JP2018143963A - Dispersant for inorganic filler - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersion agent for an inorganic filler excellent in dispersibility.SOLUTION: There is provided a dispersion agent for an inorganic filler which contains a block polymer containing a block of a polymer having a volume resistivity value of more than 1×10Ω cm and a block of a polymer having a volume resistivity value of 1×10to 1×10Ω cm as constitutional units. A number average molecular weight of the block polymer is preferably 10,000-100,000. A number average molecular weight of the polymer having the volume resistivity value of more than 1×10Ω cm is preferably 2,000-25,000.SELECTED DRAWING: None

Description

  The present invention relates to a dispersant for inorganic filler. More specifically, the present invention relates to an inorganic filler dispersant that imparts excellent dispersibility to a molded article of a thermoplastic resin composition.

  Conventionally, as a technique for dispersing an inorganic filler (inorganic silver compound or the like), a resin composition containing a polyamide elastomer, a styrene resin, and a silver inorganic filler has been proposed (Patent Document 1, etc.).

JP-A-6-116458

However, the technique of Patent Document 1 is not satisfactory with respect to dispersibility, and improvement has been demanded.
An object of this invention is to provide the dispersing agent for inorganic fillers excellent in the dispersibility.

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 relates to a block of a polymer (a) having a volume resistivity value exceeding 1 × 10 ¹¹ Ω · cm, and a polymer having a volume resistivity value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm (b And a block polymer (A) containing as a structural unit a dispersant for inorganic filler (Z).

The dispersant for inorganic filler (Z) of the present invention has the following effects.
(1) It is excellent in the dispersion characteristic (dispersibility) of an inorganic filler with respect to a thermoplastic resin. In particular, the dispersibility with respect to the polyolefin resin is excellent.
(2) The molded article of the thermoplastic resin composition containing the dispersant, the inorganic filler, and the thermoplastic resin is imparted with excellent mechanical properties and excellent appearance.

<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). These may be used in combination of two or more.
Of the above (a), polyamide (a1) and polyolefin (a2) are preferred from the viewpoint of dispersibility (dispersion characteristics of the inorganic filler), and polyolefin (a2) is more preferred.
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) benzene And bis (aminobutyl) benzene, etc.].

  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) Acids, tolylene dicarboxylic acid, xylylene dicarboxylic acid and 5-sulfoisophthalic acid alkali metal salts, etc.), alicyclic dicarboxylic acids 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. , A copolymer of nylon 6 and nylon 12, and a copolymer of nylon 6 and 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.
Among these, (a2-1) and (a2-5) having a carboxyl group at the terminal are preferable.
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, 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, from the viewpoint of ease of modification and availability when introducing a carboxyl group, a hydroxyl group, an amino group, or an isocyanate group, a degraded polyolefin (degraded polyolefin) is preferable. Further preferred is a heat-degraded polyolefin (heat-degraded polyolefin).
According to the thermal degradation, a low molecular weight polyolefin having an average number of terminal double bonds per molecule of 1.5 to 2 can be easily obtained as described later, and the low molecular weight polyolefin has a carboxyl group, a hydroxyl group, and 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). And those obtained by heat degradation 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). [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 K6760 is used, and the measurement method conforms to the method defined in JIS K7210 (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.
Among 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 molecular weight control, 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 6 from the viewpoint of dispersibility of the molded product described later. , 000.
The number of terminal double bonds in (a2-01) is preferably 1-40 per 1,000 carbon atoms, more preferably 2-30, and particularly preferably from the viewpoint of dispersibility of the molded product. 4 to 20 pieces.

  (A2-01) The average number of terminal double bonds per molecule is preferably from the viewpoint of ease of taking a repeating structure in the molecule, dispersibility of the molded product, and thermoplasticity of the block polymer (A) described later. 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 whose one end can be modified can be obtained in the same manner as (a2-01), and Mn in (a2-02) is the dispersibility of the molded product described later. From this point of view, it is preferably 2,000 to 50,000, more preferably 2,500 to 30,000, 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 dispersibility of the molded product and the molecular weight control of the block polymer (A). The number is preferably 0.5 to 15, particularly preferably 0.7 to 10.

