboxylic acid anhydrides. Specifically, (meth) acrylic acid [(meth) acrylic acid means acrylic acid or methacrylic acid. The same applies below. ], Methyl (meth) acrylate, butyl (meth) acrylate, maleic acid (anhydride), dimethyl maleate, fumaric acid, itaconic acid (anhydride), diethyl itaconate and citraconic acid (anhydride) It is done.
Of these, dicarboxylic acids, mono- or dicarboxylic acid alkyl esters and mono- or dicarboxylic acid anhydrides are preferred from the viewpoint of ease of modification, and maleic acid (anhydride) and fumaric acid are more preferred. Particularly preferred is maleic acid (anhydride).

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

(A2-1-2) can be obtained by secondary modification of (a2-1-1) with lactam or aminocarboxylic acid.
Examples of the lactam used for the secondary modification include lactams having 6 to 12 carbon atoms (preferably 6 to 8, more preferably 6), and specifically include caprolactam, enantolactam, laurolactam, undecanolactam, and the like. Is mentioned.
Examples of the aminocarboxylic acid include aminocarboxylic acids having 2 to 12 carbon atoms (preferably 4 to 12 and more preferably 6 to 12), and specifically include amino acids (glycine, alanine, valine, leucine, isoleucine). And phenylalanine), ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Among the lactams and aminocarboxylic acids, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred, and caprolactam and laurolactam are more preferred. Ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, particularly preferred are caprolactam and 12-aminododecanoic acid.

  The amount of lactam or aminocarboxylic acid used for secondary modification is based on the weight of the substance to be modified (a2-1-1), ease of repetitive structure in the molecule, dielectric heating property of the molded product, and block polymer From the viewpoint of the thermoplasticity of (A), it is preferably 0.5 to 200% by weight, more preferably 1 to 150% by weight, and particularly preferably 2 to 100% by weight.

(A2-1-3) can be obtained by introducing a carboxyl group by a method of oxidizing (a2-01) with oxygen and / or ozone (oxidation method) or hydroformylation by an oxo method.
The introduction of the carbonyl group by the oxidation method can be performed by a known method, for example, the method described in US Pat. No. 3,692,877. Introduction of the carbonyl group by hydroformylation may be carried out by various methods including known methods such as Macromolecules, VOL. 31, 5943 page.
(A2-1-4) can be obtained by secondary modification of (a2-1-3) with lactam or aminocarboxylic acid.
Examples of the lactam and aminocarboxylic acid include those exemplified as the lactam and aminocarboxylic acid used for the secondary modification of the above (a2-1-1), and preferred ranges and use amounts thereof are also the same. .

  The acid value of (a2-1) is preferably 4 to 280 mgKOH / g, more preferably 4 to 100 mgKOH / g, particularly preferably from the viewpoint of reactivity with (b) and thermoplasticity of the block polymer (A). 5-50 mg KOH / g.

Polyolefins having hydroxyl groups at both ends of the polymer (a2-2) include polyolefins having hydroxyl groups obtained by modifying the polyolefin (a2-1) having carboxyl groups at both ends of the polymer with amines having hydroxyl groups, and these 2 Mixtures of more than one species can be used.
Examples of the amine having a hydroxyl group that can be used for modification include amines having a hydroxyl group having 2 to 10 carbon atoms, and specifically include 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-amino. Examples include butanol, 5-aminopentanol, 6-aminohexanol and 3-aminomethyl-3,5,5-trimethylcyclohexanol.
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 preferred from the viewpoint of ease of modification. Hexanol and the like), 2-aminoethanol and 4-aminobutanol are more preferable, and 2-aminoethanol is particularly preferable.

The amount of the amine having a hydroxyl group used for modification is based on the weight of the object to be modified (a2-1), ease of repetitive structure in the molecule, dielectric heating property of the molded product, and a polyolefin resin composition for dielectric heating described later. From the viewpoint of the dispersibility of the block polymer (A) in the product and the mechanical properties of the molded product, it is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight, particularly preferably 2 to 30% by weight. %.
The hydroxyl value of (a2-2) is preferably 4 to 280 mgKOH / g, more preferably 4 to 100 mgKOH / g, particularly from the viewpoint of the reactivity with (b) and the thermoplasticity of the block polymer (A). Preferably it is 5-50 mgKOH / g.

Polyolefins having amino groups at both ends of the polymer (a2-3) include polyolefins having amino groups obtained by modifying the polyolefin (a2-1) having carboxyl groups at both ends of the polymer with diamine (Q1) and these A mixture of two or more of these can be used.
As diamine (Q1), C2-C12 diamine etc. can be used, Specifically, ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, etc. are mentioned.
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 (Q1) used for modification of (a2-1) is the ease of taking a repeating structure in the molecule, the dielectric heating property of the molded product, and the dispersibility of the block polymer (A) in the polyolefin resin composition for dielectric heating. From the viewpoint of mechanical properties of the molded product, it is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight, particularly preferably 2 to 30% by weight based on the weight of (a2-1). It is.
The modification of (a2-1) by (Q1) is preferably 0.5 to 1,000% by weight, based on the weight of (a2-1), from the viewpoint of preventing polyamide (imide) formation. It is preferable to use 1 to 500% by weight, particularly preferably 2 to 300% by weight of (Q1), and then remove unreacted (Q1) at 120 to 230 ° C. under reduced pressure.

  The amine value of (a2-3) is preferably 4 to 280 mgKOH / g, more preferably 4 to 100 mgKOH / g, particularly from the viewpoint of the reactivity with (b) and the thermoplasticity of the block polymer (A). Preferably it is 5-50 mgKOH / g.

As the polyolefin (a2-4) having an isocyanate group at both ends, an isocyanate obtained by modifying (a2-2) or (a2-3) with poly (2-3 or more) isocyanate (hereinafter abbreviated as PI). Examples thereof include polyolefin having a group and a mixture of two or more thereof.
PI includes aromatic PI having 6 to 20 carbon atoms (excluding carbon atoms in the NCO group, the same shall apply hereinafter), aliphatic PI having 2 to 18 carbon atoms, alicyclic PI having 4 to 15 carbon atoms, carbon Included are araliphatic PIs of several 8-15, modified products of these PIs, and mixtures of two or more thereof.

  As aromatic PI, 1,3- or 1,4-phenylene diisocyanate, 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, Examples include 5-naphthylene diisocyanate.

  Aliphatic PIs include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and the like.

  Alicyclic PI includes isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) Examples include -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the araliphatic PI include m- or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).

Examples of modified PI include urethane-modified, urea-modified, carbodiimide-modified, and uretdione-modified.
Among the PIs, TDI, MDI and HDI are preferable, and HDI is more preferable.

Reaction of PI and (a2-2) can be performed by the method similar to a urethanation reaction, for example.
The molar equivalent ratio (NCO / OH) between PI and (a2-2) is preferably 1.8 / 1 to 3/1, and more preferably 2/1.
In order to accelerate the urethanization reaction, a known catalyst used for the urethanization reaction may be used if necessary. Catalysts include metal catalysts {tin catalysts [dibutyltin dilaurate and stannous octoate, etc.], lead catalysts [lead 2-ethylhexanoate, lead octenoate, etc.], other metal catalysts [metal naphthenate (cobalt naphthenate) Etc.) and phenylmercurypropionate etc.}; amine catalysts {triethylenediamine, diazabicycloalkenes [1,8-diazabicyclo [5,4,0] undecene-7 etc.], dialkylaminoalkylamines (dimethylaminoethylamine and Dimethylaminooctylamine etc.), heterocyclic aminoalkylamine [2- (1-aziridinyl) ethylamine and 4- (1-piperidinyl) -2-hexylamine etc.] carbonate or organic acid (formic acid etc.) salt, N Methyl or ethylmorpholine, triethylamine and diethyl or dimethyl Ethanolamine}; and use of two or more types of system thereof.
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 PI and (a2-2).