(A2-02) The average number of double bonds per molecule is preferably 0 from the viewpoints of easy repeat structure in the molecule, dispersibility of the molded product, and thermoplasticity of the block polymer (A) described later. 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 the 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 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.

  The polyolefin (a2-1) having a carboxyl group at both ends of the polymer includes (a2-01) having an α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, its alkyl) (C1-C4) means an ester or its anhydride. The same shall apply hereinafter.) Polyolefins (a2-1-1) and (a2-1-1) having a structure modified with lactam or aminocarboxylic acid Polyolefin (a2-1-2) having a modified structure (a2-1-2), polyolefin (a2-1-3) having a structure modified by oxidation or hydroformylation (a2-1-01), and lactam or (a2-1-3) Polyolefin (a2-1-4) having a structure secondarily modified with aminocarboxylic acid and a mixture 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 acid, mono- or dicarboxylic acid alkyl ester, and mono- or dicarboxylic acid anhydride are preferable from the viewpoint of ease of modification, and maleic acid (anhydride) and fumaric acid are more preferable. 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, dispersibility of the molded product, and heat described later. From the viewpoint of dispersibility of the block polymer (A) in the plastic resin composition, it is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight, and particularly preferably 2 to 20% by weight.
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.

(A2-1-1) can be obtained by secondary modification of (a2-1) 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.
Of the lactams and aminocarboxylic acids, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred, and caprolactam, laurolactam, Omega-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 the secondary modification is based on the weight of the substance to be modified (a2-1), ease of repetitive structure in the molecule, dispersibility of the molded product, and block polymer (A). From the viewpoint of thermoplasticity, it is preferably 0.5 to 200% by weight, more preferably 1 to 150% by weight, and particularly preferably 2 to 100% by weight.

(A2-3) 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.
(A2-4) can be obtained by secondary modification of (a2-3) with a lactam or an 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), and preferred ranges and use amounts thereof are also the same.

Mn of (a2-1) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably from the viewpoint of heat resistance and reactivity with the polymer (b) described later. 2,500 to 10,000.
The acid value of (a2-1) 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 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 preferable 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 determined based on the weight of the object to be modified (a2-1), ease of repetitive structure in the molecule, dispersibility of the molded product, and the thermoplastic resin composition described later. From the viewpoint of dispersibility of the block polymer (A) and 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. .
Mn of (a2-2) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably from the viewpoint of heat resistance and reactivity with the polymer (b) described later. 2,500 to 10,000.
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.
Among 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 dispersibility of the molded product, the dispersibility of the block polymer (A) in the thermoplastic resin composition, and the molded product. From the viewpoint of mechanical properties of (a2-1), it is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight, and particularly preferably 2 to 30% by weight based on the weight of (a2-1).
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.

Mn of (a2-3) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably from the viewpoint of heat resistance and reactivity with the polymer (b) described later. 2,500 to 10,000.
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.

Polyolefin (a2-4) having an isocyanate group at both ends includes a polyolefin having an isocyanate group obtained by modifying (a2-2) with poly (2-3 or more) isocyanate (hereinafter abbreviated as PI) and these The mixture of 2 or more types of these is mentioned.
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 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).

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

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

  (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, etc.), and These anhydrides] and the like.

As the 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 a method of ring-opening polymerization or polycondensation of the amidimide-forming monomer in the presence thereof.
The amount used of the molecular weight modifier is preferably 2 to 80% by weight, more preferably 4 to 4%, from the viewpoint of dispersibility and heat resistance of the molded product, based on the total weight of the amidoimide-forming monomer and the molecular weight modifier. 75% by weight.

  Mn of (a3) is preferably 200 to 5,000, more preferably 500 to 4,000, from the viewpoints of moldability and production of the dispersant.