  Examples of the polyamideimide (a3) include the amide-forming monomer (α), a trivalent or tetravalent aromatic polycarboxylic acid that can form at least one imide ring with (α), or an anhydride thereof (δ). And a mixture thereof are included.

  (Δ) is a trivalent carboxylic acid [monocyclic trivalent carboxylic acid (such as trimellitic acid), polycyclic trivalent carboxylic acid (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 diphenylether-3,3 ′, 4-tricarboxylic acid) and the like Anhydrides] and tetravalent carboxylic acids [monocyclic tetravalent carboxylic acids (pyromellitic acid, etc.), polycyclic tetravalent carboxylic acids (biphenyl-2,2 ', 3,3'-tetracarboxylic acid, benzophenone-2,2 ', 3,3'-tetracarboxylic acid, diphenylsulfone-2,2', 3,3'-tetracarboxylic acid and diphenyl ether-2,2 ', 3,3'-tetracarboxylic acid) Anhydrides al] and the like.

As a method for producing the polyamideimide (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 molecular weight regulators. And the amide-forming monomer (α) in the presence of a trivalent or tetravalent aromatic polycarboxylic acid or anhydride (δ) capable of forming at least one imide ring with the amide-forming monomer (α). ) Is subjected to ring-opening polymerization or polycondensation.
The use amount of the molecular weight modifier is preferably 2 to 80% by weight, more preferably 4 based on the total weight of the amide-forming monomer and the molecular weight modifier from the viewpoint of dielectric heating property and heat resistance of the molded product. ~ 75 wt%.

  Mn of the polymer (a) is preferably 200 to 25,000, more preferably 800 to 25,000, particularly preferably 1, from the viewpoint of dispersibility of the block polymer (A) and mechanical properties of the molded product. 000 to 20,000, particularly preferably 1,500 to 10,000, most preferably 2,000 to 5,000.

<Polymer (b)>
The polymer (b) in the present invention has a volume resistivity of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm, and the volume resistivity of (b) is more preferably 1 × 10 ⁶ to 1 ×. 10 ⁹ Ω · cm, particularly preferably 1 × 10 ⁶ to 1 × 10 ⁸ Ω · cm.
Those having a volume resistivity of less than 1 × 10 ⁵ Ω · cm are substantially difficult to obtain, and if it exceeds 1 × 10 ¹¹ Ω · cm, the dielectric heating property of the molded product described later is lowered.
Specific examples of the polymer (b) include polyether (b1), polyether-containing polymer (b2), cationic polymer (b3), and anionic polymer (b4).

Examples of the polyether (b1) include polyether diol (b1-1), polyether diamine (b1-2), and modified products (b1-3) thereof.
Examples of the polyether diol (b1-1) include those obtained by addition reaction of alkylene oxide (hereinafter abbreviated as AO) to the diol (b0). Specifically, the polyether diol (b1-1) is represented by the general formula (1). What is done.

H— (OR ¹ ) _m —O—E ¹ —O— (R ² O) _n —H (1)

E ¹ in the general formula (1) is a residue obtained by removing all hydroxyl groups from the diol (b0).
Examples of the diol (b0) include aliphatic dihydric alcohols having 2 to 12 carbon atoms, alicyclic dihydric alcohols having 5 to 12 carbon atoms, aromatic aliphatic dihydric alcohols having 6 to 18 carbon atoms, and 6 to 6 carbon atoms. 18 dihydric phenols and tertiary amino group-containing diols.

Examples of the aliphatic dihydric alcohol having 2 to 12 carbon atoms include ethylene glycol (hereinafter abbreviated as EG), 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,12-dodecanediol is mentioned.
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 araliphatic dihydric alcohol having 6 to 18 carbon atoms include m- or p-xylylene diol, bis (hydroxyethyl) benzene and bis (hydroxyethoxy) benzene.

Examples of the dihydric phenol having 6 to 18 carbon atoms include monocyclic dihydric phenols (hydroquinone, catechol, resorcin, urushiol, bisphenol A, bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-2,2-butane and Dihydroxybiphenyl, etc.) and polycyclic dihydric phenols (dihydroxynaphthalene, binaphthol, etc.). In addition, the phenol in this invention means the general term for the compound by which the hydrogen atom of the aromatic ring was substituted by the hydroxyl group.
The tertiary amino group-containing diol includes aliphatic or alicyclic primary amines having 1 to 12 carbon atoms (methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, pentylamine, isopentylamine. Bishydroxyalkylated products such as cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine and dodecylamine) and aromatic primary amines having 6 to 12 carbon atoms (such as aniline and benzylamine) Bishydroxyalkylated products can be mentioned.

  Of these, preferred are aliphatic dihydric alcohols having 2 to 12 carbon atoms and dihydric phenols having 6 to 18 carbon atoms, and more preferred are EG and bisphenol A.

R ¹ and R ² in the general formula (1) are each independently an alkylene group having 2 to 12 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms (ethylene group, 1,2- or 1,3). -Propylene group and 1,2-, 1,3-, 1,4- or 2,3-butylene group).
M and n in General formula (1) are the numbers of 1-300 each independently, Preferably it is 2-250, More preferably, it is 10-100.
In the general formula (1), when m and n are each 2 or more, R ¹ and R ² may be the same or different, and the (OR ¹ ) _m and (R ² O) _n portions may be random bonds or blocked. It may be a bond.

The polyether diol (b1-1) can be produced by adding AO to the diol (b0).
As AO, C2-C4 AO [ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3-propylene oxide, 1,2-, 1,3-, 1,4-, 2,3- or butylene oxide and a combination of two or more of these are preferably used. If necessary, other AO [alpha-olefin oxide having 5 to 12 carbon atoms, styrene oxide, epihalohydrin (such as epichlorohydrin), etc. ] Can also be used in a small proportion (30 wt% or less based on the total weight of AO).
When two or more kinds of AO are used in combination, the bond form may be either random bond or block bond. Preferred as AO is EO alone or a combination of EO and another AO.

The addition reaction of AO can be performed by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst.
The content of (OR ¹ ) _m and (R ² O) _n based on the weight of the polyether diol (b1-1) represented by the general formula (1) is preferably 5 to 99.8% by weight. More preferably, it is 8 to 99.6% by weight, particularly preferably 10 to 98% by weight.
The content of the oxyethylene group based on the weight of (OR ¹ ) _m and (R ² O) _{n in} the general formula (1) is preferably 5 to 100% by weight, more preferably 10 to 100% by weight, particularly Preferably it is 50-100 weight%, Most preferably, it is 60-100 weight%.

Examples of the polyether diamine (b1-2) include those represented by the general formula (2).

H ₂ N—R ³ — (OR ⁴ ) _p —O—E ² —O— (R ⁵ O) _q —R ⁶ —NH ₂ (2)

E ² in the general formula (2) is a residue obtained by removing all hydroxyl groups from the diol (b0). Examples of the diol (b0) include the same ones as described above, and preferred ranges thereof are also the same.
R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula (2) are each independently an alkylene group having 2 to 12 carbon atoms, and are the same as those exemplified as R ¹ and R ² in the general formula (1). The preferable range is also the same.
P and q in General formula (2) are the numbers of 1-300 each independently, Preferably it is 2-250, More preferably, it is 10-100.
In the general formula (2), when p and q are 2 or more, R ⁴ and R ⁵ may be the same or different, and the (OR ⁴ ) _p and (R ⁵ O) _n portions are random bonds or block bonds. But you can.