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

<Polymer (b)>
The polymer (b) in the present invention has a volume resistivity value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm, more preferably 1 × 10 ⁶ to 1 × 10 ⁹ Ω · cm, and particularly preferably. Is 1 × 10 ⁶ to 1 × 10 ⁸ Ω · cm.
Those having a volume resistivity value of less than 1 × 10 ⁵ Ω · cm are substantially difficult to obtain, and if it exceeds 1 × 10 ¹¹ Ω · cm, the dispersibility of the molded product described later decreases.
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).

The diol (b0) includes 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. Etc.
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), 1,4-butanediol (hereinafter referred to as 1, 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 (xylylene diol, hydroquinone, catechol, resorcin, urushiol, bisphenol A, bisphenol F, bisphenol S, 4,4′-dihydroxy. Diphenyl-2,2-butane and dihydroxybiphenyl) and polycyclic aromatic dihydric alcohols (dihydroxynaphthalene, binaphthol and the like).

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 aromatic dihydric alcohols having 6 to 18 carbon atoms, and more preferred is EG from the viewpoint of reactivity with bishydroxyalkylated products. And bisphenol A.

R ¹ and R ² in the general formula (1) are each independently an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include ethylene group, 1,2- or 1,3-propylene group and 1,2-, 1,3-, 1,4- or 2,3-butylene group. It is done.
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 are random bonds or block bonds. But you can.

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 (hereinafter abbreviated as PO), 1,2-, 1, 3-, 1,4-, 2,3- or butylene oxide (hereinafter abbreviated as BO) and a combination system of two or more of these are used, but other AO [having 5 to 12 carbon atoms] if necessary. α-olefin oxide, styrene oxide, and epihalohydrin (such as epichlorohydrin) can be used in a small proportion (30% by weight 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, 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 4 carbon atoms. The alkylene group having 2 to 4 carbon atoms, the general formula (1) the same as those exemplified as R ¹ and R ² can be mentioned in the preferred 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 moieties may be 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).

  Mn of the polyether (b1) is preferably 500 to 20,000, more preferably 700 to 18,000, and particularly preferably 1,000 from the viewpoints of heat resistance and reactivity with the polymer (a). ˜15,000, most preferably 1,200 to 8,000.

  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). Is mentioned.
Among (a1 ′), from the viewpoint of dispersibility, a ring-opening polymer of caprolactam, a polycondensate of 12-aminododecanoic acid, and a polyamide of adipic acid and hexamethylenediamine are more preferable. 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).
As polyether urethane (b2-5), diisocyanate in the above PI, polyether diol (b1-1) or polyether diamine (b1-2) and, if necessary, 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 viewpoints of dispersibility and moldability.
The lower limit of Mn in (b2) is preferably 500 from the viewpoint of heat resistance, and more preferably 1,000. The upper limit of Mn in (b2) is preferably 50,000, more preferably 30,000, particularly preferably 20,000, from the viewpoint of reactivity with the polymer (a).

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, 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 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 ⁻ , ClO ₄ ^{− and the} like. Can be mentioned.
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.

  Mn of (b3) is preferably 500 to 20,000, more preferably 1,000 to 15,000, and particularly preferably 1,200 from the viewpoint of dispersibility and reactivity with the polymer (a). ~ 8,000.

The anionic polymer (b4) comprises a dicarboxylic acid (γ ′) having a sulfonyl group and a diol (b0) or a polyether (b1) as essential constituent units, and 2 to 80, preferably 3 to 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 a salt. And aromatic dicarboxylic acids or aliphatic dicarboxylic acids having a sulfonyl group.

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) esters (such as methyl ester and ethyl ester) and acid anhydrides].
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. .

Among (b0) and (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 (addition mole number: 2 to 60 mol) of bisphenol A and the like, and a mixture of two or more thereof.
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).

  Mn of (b4) is preferably 500 to 20,000, more preferably 1,000 to 15,000, and particularly preferably 1,200 from the viewpoints of dispersibility and reactivity with the polymer (a). ~ 8,000.

Of the above (b1) to (b4), from the viewpoint of dispersibility and the dispersibility of (A), (b1) and (b2) are preferable, and (b1) is more preferable.
The number average molecular weight (Mn) of (b) is preferably 500 to 20,000 from the viewpoints of dispersibility and mechanical properties.

<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 dispersibility, 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 80/20 from the viewpoint of mechanical properties and dispersibility. More preferably, it is 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 dispersibility and mechanical properties.
[(A)-(b)] n in the n-type structure is preferably 2 to 50, more preferably 2.3 from the viewpoints of dispersibility, mechanical properties of the molded product, and anchor effect on the resin. 30, particularly preferably 2.7 to 20, most preferably 3 to 10. n can be determined by Mn of the block polymer (A), Mn of (a) and (b), and ¹ H-NMR analysis.

  Mn in (A) is preferably 2,000 to 1,000,000, more preferably 4,000 to 500,000, and particularly preferably 10 from the viewpoint of mechanical properties and dispersibility of the molded product described later. , 100,000 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) are charged into a reaction vessel, and water produced by amidation reaction, esterification reaction or imidization reaction at a reaction temperature of 100 to 250 ° C. and a pressure of 0.003 to 0.1 MPa with stirring ( Hereinafter, it is abbreviated as generated water.), And a method of reacting for 1 to 50 hours while removing from the reaction system. The weight ratio of (a) and (b) is 10/90 to 80/20, more preferably 20/80 to 75/25, from the viewpoint of dispersibility 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.
There is a method in which (a) is charged into a reaction vessel, heated to 30 to 100 ° C. with stirring, and then (b) is charged and reacted at the same temperature for 1 to 20 hours. The weight ratio of (a) and (b) is 10/90 to 80/20, more preferably 20/80 to 75/25, from the viewpoint of dispersibility 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 1-8 carbon atoms (trimethylamine, tributylamine). , And trioctylamine), diazabicycloalkenes [1,8-diazabicyclo [5,4,0] undecene-7] and the like}; and combinations of two or more thereof.

<Dispersant for inorganic filler>
The dispersant for inorganic filler (Z) of the present invention contains the block polymer (A).
The (Z) can be suitably used as an inorganic filler dispersant for the thermoplastic resin (Y) described later, particularly as an inorganic filler dispersant for a polyolefin resin.

<Inorganic filler-containing masterbatch composition (M)>
The inorganic filler-containing masterbatch composition (M) of the present invention contains the dispersant (Z) and an inorganic filler (B) described later.
The master batch composition (M) is preferably (Z) and (B). The master batch composition (M) can be preferably produced by melt-kneading the (Z) and the (B). Furthermore, it can be applied to the thermoplastic resin composition (X) described later.
In the masterbatch composition (M), the weight ratio [(Z) / (B)] is preferably 40/60 to 99/1, and more preferably 60/40 to 97/3.

<Thermoplastic resin composition (X)>
The thermoplastic resin composition (X) in this invention contains the said dispersing agent for inorganic fillers (Z), the below-mentioned inorganic filler (B), and the below-mentioned thermoplastic resin (Y).

<Inorganic filler (B)>
As an inorganic filler (B), various things, for example, the following (B1)-(B9), and a mixture thereof are mentioned.
(B1) oxides (for example, silica, alumina, titanium oxide, wollastonite, calcined kaolin, silica, iron oxide, zinc oxide, calcium oxide, aluminum oxide, magnesium oxide, zirconium oxide, chromium oxide);
(B2) hydroxide (for example, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, zirconium hydroxide, ferrous hydroxide, copper hydroxide);
(B3) Silicates (for example, talc, mica, clay, dolomite, bentonite, silica, calcium silicate, aluminum silicate, diatomaceous earth, perlite, zeolite, silver, copper, zinc, manganese, etc. may be used as constituent elements. , Which may carry an amino compound);
(B4) carbonate (for example, calcium carbonate, magnesium carbonate);
(B5) metal salts (eg barite, fluorite, calcium sulfate, aluminum sulfate);
(B6) metal sulfide (for example, molybdenum disulfide);
(B7) inorganic microballoons (eg, glass, shirasu);
(B8) Metal powder (for example, aluminum powder, copper powder).
(B9) Inorganic phosphate (for example, aluminum tripolyphosphate, zirconium phosphate, titanium phosphate, tin phosphate):