  The polyether diamine (b1-2) can be obtained by converting all the hydroxyl groups of the polyether diol (b1-1) into amino groups. For example, it can be produced by reacting (b1-1) with acrylonitrile and hydrogenating the obtained cyanoethylated product.

Modified products (b1-3) include (b1-1) or (b1-2) aminocarboxylic acid modified products (terminal amino groups), isocyanate modified products (terminal isocyanate groups) and epoxy modified products (terminal epoxy groups). Etc.
The aminocarboxylic acid-modified product can be obtained by reacting (b1-1) or (b1-2) with aminocarboxylic acid or lactam.
The isocyanate-modified product can be obtained by reacting (b1-1) or (b1-2) with polyisocyanate or reacting (b1-2) with phosgene.
The epoxy-modified product is obtained by reacting (b1-1) or (b1-2) with diepoxide (epoxy resins such as diglycidyl ether, diglycidyl ester and alicyclic diepoxide: epoxy equivalents 85 to 600). It can be obtained by reacting b1-1) with epihalohydrin (such as epichlorohydrin).

  As the polyether-containing polymer (b2), polyether ester amide (b2-1) having a segment of polyether diol (b1-1), polyether amide imide (b2-2) having a segment of (b1-1) , Polyether ester (b2-3) having a segment of (b1-1), polyether amide (b2-4) having a segment of polyetherdiamine (b1-2) and (b1-1) or (b1-2) ) Polyether urethane (b2-5) having a segment.

The polyether ester amide (b2-1) is composed of a polyamide (a1 ′) having a carboxyl group at both ends of the polyamide (a1) and a polyether diol (b1-1).
Examples of (a1 ′) include a ring-opening polymer of the lactam (α1-1), a polycondensate of the aminocarboxylic acid (α1-2), and a polyamide of the diamine (β) and a dicarboxylic acid (γ). Can be mentioned.
Among (a1 ′), preferred from the viewpoint of dielectric heating properties are a ring-opening polymer of caprolactam, a polycondensate of 12-aminododecanoic acid, and a polyamide of adipic acid and hexamethylenediamine, and more preferred. It is 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).
As (a3), a polymer composed of lactam (α1-1) and the above-mentioned trivalent or tetravalent aromatic polycarboxylic acid (δ) capable of forming at least one imide ring, aminocarboxylic acid ( Examples thereof include a polymer composed of α1-2) and (δ), a polymer composed of polyamide (a1 ′) and (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 (Q) include polyesters of dicarboxylic acid (γ) and diol (b0).
Examples of the polyether amide (b2-4) include those composed of polyamide (a1) and polyether diamine (a212).
Polyether urethane (b2-5) includes diisocyanate in the PI, polyether diol (b1-1) or polyether diamine (b1-2), and optionally a chain extender [the diol (b0) and diamine. (Β) etc.].

From the viewpoint of moldability, the content of the polyether (b1) segment in the polyether-containing polymer (b2) is preferably 30 to 80% by weight, more preferably 40 to 70% by weight, based on the weight of (b2). %.
The content of the oxyethylene group in (b2) is preferably 30 to 80% by weight, more preferably 40 to 70% by weight, based on the weight of (b2), from the viewpoint of dielectric heating properties and moldability. .

Examples of the cationic polymer (b3) include a polymer having a cationic group separated by a nonionic molecular chain in the molecule.
The nonionic molecular chain includes a divalent hydrocarbon group, ether bond, thioether bond, carbonyl bond, ester bond, imino bond, amide bond, imide bond, urethane bond, urea bond, carbonate bond and siloxy bond. And a divalent hydrocarbon group having one or more groups selected from the above, and a hydrocarbon group having a heterocyclic structure having a nitrogen atom or an oxygen atom.

Among the nonionic molecular chains, preferred are a divalent hydrocarbon group and a divalent hydrocarbon group having an ether bond.
Examples of the cationic group include a group having a quaternary ammonium salt or a phosphonium salt. Examples of counter anions that form quaternary ammonium salts or phosphonium salts include super strong acid anions and other anions.
Examples of the super strong acid anion include an anion of a super strong acid (such as tetrafluoroboric acid and hexafluorophosphoric acid) 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 ^{− and the} like), OH ⁻ , PO ₄ ⁻ , CH ₃ OSO ₄ ⁻ , C ₂ H ₅ OSO ₄ ⁻ and ClO ₄ ^{− and the} like. It is done.
Examples of the protonic acid that induces a super strong acid include hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide.
Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, and tantalum pentafluoride.
(B3) The number of cationic groups in one molecule is preferably 2 to 80, and more preferably 3 to 60.

  Specific examples of (b3) include cationic polymers described in JP-A No. 2001-278985.

The anionic polymer (b4) comprises a dicarboxylic acid (γ ′) having a sulfonyl group and the diol (b0) or the polyether (b1) as essential constituent units, and 2 to 80, preferably 3 in the molecule. It is a polymer having -60 sulfonyl groups.
Examples of (γ ′) include those obtained by introducing a sulfonyl group into the dicarboxylic acid (γ), and only an aromatic dicarboxylic acid having a sulfonyl group, an aliphatic dicarboxylic acid having a sulfonyl group, and a sulfonyl group become salts. Aromatic dicarboxylic acids or aliphatic dicarboxylic acids having a sulfonyl group can be mentioned.

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 ( C1-C4) ester (such as methyl ester and ethyl ester) and acid anhydride].
Examples of the aliphatic dicarboxylic acid having a sulfonyl group include sulfosuccinic acid and ester-forming derivatives thereof [alkyl (carbon number 1 to 4) ester (such as methyl ester and ethyl ester) and acid anhydrides].

Examples of the salt that forms an aromatic dicarboxylic acid or aliphatic dicarboxylic acid having a sulfonyl group in which only the sulfonyl group is converted to a salt include alkali metal (lithium, sodium, potassium, etc.) salts, alkaline earth metals (magnesium, calcium, etc.) Of amines such as salts, ammonium salts, mono-, di- or triamines (mono-, di- or triethylamine, mono-, di- or triethanolamine and diethylethanolamine, etc.) having a hydroxyalkyl group (2 to 4 carbon atoms) A quaternary ammonium salt etc. are mentioned.
Among these, preferred are aromatic dicarboxylic acids having a sulfonyl group, more preferred are 5-sulfoisophthalate, and particularly preferred are sodium 5-sulfoisophthalate and potassium 5-sulfoisophthalate. is there.

Among (b0) or (b1) constituting (b4), alkanediol having 2 to 10 carbon atoms, EG, polyethylene glycol (hereinafter abbreviated as PEG) (degree of polymerization 2 to 20), bisphenol EO adduct (number of added moles: 2 to 60 mol) of bisphenol A and the like, and a mixture of two or more of these.
As a manufacturing method of (b4), the manufacturing method of well-known polyester can be applied as it is. The polyesterification reaction is performed in a temperature range of 150 to 240 ° C. under reduced pressure, and the reaction time is preferably 0.5 to 20 hours. Moreover, you may use the catalyst used for well-known esterification reaction as needed. Examples of esterification catalysts include antimony catalysts (such as antimony trioxide), tin catalysts (such as monobutyltin oxide and dibutyltin oxide), titanium catalysts (such as tetrabutyl titanate), zirconium catalysts (such as tetrabutylzirconate), and metal acetates Examples include catalysts (such as zinc acetate).