Among these (B), (B1), (B2) and (B3) are preferable from the mechanical strength and industrial viewpoint of the molded product, and (B2) and (B3) are particularly preferable. Are zeolite and magnesium hydroxide.
The volume average particle size of (B) is preferably 0.01 μm to 30 μm, more preferably 0.5 μm to 15 μm, and particularly preferably 1 μm to 10 μm from the viewpoints of mechanical properties, dispersibility, and moldability.

<Thermoplastic resin (Y)>
As the thermoplastic resin (Y) in the present invention, polyphenylene ether resin (PPE) (Y1); vinyl resin {polyolefin resin (Y2) [for example, polypropylene (PP), polyethylene, ethylene-vinyl acetate copolymer resin (EVA) and Ethylene-ethyl acrylate copolymer resin, etc.], polyacryl resin (Y3) [for example, polymethyl methacrylate, etc.], polystyrene resin (Y4) [vinyl group-containing aromatic hydrocarbon alone, and vinyl group-containing aromatic hydrocarbon, Copolymers comprising at least one selected from the group consisting of (meth) acrylic acid esters, (meth) acrylonitrile and butadiene; for example, polystyrene (PS), styrene / acrylonitrile copolymer (AN resin), acrylonitrile / Butadiene / styrene copolymer ( BS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin) and styrene / methyl methacrylate copolymer (MS resin) etc.]}; polyester resin (Y5) [for example, polyethylene terephthalate, polybutylene terephthalate, Polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene adipate, etc.]; polyamide resin (Y6) (for example, nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66 and nylon 6) Polycarbonate resin (Y7) (for example, polycarbonate and polycarbonate / ABS alloy resin, etc.); polyacetal resin (Y8); biodegradable resin (Y9), and a mixture of two or more thereof And the like.
Of these, (Y1), (Y2), (Y3), (Y4), (Y5), and (Y7) are preferable from the viewpoint of the mechanical properties of the molded product and the dispersibility of the inorganic filler to be described later. More preferred are (Y2), (Y4) and (Y7), and particularly preferred is (Y2).

  The ratio based on (Z), (B), (Y) and the total weight in the thermoplastic resin composition (X) is preferably (Z) of 0.09 to 15 weights from the viewpoint of mechanical properties and dispersibility. %, (B) 0.01 to 10% by weight, (Y) 75 to 99.9% by weight, more preferably (Z) 0.5 to 10% by weight, and (B) 0.1 to 5%. % By weight and (Y) is 85 to 99% by weight.

  The ratio based on the weight of (Z), (B) and (Y) in the thermoplastic resin composition (X) is preferably (Z) / (Y) of 0.0009 from the viewpoint of mechanical properties and dispersibility. -0.2, (B) / (Y) is 0.0001-0.14, (B) / (Z) is 0.05-0.67, more preferably (Z) / (Y) is 0.00. 02 to 0.1, (B) / (Y) is 0.001 to 0.05, and (B) / (Z) is 0.1 to 0.5.

  In the thermoplastic resin composition (X) of the present invention, other known additives (E) [antioxidants, ultraviolet absorbers, flame retardants, mold release agents, etc.] within a range not impairing the effects of the present invention. Can be contained.

The thermoplastic resin composition (X) for use in the present invention can be obtained by melt-mixing the dispersant (Z), the (B), the thermoplastic resin (Y), and, if necessary, (E). 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 (B), (Y) and, if necessary, (E) are collectively added and melt-mixed.
[2] After (Z) is melt-mixed, (B) and a part of (Y) are melt-mixed in advance to prepare a high concentration composition (masterbatch resin composition) of (Z), and then the remaining (Y) and, if necessary, a method of melting and mixing (E) (a master batch method or a 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>
The molded product in the present invention is obtained by molding the thermoplastic resin composition (X). Examples of molding methods include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.), etc., depending on the purpose. Molding, multilayer molding or foam molding can be used for any molding method.

  The molded article has excellent mechanical properties and an excellent appearance. This is presumably because the dispersant for inorganic filler of the present invention is excellent in the dispersion characteristics of the inorganic filler in the molded article of the thermoplastic resin composition. Moreover, it is estimated that the filler concentration on the surface of the molded product becomes large and is uniformly dispersed. In particular, it can be presumed that the functionality derived from the inorganic filler is excellent.

  Examples of the present invention will be described below, but the present invention is not limited thereto. In the following, parts indicate parts by weight, and% indicates% by weight.

<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, and Mn was 1,000.

<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 up to 200 ° C. with stirring and sealing, 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, and Mn was 3,600.

<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, and Mn was 4,000.

<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, 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, two 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, the amine value was 0.01, and Mn was 10,200.

<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, and Mn was 1,700. The low molecular weight polypropylene obtained by the above thermal degradation method (Mn: 1,500, the number of double bonds per 1,000 carbon atoms: 17.8, the 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, and Mn was 1,700.

<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 (hydroxyl value: 30.1, acid value: 0.5, 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. An anionic polymer (b4α) having an average of 6 sodium sulfonate bases in one molecule (hydroxyl value is 49, acid value is 0.6 The volume resistivity value 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 reactor 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, Acid value: 0.4, 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). Thus obtained dispersant for inorganic filler (Z-1) 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 dispersant for inorganic filler (Z-2) containing a 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) Polymerization was performed at the same temperature for 3 hours to obtain a dispersant for inorganic filler (Z-3) 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. An inorganic filler dispersant (Z-4) 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 dispersing agent (Z-5) for inorganic fillers 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 dispersing agent (Z-6) for inorganic fillers 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. Thus obtained dispersant for inorganic filler (Z-7) 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) An inorganic filler dispersant (Z-8) containing a block polymer (A2-6) was obtained in the same manner as in Example 3 except that the content was changed to 3 parts.
In addition, Mn of (A2-6) was 100,000.

<Example 9>
90 parts of dispersant for inorganic filler (Z-4) and 10 parts of inorganic filler (B-2) [magnesium hydroxide [trade name “Sukima 5A”, manufactured by Kyowa Chemical Industry Co., Ltd., volume average particle diameter 1 μm] After blending for 3 minutes with a Henschel mixer, the mixture was melt-kneaded with a vented twin-screw extruder at 100 rpm, 200 ° C., and a residence time of 5 minutes to obtain an inorganic filler-containing masterbatch composition (M).

<Comparative Example 1>
The polyamide (a1-1) obtained in Production Example 1 was used as it was to prepare a dispersant for inorganic filler (ratio Z-1) for comparison.

<Evaluation Examples 1 to 15 and Comparative Evaluation Example 1>
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 thermoplastic resin composition (X) was obtained. About the obtained thermoplastic resin composition (X), the <performance test> mentioned later was done. The results are shown in Table 1.

<Performance test>
(1) Surface appearance <Appearance, dispersibility>
Using an extruder equipped with a T-shaped die [Laboplast Mill 2D20C, manufactured by Toyo Seiki Seisakusho Co., Ltd.], melt extrusion at a cylinder temperature of 230 ° C., and quenching with a cooling roll at 20 ° C. An extruded sheet was obtained. About the obtained extruded sheet, the surface appearance of the test piece (80 mm × 80 mm × 2 mm) was visually observed and evaluated according to the following criteria.
<Evaluation criteria>
A: The inorganic filler is uniformly dispersed.
○: The inorganic filler is almost uniformly dispersed.
Δ: The inorganic filler is slightly non-uniformly dispersed.
X: An inorganic filler has a nonuniform part.