Among (b1) to (b4), (b1) and (b2) are preferable from the viewpoint of dielectric heating property and (A) dispersibility, and (b1) is more preferable.
The number average molecular weight (Mn) of (b) is preferably 500 to 20,000, more preferably 700 to 18,000, particularly preferably 1,000 to 15,000, from the viewpoints of dielectric heating properties and mechanical properties. Particularly preferred is 1,200 to 8,000, and most preferred is 2,000 to 4,000.

<Block polymer (A)>
The block polymer (A) in the present invention contains the polymer (a) block and the polymer (b) block as structural units.

Among (A), the following (A1) and (A2) are preferable from the viewpoint of mechanical properties and dielectric heating characteristics, and (A2) is more preferable.
(A1): (a) is a polyamide (a1), (b) is a polyether (b1) or a polyether-containing polymer (b2), and (a1), (b1) and / or (b2) A polyether ester amide obtained by reacting
(A2): (a) is polyolefin (a2), and the block of (a2) and the block of polymer (b) are composed of an ester bond, an amide bond, an ether bond, an imide bond, a urethane bond and a urea bond. A block polymer having a structure bonded through at least one bond selected from the group consisting of.

  The weight ratio [(a) / (b)] of the block (a) and the block (b) constituting (A) is preferably 10/90 to 80 / from the viewpoint of mechanical properties and dielectric heating characteristics. 20, more preferably 20/80 to 75/25.

The structure in which the block (a) and the block (b) constituting (A) are combined includes (a)-(b) type, (a)-(b)-(a) type, (b )-(A)-(b) type and [(a)-(b)] n type (n represents the average number of repetitions).
The structure of the block polymer (A) is preferably an [(a)-(b)] n type in which (a) and (b) are repeatedly and alternately bonded from the viewpoints of dielectric heating characteristics and mechanical properties.
[(A)-(b)] n in the n-type structure is preferably 2 to 50, more preferably 2.3 from the viewpoints of dielectric heating characteristics, mechanical characteristics of the molded product, and anchor effect on the resin. -30, particularly preferably 2.7-20, most preferably 3-10. n can be determined by Mn and ¹ H-NMR analysis of the block polymers (A), (a) and (b).

  Mn in (A) is preferably from 2,000 to 1,000,000, more preferably from 4,000 to 500,000, and particularly preferably from the viewpoint of mechanical properties and dielectric heating characteristics of the molded product described later. 10,000 to 100,000.

When (A) has a structure in which the block of (a) and the block of (b) are bonded via an ester bond, an amide bond, an ether bond, or an imide bond, it is produced by the following method. Can do.
(A) and (b) having a reactive group necessary for forming the above bond are selected and put into a reaction vessel, with stirring, a reaction temperature of 100 to 250 ° C., a pressure of 0.003 to 0.1 MPa. Then, a method of reacting for 1 to 50 hours while removing water generated by amidation reaction, esterification reaction or imidation reaction (hereinafter abbreviated as generated water) from the reaction system can be mentioned. The weight ratio of (a) and (b) is from 10/90 to 80/20, more preferably from 20/80 to 75/25, from the viewpoints of dielectric heating properties and water resistance.

In the case of the esterification reaction, it is preferable to use 0.05 to 0.5% by weight of catalyst based on the weight of (a) and (b) in order to accelerate the reaction. Catalysts include inorganic acids (such as sulfuric acid and hydrochloric acid), organic sulfonic acids (such as methane sulfonic acid, paratoluene sulfonic acid, xylene sulfonic acid, and naphthalene sulfonic acid), and organometallic compounds (dibutyltin oxide, tetraisopropoxy titanate, bistrimethyl). Ethanolamine titanate and potassium oxalate titanate). When a catalyst is used, the catalyst can be neutralized as necessary after completion of the esterification reaction 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 of removing only generated water from the reaction system by azeotropically boiling the organic solvent and generated water under reflux using an organic solvent incompatible with water (for example, toluene, xylene, cyclohexane, etc.) .
(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 of removing the generated water from the reaction system by reducing the pressure in the reaction system.

When (A) has a structure in which the block of (a) and the block of (b) are bonded via a urethane bond or a urea bond, it can be produced by the following method.
After selecting (a) and (b) having a reactive group necessary for forming the bond, (a) is put into a reaction vessel and heated to 30 to 100 ° C. with stirring (b ) And reacting at the same temperature for 1 to 20 hours. The weight ratio of (a) and (b) is from 10/90 to 80/20, more preferably from 20/80 to 75/25, from the viewpoints of dielectric heating properties and water resistance.

  In order to promote the reaction, it is preferable to use 0.001 to 5% by weight of catalyst based on the weight of (a) and (b). Catalysts include organometallic compounds (dibutyltin dilaurate, dioctyltin dilaurate, lead octoate, bismuth octoate, etc.), tertiary amines {triethylenediamine, trialkylamines having an alkyl group of 1 to 8 carbon atoms (trimethylamine, tributylamine) And trioctylamine etc.), diazabicycloalkenes [1,8-diazabicyclo [5,4,0] undecene-7] etc.]; and combinations of two or more thereof.

<Dielectric heating property imparting agent for polyolefin resin (Z)>
The dielectric heatability imparting agent (Z) for polyolefin resin of the present invention comprises the block polymer (A).
(Z) can be suitably used as a dielectric heating property imparting agent for the polyolefin resin (Y) described later.

<Dielectric heating improver (C)>
The dielectric heating property-imparting agent (Z) can further contain a dielectric heating property improving agent (C) as long as the effects of the present invention are not impaired.
As the dielectric heatability improver (C), an alkali metal or alkaline earth metal salt (C1) having a melting point exceeding 25 ° C., a quaternary ammonium salt (C2) having a melting point exceeding 25 ° C., a melting point of 25 ° C. or less. Examples include ionic liquid (C3) and inorganic oxide (C4). (C1) to (C4) may be used in combination of two or more.

  As an alkali metal or alkaline earth metal salt (C1) having a melting point of more than 25 ° C., an alkali metal (lithium, sodium, potassium, etc.) or an alkaline earth metal (magnesium, calcium, etc.)] and an organic acid [carbon number 1-20 mono- or dicarboxylic acids (formic acid, acetic acid, propionic acid, benzoic acid, oxalic acid, succinic acid, etc.), C1-C20 sulfonic acids (methanesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid) Etc.) and thiocyanic acid etc.] and salts of the organic acids and inorganic acids [hydrohalic acid (hydrochloric acid and hydrobromic acid etc.), perchloric acid, sulfuric acid, nitric acid and phosphoric acid etc.] Examples thereof include compounds having a melting point exceeding 25 ° C.

  The quaternary ammonium salt (C2) having a melting point exceeding 25 ° C. includes amidinium (1-ethyl-3-methylimidazolium, etc.) or guanidinium (2-dimethylamino-1,3,4-trimethylimidazolinium, etc.) A salt with the organic acid or inorganic acid, for example, 1-ethyl-3-methylimidazolium chloride (melting point: 80 ° C.), 1,2,3-trimethylimidazolium methyl sulfate (melting point: 113 ° C.), 1 -Ethyl-3-methylimidazolium dodecylbenzenesulfonate (melting point: 127 ° C.).

  As the ionic liquid (C3) having a melting point of 25 ° C. or lower, at least one of the constituent cations or anions is an organic ion, and the initial conductivity is 1 to 200 ms / cm (preferably 10 to 200 ms / cm). Specific molten salts are mentioned, and specific examples include molten salts exemplified in International Publication No. 95/15572. From the viewpoint of dielectric heating properties, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (melting point: −9 ° C.), 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) is preferable. It is an imide salt (melting point: −17 ° C.).

Examples of the inorganic oxide (C4) include titanium oxide, iron oxide, barium titanate, aluminum oxide, zinc oxide and magnesium oxide, with titanium oxide being preferred.
The volume average particle diameter of (C4) is preferably 2 nm to 5 μm, more preferably 5 nm to 2 μm, and particularly preferably 10 nm to 300 nm.

The content of each of (C1) to (C4) based on the weight of the dielectric heating property imparting agent (Z) is preferably 0 from the viewpoint of providing a resin molded product having a good appearance without being deposited on the resin surface. 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 3% by weight.
The total content of (C) when two or more of (C1) to (C4) are used in combination is that of (Z) from the viewpoint of giving a molded article having a good appearance without being deposited on the surface of the dielectric and the resin. Based on weight, it is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 3% by weight.

  When (C) is used, it is preferably dispersed in advance in the dielectric heating property-imparting agent (Z) so as not to impair the appearance of the molded product to be described later. When the block polymer (A) is produced, (C) It is still more preferable to contain. There is no restriction | limiting in particular about the time to contain (C) at the time of manufacture of (A), Although it may be any before superposition | polymerization, the time of superposition | polymerization, or superposition | polymerization, It is preferable to make it contain in the raw material before superposition | polymerization.

<Diolefin heating polyolefin resin composition (X)>
The polyolefin resin composition (X) for dielectric heating of the present invention comprises the dielectric heating property-imparting agent (Z) for polyolefin resin of the present invention and a polyolefin resin (Y).

Examples of the polyolefin resin (Y) include polypropylene (PP), polyethylene (PE), ethylene-vinyl acetate copolymer resin (EVA), and ethylene-ethyl acrylate copolymer resin.
Of (Y), preferred are polypropylene (PP) and polyethylene (PE).

  The weight ratio [(Z) / (Y)] of (Z) and (Y) in the polyolefin resin composition (X) for dielectric heating is preferably 1 / From the viewpoint of dielectric heating properties and mechanical properties of the molded product. It is 99-50 / 50, More preferably, it is 3 / 97-40 / 60, Most preferably, it is 5 / 95-30 / 70.

  The polyolefin resin composition for dielectric heating (X) of the present invention can contain other additives (E) within a range not inhibiting the effects of the present invention. (E) includes a colorant (E1), a release agent (E2), an antioxidant (E3), a flame retardant (E4), an ultraviolet absorber (E5), an antibacterial agent (E6), and a dispersant (E7). And a filler (E8). (E) may use 2 or more types together.

  Examples of the colorant (E1) include inorganic pigments (white pigments, cobalt compounds, iron compounds, sulfides, etc.), organic pigments (azo pigments, polycyclic pigments, etc.), and dyes (azo, indigoid, sulfide, alizarin). System, acridine system, thiazole system, nitro system, aniline system, etc.).

  As a mold release agent (E2), C12-18 fatty acid alkyl (C1-4) ester (butyl stearate etc.), C2-18 fatty acid glycol (C2-8) ester (Ethylene glycol monostearate, etc.), polyhydric (trivalent or higher) alcohol esters (hardened castor oil, etc.) of fatty acids having 2 to 18 carbon atoms, liquid paraffin and the like.

  Antioxidants (E3) include phenolic compounds [monocyclic phenols (2,6-di-t-butyl-p-cresol, etc.), bisphenols [2,2′-methylenebis (4-methyl-6-t-butylphenol). And the like] and polycyclic phenols [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, etc.]], sulfur compounds (dilauryl- 3,3′-thiodipropionate etc.), phosphorus compounds (triphenyl phosphite etc.), amine compounds (octylated diphenylamine etc.) and the like.

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

  Examples of the ultraviolet absorber (E5) include benzotriazole [2- (2′-hydroxy-5′-methylphenyl) benzotriazole and the like], benzophenone (2-hydroxy-4-methoxybenzophenone and the like), salicylate (phenyl salicylate). Etc.) and acrylates (such as 2-ethylhexyl-2-cyano-3,3′1-diphenyl acrylate).

  As the antibacterial agent (E6), benzoic acid, sorbic acid, halogenated phenol, organic iodine, nitrile (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylene bisthocyanocyanate, etc.), N- Examples thereof include haloalkylthioimides, copper agents (such as 8-oxyquinoline copper), benzimidazoles, benzothiazoles, trihaloallyls, triazoles, organic nitrogen sulfur compounds (such as Suraoff 39), quaternary ammonium compounds and pyridine compounds.

  As the dispersant (E7), a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group (for example, a special vinyl polymer) Polymers described in Kaihei 3-258850, modified vinyl polymers having a sulfonic acid group described in JP-A-6-345927, and block polymers having a polyolefin portion and an aromatic vinyl polymer portion, etc.) Is mentioned.

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

The total content of (E) based on the weight of the polyolefin resin (Y) is preferably 45% by weight or less, more preferably 0.001 to 40% by weight, particularly preferably from the viewpoint of mechanical properties of the molded product. 0.01 to 35% by weight.
The content of (E1) based on the weight of the polyolefin resin (Y) is preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, from the viewpoint of mechanical properties of the molded product. .
Each content of (E2), (E3) and (E5) based on the weight of the polyolefin resin (Y) is preferably 0.01 to 3% by weight, more preferably from the viewpoint of mechanical properties of the molded product. Is 0.05 to 1% by weight.
Each content of (E4) and (E6) based on the weight of the polyolefin resin (Y) is preferably 0.5 to 20% by weight, and more preferably 1 to 10%, from the viewpoint of mechanical properties of the molded product. % By weight.
Each content of (E7) and (E8) based on the weight of the polyolefin resin (Y) is preferably 0.5 to 10% by weight, and more preferably 1 to 5%, from the viewpoint of mechanical properties of the molded product. % By weight.

The polyolefin resin composition for dielectric heating (X) of the present invention can be obtained by melt-mixing the dielectric heatability imparting agent (Z), the polyolefin resin (Y) and (E) if necessary. As a method of melting and mixing, generally, a method of mixing each component in pellet form or powder form with an appropriate mixer (Henschel mixer etc.) and then melt mixing and pelletizing with an extruder is applied. it can.
There is no particular limitation on the order of addition of each component during melt mixing, for example,
[1] A method in which (Z) is melt-mixed, and then (Y) and, if necessary, (E) are collectively charged and melt-mixed.
[2] After (Z) is melt-mixed, a part of (Y) is melt-mixed in advance to prepare a high-concentration composition (masterbatch resin composition) of (Z), and then the remaining (Y) and A method of melting and mixing (E) as necessary (master batch method or master pellet method).
Etc.
The concentration of (Z) in the masterbatch resin composition in the method [2] 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 (Z) can be efficiently dispersed in (Y).

<Molded product for dielectric heating>
The molded article for dielectric heating of the present invention is obtained by molding a polyolefin resin composition (X) for dielectric heating. Examples of the molding method include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.) and the like. Molding, multilayer molding or foam molding can be used for any molding method.

  The molded article of the present invention has excellent mechanical properties and excellent dielectric heating properties. A molded article is obtained by dielectric heating, preferably dielectric heating bonding of the molded product. Examples of the dielectric heating apparatus include known ones, and the dielectric heating conditions can be appropriately selected depending on the size and use of the molded product.

  Examples of the present invention will be described below, but the present invention is not limited thereto. Below, a part shows a weight part.

<Production Example 1>
[Production of polyamide (a1-1)]
In a stainless steel pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen introducing tube and a decompression device, 173 parts of ε-caprolactam, 33.2 parts of terephthalic acid, an antioxidant [“Irganox 1010”, Ciba Specialty Chemicals Co., Ltd.] 0.4 parts and 10 parts of water were added, and after purging with nitrogen, the temperature was raised to 220 ° C. with stirring in a sealed state, and the same temperature (pressure: 0.2 to 0.3 MPa) Was stirred for 4 hours to obtain a polyamide (a1-1) having carboxyl groups at both ends. The acid value of (a1-1) was 111 mgKOH / g, Mn was 1,000, and the volume resistivity value was 1 × 10 ¹² Ω · cm.

<Production Example 2>
[Production of polyolefin (a2-1-1α) having carboxyl groups at both ends]
In the same pressure resistant reactor as in Production Example 1, low molecular weight polypropylene obtained by the thermal degradation method [polypropylene (MFR: 10 g / 10 min) is 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Obtained by heat degradation. 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 polyolefin 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, purged with nitrogen, melted by heating to 200 ° C. with stirring and sealed, and reacted at the same temperature for 10 hours. I let you. Next, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin (a2-1-1α) 95 having carboxyl groups at both ends of the polymer. Got a part. The acid value of (a2-1-1α) was 27.5 mgKOH / g, Mn was 3,600, and the volume resistivity value was 1 × 10 ¹⁸ Ω · cm.

<Production Example 3>
[Production of polyolefin (a2-1-2) obtained by secondary modification of (a2-1-1α)]
88 parts of (a2-1-1α) and 12 parts of 12-aminododecanoic acid are introduced into a pressure-resistant reaction vessel similar to Production Example 1, mixed uniformly, and then heated to 200 ° C. with stirring in a nitrogen gas atmosphere. The mixture was reacted at the same temperature under reduced pressure (0.013 MPa or less) for 3 hours to obtain 96 parts of polyolefin (a2-1-2) obtained by secondary modification of (a2-1-1α). The acid value of (a2-1-2) was 24.8 mgKOH / g, Mn was 4,000, and the volume resistivity value was 1 × 10 ¹⁸ Ω · cm.

<Production Example 4>
[Production of polyolefin having hydroxyl groups at both ends (a2-2)]
In Production Example 2, 90 parts of low molecular weight polypropylene and 10 parts of maleic anhydride obtained by the thermal degradation method were replaced with 94 parts of low molecular weight ethylene / propylene random copolymer obtained by the thermal degradation method and 6 parts of maleic anhydride. Except having changed into the part, it carried out similarly to manufacture example 2, and obtained 98 parts of polyolefin (a2-1-1β) which has a carboxyl group in the both ends of a polymer. The acid value of (a2-1-1β) was 9.9 mgKOH / g, and Mn was 10,200. The low molecular weight ethylene / propylene random copolymer obtained by the above thermal degradation method (Mn: 10,000, number of double bonds per 1,000 carbon atoms: 2.5, 2 per molecule) The average number of heavy bonds: 1.8, the content of polyolefin that can be modified at both ends: 90% by weight) is 410 ethylene / propylene random copolymer (ethylene content: 2% by weight, MFR: 10 g / 10 min). It was obtained by thermal degradation for 14 minutes at ± 0.1 ° C. under nitrogen aeration (80 mL / min).
Next, 97 parts of (a2-1-1β) and 5 parts of ethanolamine were put into a pressure-resistant reaction vessel similar to Production Example 1, and the temperature was raised to 180 ° C. with stirring in a nitrogen gas atmosphere. Reacted for hours. Excess ethanolamine was distilled off under reduced pressure (0.013 MPa or less) at 180 ° C. over 2 hours to obtain a polyolefin (a2-2) having hydroxyl groups at both ends of the polymer. The hydroxyl value of (a2-2) was 9.9 mgKOH / g, the amine value was 0.01 mgKOH / g, Mn was 10,200, and the volume resistivity value was 1 × 10 ¹⁸ Ω · cm.

<Production Example 5>
[Production of modified polyolefin (a2-4) having amino groups at both ends]
In Production Example 2, except that 90 parts of low molecular weight polypropylene and 10 parts of maleic anhydride obtained by the thermal degradation method were changed to 80 parts of low molecular weight polypropylene obtained by the thermal degradation method and 20 parts of maleic anhydride. In the same manner as in Production Example 2, 92 parts of polyolefin (a2-1-1γ) having carboxyl groups at both ends of the polymer was obtained. The acid value of (a2-1-1γ) was 64.0 mgKOH / g, and Mn was 1,700. The low molecular weight polypropylene obtained by the above thermal degradation method (Mn: 1,500, number of double bonds per 1,000 carbon atoms: 17.8, average number of double bonds per molecule: 1.94, the 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) of 410 ± 0.1 ° C., It was obtained by heat degradation for 18 minutes.
Next, 90 parts of (a2-1-1γ) and 10 parts of bis (2-aminoethyl) ether are put into a pressure resistant reactor similar to Production Example 1, and the temperature is raised to 200 ° C. with stirring in a nitrogen gas atmosphere. And reacted at the same temperature for 2 hours. Excess bis (2-aminoethyl) ether was distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 2 hours to obtain a modified polyolefin (a2-4) having amino groups at both ends. The amine value of (a2-4) was 64.0 mgKOH / g, Mn was 1,700, and the volume resistivity value was 1 × 10 ¹⁸ Ω · cm.

<Production Example 6>
[Production of Cationic Polymer (b3)]
In a pressure-resistant reaction vessel similar to Production Example 1, 41 parts of N-methyldiethanolamine, 49 parts of adipic acid and 0.3 part of zirconyl acetate were added, and the temperature was raised to 220 ° C. over 2 hours, followed by 1 hour. The pressure was reduced to 0.013 MPa over a polyester reaction. After completion of the reaction, the reaction mixture was cooled to 50 ° C. and dissolved by adding 100 parts of methanol. While stirring, the temperature in the reaction vessel was kept at 120 ° C., 31 parts of dimethyl carbonate was added dropwise over 3 hours, and the mixture was aged at the same temperature for 6 hours. After cooling to room temperature, 100 parts of a 60 wt% hexafluorophosphoric acid aqueous solution was added and stirred at room temperature for 1 hour. Subsequently, methanol was distilled off under reduced pressure, and a cationic polymer (b3) having an average of 12 quaternary ammonium groups in one molecule (hydroxyl value: 30.1 mgKOH / g, acid value: 0.5 mgKOH / g, Mn: 3, 800, volume resistivity: 1 × 10 ⁵ Ω · cm).

<Production Example 7>
[Production of anionic polymer (b4α)]
In a pressure-resistant reaction vessel similar to Production Example 1, 114 parts of diethylene glycol, 268 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 part of dibutyltin oxide were added, and the temperature was increased to 190 ° C. under a reduced pressure of 0.067 MPa. The mixture was transesterified 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 mgKOH / g, acid value 0 0.6 mg KOH / g, Mn: 2,300, and the volume resistivity was 3 × 10 ⁸ Ω · cm).

<Production Example 8> [Production 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 Production Example 1, and the pressure was reduced to 0.067 MPa. The temperature was raised to 190 ° C., and the ester exchange reaction was carried out at the same temperature for 6 hours while distilling off methanol. An anionic polymer (b4β) having an average of 5 sodium sulfonate groups in one molecule (hydroxyl value: 29.6 mgKOH / g, acid value: 0.4 mg KOH / g, Mn: 3,800, volume resistivity: 2 × 10 ⁶ Ω · cm).

<Example 1>
In a reaction vessel equipped with a stirrer, a thermometer and a heating / cooling device, 199 parts of (a1-1) and bisphenol A EO adduct (Mn: 4,000, volume resistivity: 2 × 10 ⁷ Ω · cm) 780 parts and 0.6 parts of zirconyl acetate were added, the temperature was raised to 240 ° C. with stirring, and the mixture was polymerized at the same temperature under reduced pressure (0.013 MPa or less) for 6 hours to contain the block polymer (A1-1). A dielectric heating property-imparting agent (Z-1) for polyolefin resin was obtained.
In addition, Mn of (A1-1) was 24,000.

<Example 2>
In a pressure resistant reactor similar to that in Example 1, 143 parts of (a1-1), 320 parts of (b4α) and 0.3 part of the antioxidant “Irganox 1010” were added, and the temperature was raised to 240 ° C. while stirring. Then, polymerization was performed at the same temperature under reduced pressure (0.013 MPa or less) for 5 hours to obtain a dielectric heating property-imparting agent (Z-2) for polyolefin resin containing the block polymer (A1-2).
In addition, Mn of (A1-2) was 21,000.

<Example 3>
In a pressure resistant reactor similar to that in Example 1, 67.1 parts of (a2-1-1α), polyetherdiamine (b1-2) [α, ω-diaminoPEG (Mn: 2,000, volume resistivity: 1 × 10 ⁷ Ω · cm)] 32.9 parts, 0.3 parts of the antioxidant “Irganox 1010” and 0.5 parts of zirconyl acetate were added, the temperature was raised to 220 ° C. with stirring, and the pressure was reduced ( 0.013 MPa or less) The polymer was polymerized at the same temperature for 3 hours to obtain a dielectric heating property-imparting agent (Z-3) for polyolefin resin containing the block polymer (A2-1).
In addition, Mn of (A2-1) was 50,000.

<Example 4>
In Example 3, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2), 60.1 parts of (a2-1-2) and polyether diol (b1-1α) [PEG (Mn: 3,000, volume resistivity: 1 × 10 ⁷ Ω · cm)] Except for the change to 39.9 parts, the block polymer (A2-2) was contained in the same manner as in Example 3. A dielectric heatability-imparting agent (Z-4) for polyolefin resin was obtained.
In addition, Mn of (A2-2) was 30,000.

<Example 5>
In Example 3, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2) were replaced with 48.0 parts of (a2-2), 48.0 parts of (b3) and dodecanedioic acid 4 Except having changed into the part, it carried out similarly to Example 3, and obtained the dielectric heating property imparting agent (Z-5) for polyolefin resins containing a block polymer (A2-3).
In addition, Mn of (A2-3) was 100,000.

<Example 6>
In Example 3, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2), 31.6 parts of (a2-4), 68.4 parts of (b4β), and dodecanedioic acid 8 Except having changed into the part, it carried out similarly to Example 3, and obtained the dielectric-heat-ability imparting agent (Z-6) for polyolefin resins containing a block polymer (A2-4).
In addition, Mn of (A2-4) was 10,000.

<Example 7>
In Example 3, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2), 71.5 parts of (a2-1-2) and polyether diol (b1-1β) [poly A block polymer (A2-5) was contained in the same manner as in Example 3 except that tetramethylene glycol (Mn: 1,800, volume resistivity: 1 × 10 ¹¹ Ω · cm) was changed to 28.5 parts. Dielectric heating property imparting agent (Z-7) for polyolefin resin was obtained.
In addition, Mn of (A2-5) was 40,000.

<Example 8>
In Example 3, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2) were replaced with 48.0 parts of (a2-2), 48.0 parts of (b3) and hexamethylene diisocyanate ( (HDI) Except for changing to 3 parts, a dielectric heating property-imparting agent (Z-8) for polyolefin resin containing a block polymer (A2-6) was obtained in the same manner as in Example 3.
In addition, Mn of (A2-6) was 100,000.

<Example 9>
In the same pressure resistant reactor as in Example 1, 60.1 parts of (a2-1-2), polyether diol (b1-1α) [PEG (Mn: 3,000, volume resistivity: 1 × 10 ⁷ Ω) Cm)] 39.9 parts, 10 parts of lithium trifluoromethanesulfonate (C-1), 0.3 part of antioxidant “Irganox 1010” and 0.5 part of zirconyl acetate were added and stirred at 220 ° C. The polymer was polymerized at the same temperature for 3 hours under reduced pressure (0.013 MPa or less) to obtain a dielectric heating property-imparting agent (Z-9) for polyolefin resin containing the block polymer (A2-7). .
In addition, Mn of (A2-7) was 30,000.

<Example 10>
In the same pressure resistant reactor as in Example 1, 60.1 parts of (a2-1-2), polyether diol (b1-1α) [PEG (Mn: 3,000, volume resistivity: 1 × 10 ⁷ Ω) Cm)] 39.9 parts, ethyl methyl imidazolium dodecylbenzenesulfonate (C-2) [melting point: 127 ° C.] 10 parts, antioxidant “Irganox 1010” 0.3 part and zirconyl acetate 0.5 part , Heated to 220 ° C. with stirring, polymerized under reduced pressure (0.013 MPa or less) at the same temperature for 3 hours to provide dielectric heating property for polyolefin resin containing block polymer (A2-8) Agent (Z-10) was obtained.
In addition, Mn of (A2-8) was 30,000.

<Example 11>
In the same pressure resistant reactor as in Example 1, 60.1 parts of (a2-1-2), polyether diol (b1-1α) [PEG (Mn: 3,000, volume resistivity: 1 × 10 ⁷ Ω) Cm)] 39.9 parts, titanium oxide fine particles (C-3) ["CR-SUPER70" manufactured by Ishihara Sangyo Co., Ltd.] 10 parts, antioxidant "Irganox 1010" 0.3 parts and zirconyl acetate 0. 5 parts is charged, heated to 220 ° C. with stirring, polymerized at the same temperature under reduced pressure (0.013 MPa or less) for 3 hours, and dielectric heating for polyolefin resin containing block polymer (A2-9) The property imparting agent (Z-11) was obtained.
In addition, Mn of (A2-9) was 30,000.

<Example 12>
In Example 3, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2), 25 parts of (a2-1-2) and polyether diol (b1-1α) [PEG (Mn : 3,000, volume resistivity: 1 × 10 ⁷ Ω · cm)] for polyolefin resin containing a block polymer (A2-10) in the same manner as in Example 3 except that it was changed to 475 parts. A dielectric heating property imparting agent (Z-12) was obtained.
In addition, Mn of (A2-10) was 15,000.

<Example 13>
In Example 3, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2), 425 parts of (a2-1-2) and polyether diol (b1-1α) [PEG (Mn : 3,000, volume resistivity value: 1 × 10 ⁷ Ω · cm)] for polyolefin resin containing block polymer (A2-11) in the same manner as in Example 3 except that it was changed to 75 parts. A dielectric heatability imparting agent (Z-13) was obtained.
In addition, Mn of (A2-11) was 20,000.

<Example 14>
In Example 3, except that (a2-1-1α) 67.1 parts and (b1-2) 32.9 parts were changed to (a2-1-1α) 80 parts and (b1-2) 20 parts. In the same manner as in Example 3, a dielectric heating property-imparting agent (Z-14) for polyolefin resin containing a block polymer (A2-12) was obtained.
In addition, Mn of (A2-12) was 25,000.

<Example 15>
In the same pressure resistant reactor as in Example 1, 60.1 parts of (a2-1-2), polyether diol (b1-1α) [PEG (Mn: 3,000, volume resistivity: 1 × 10 ⁷ Ω) Cm)] 39.9 parts, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide salt (C-4) [melting point: −17 ° C.] 10 parts, antioxidant “Irganox 1010 "0.3 parts and 0.5 parts of zirconyl acetate were added, the temperature was raised to 220 ° C. with stirring, and polymerization was carried out under reduced pressure (0.013 MPa or less) at the same temperature for 3 hours to produce a block polymer (A2-13 The dielectric heating property imparting agent (Z-15) for polyolefin resin containing) was obtained.
In addition, Mn of (A2-13) was 30,000.

<Comparative Example 1>
Commercially available carbon black [trade name “Denka Black” manufactured by Denka Co., Ltd.] was used as it was, and used as a dielectric heating property imparting agent for polyolefin (ratio Z-1) for comparison.

<Examples 16 to 35 and Comparative Examples 2 to 4>
According to the composition (parts) shown in Table 1, the blended components were blended for 3 minutes with a Henschel mixer, then melt-kneaded in a vented twin-screw extruder at 100 rpm, 220 ° C., and a residence time of 5 minutes. A polyolefin resin composition (X) for dielectric heating was obtained. Table 1 shows the results of the following performance tests performed on the obtained dielectric resin composition for dielectric heating (X).

The contents of the polyolefin resin in Table 1 are as follows.
(Y-1): PP resin ["PM771M", manufactured by Sun Allomer Co., Ltd.]
(Y-2): PE resin [low density polyethylene “NUC8321”, manufactured by Dow Chemical Co., Ltd.]

<Performance test>
(1) Dielectric Heating Properties Each polyolefin heating composition for dielectric heating is melt extruded under the condition of a cylinder temperature of 230 ° C. using an extruder equipped with a T-type die [Labplast Mill 2D20C, manufactured by Toyo Seiki Seisakusho Co., Ltd.]. The extruded sheet with a thickness of 0.2 mm was obtained by quenching with a 20 ° C. cooling roll.
With respect to the obtained sheet, high frequency was given to the sheet (each thickness 0.2 mm) which was overlapped with a high frequency welder [YTO-5A, manufactured by Yamamoto Vinita Co., Ltd.] under the following dielectric heating conditions. A molded article was obtained by heat (high frequency) sealing.
<Dielectric heating conditions>
-Mold: 10mm x 100mm
・ Frequency: 40.46MHz
・ Output: 5kW
・ Anode current: 0.22A
-Welding time: 0.5 seconds-Surface plate temperature: 30 ° C
The molded article obtained above was evaluated based on the following evaluation criteria.
<Evaluation criteria>
◎: Not peeled by 180 degree peel test ○: Visual confirmation that the entire seal part (90% or more of the seal part area) is welded △: Part (seal part area of 10% to less than 90%) welding ×: Visual confirmation of no welding (less than 10% of seal area) XX: Visual confirmation that burn occurred and the appearance was poor.

(2) Izod impact strength (mechanical properties)
For each dielectric heating polyolefin resin composition, an injection molding machine [“PS40E5ASE” manufactured by Nissei Plastic Industry Co., Ltd.] was used to produce a molding test piece at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C., and ASTM D256. Izod impact strength (unit: J / m) was measured according to Method A (notched, 3.2 mm thickness).

(3) Surface appearance <Appearance>
Each dielectric heating polyolefin resin composition is melt-extruded using an extruder equipped with a T-type die [Labplast Mill 2D20C, manufactured by Toyo Seiki Seisakusho Co., Ltd.] at a cylinder temperature of 230 ° C., and a cooling roll at 20 ° C. The extruded sheet was 0.2 mm thick. About the obtained extruded sheet, the surface appearance of the test piece (length 100 mm × width 100 mm × thickness 2 mm) was visually observed and evaluated according to the following criteria.
<Evaluation criteria>
○: Good without abnormality (equivalent to thermoplastic resin not containing dielectric heating agent)
X: Surface roughness, swelling, etc. are observed

  From Table 1, it can be seen that the dielectric heating property-imparting agent for polyolefin resin of the present invention can impart excellent dielectric heating properties to the polyolefin resin without impairing mechanical properties as compared with the comparative one. Moreover, it turns out that a molded article is excellent in dielectric heating property and an external appearance.

  The dielectric heating property-imparting agent for polyolefin resins of the present invention can impart excellent dielectric heating properties to molded products without impairing the mechanical strength and good appearance of the polyolefin resin molded products. Housing products (home appliances / OA equipment, game machines and office work) molded by molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, foam molding and film molding (casting method, tenter method and inflation method), etc. Equipment), plastic container materials [tray used in clean rooms (IC trays, etc.) and other containers], various cushioning materials, covering materials (wrapping film, protective film, etc.), flooring sheets, artificial grass Widely used as materials for mats, tape base materials (for semiconductor manufacturing processes, etc.) and various molded products (automobile parts, etc.) Can be, it is extremely useful.

Claims (11)

A block of polymer (a) having a volume resistivity exceeding 1 × 10 ¹¹ Ω · cm and a block of polymer (b) having a volume resistivity of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm are constituted. Dielectric heating property imparting agent (Z) for polyolefin resin comprising block polymer (A) contained as a unit. The dielectric heating property imparting agent for polyolefin resin according to claim 1, wherein the block polymer (A) is the following (A1) and / or (A2).
(A1): (a) is a polyamide (a1), (b) is a polyether (b1) and / or a polyether-containing polymer (b2), and (a1), (b1) and / or ( polyether ester amide having a structure obtained by reacting with b2).
(A2): (a) is polyolefin (a2), and the block of (a2) and the block of polymer (b) are composed of an ester bond, an amide bond, an ether bond, an imide bond, a urethane bond and a urea bond. A block polymer having a structure bonded via one or more bonds selected from the group consisting of:   The weight ratio [(a) / (b)] of the block (a) and the block (b) constituting the block polymer (A) is 10/90 to 80/20. Dielectric heat resistance imparting agent for polyolefin resin.   The number average molecular weight of the said block polymer (A) is 2,000-1,000,000, The dielectric heating property imparting agent for polyolefin resins in any one of Claims 1-3.   The number average molecular weight of the polymer (a) is 200 to 25,000, The dielectric heating property imparting agent for polyolefin resin according to any one of claims 1 to 4.   The number average molecular weight of the polymer (b) is 500 to 20,000, The dielectric heating property imparting agent for polyolefin resin according to any one of claims 1 to 5.   Further, an alkali metal or alkaline earth metal salt (C1) having a melting point exceeding 25 ° C., a quaternary ammonium salt (C2) having a melting point exceeding 25 ° C., an ionic liquid (C3) having a melting point of 25 ° C. or less, and inorganic oxidation The dielectric heating property imparting agent for polyolefin resin according to any one of claims 1 to 6, comprising at least one dielectric heating property improving agent (C) selected from the group consisting of the product (C4).   A polyolefin resin composition (X) for dielectric heating comprising the dielectric heating property-imparting agent (Z) for polyolefin resin according to any one of claims 1 to 7 and a polyolefin resin (Y).   The polyolefin resin composition for dielectric heating according to claim 8, wherein the weight ratio [(Z) / (Y)] of (Z) and (Y) is from 1/99 to 50/50.   A molded product for dielectric heating, wherein the polyolefin resin composition (X) for dielectric heating according to claim 8 or 9 is molded.   A molded article obtained by subjecting the molded article according to claim 10 to dielectric heating.