(2) Dispersibility <Dispersibility of (B)>
Using an injection molding machine “PS40E5ASE” [manufactured by Nissei Plastic Industry Co., Ltd.], a test piece (80 mm × 80 mm × 2 mm) was obtained by molding at a cylinder temperature of 220 ° C. and a mold temperature of 50 ° C. About the obtained test piece, the quantity of the inorganic filler (B) of the test piece surface was measured and calculated by SEM-EDX [JSM-7000, JEOL Co., Ltd.] [((alpha)), unit:%].
Next, the surface of the test piece was polished 1 mm using a desktop test polishing machine “IM-P2” [manufactured by IM T. Co., Ltd.], and then the inorganic filler (B) inside the test piece was similarly processed. The amount was measured and calculated by SEM-EDX [JSM-7000, manufactured by JEOL Ltd.] [(β), unit:%].
Dispersibility (%) was evaluated by the following formula (1).

[Dispersibility (%)] = (α) × 100 / (β) (1)

(3) Izod impact strength (unit: J / m) <mechanical properties>
Using an injection molding machine [“PS40E5ASE”, manufactured by Nissei Plastic Industry Co., Ltd.], a molding test piece was prepared at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C., and in accordance with ASTM D256 Method A (notched). It was measured.

The contents of the symbols in Table 1 are as follows.
(B-1): Alumina [trade name “A-43-M”,
Showa Denko KK, volume average particle size 0.8μm]
(B-2): Magnesium hydroxide [trade name “Sukima 5A”,
Manufactured by Kyowa Chemical Industry Co., Ltd., volume average particle size 1 μm]
(B-3): Zeolite [“Zeostar CA-110P”,
Nippon Chemical Industry Co., Ltd., volume average particle size 3 μm]
(Y-1): PP resin ["PM771M", manufactured by Sun Allomer Co., Ltd.]
(Y-2): PE resin [low density polyethylene “NUC8321”,
Made by Dow Chemical Co., Ltd.]
(Y-3): Modified PPE resin [“Noryl V-095”,
SABIC Innovative Plastics Japan GK]

  From Table 1, the dispersant for inorganic fillers of the present invention is superior in dispersion properties (dispersibility) of inorganic fillers to thermoplastic resins compared to comparative ones. Moreover, it turns out that the outstanding mechanical property and the outstanding external appearance are provided to the molded article of a thermoplastic resin composition.

  Since the dispersant for inorganic filler of the present invention can impart excellent inorganic filler dispersibility to a molded product without impairing the mechanical strength and good appearance of the molded product of thermoplastic resin, various molding methods [injection molding, compression 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 Can be widely used as materials for mats, tape base materials (for semiconductor manufacturing processes, etc.) and various molded products (automobile parts, etc.) It is useful.

Claims (7)

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. Dispersant (Z) for inorganic filler containing block polymer (A) included as a unit. The dispersant for inorganic filler according to claim 1, wherein the block polymer (A) is the following (A1) and / or (A2).
(A1): (a) is polyamide (a1), (b) is a polyether (b1) and / or a polyether-containing polymer (b2), and (a1), (b1) and / or ( polyether ester amide (A2) having a structure reacted with b2): (a) is polyolefin (a2), and the block of (a2) and the block of polymer (b) are ester bonds and amide bonds , A block polymer having a structure bonded through one or more bonds selected from the group consisting of an ether bond, an imide bond, a urethane bond and a urea bond   The weight ratio [(a) / (b)] of the block (a) and the block (b) constituting the block polymer (A) is 10/90 to 80/20. Dispersant for inorganic filler.   The number average molecular weight of the said block polymer (A) is 10,000-100,000, The dispersing agent for inorganic fillers in any one of Claims 1-3.   The dispersant for inorganic filler according to any one of claims 1 to 4, wherein the polymer (a) has a number average molecular weight of 2,000 to 25,000.   The dispersant for inorganic filler according to any one of claims 1 to 5, wherein the polymer (b) has a number average molecular weight of 500 to 20,000.   An inorganic filler-containing masterbatch composition (M) comprising the dispersant for inorganic filler (Z) according to any one of claims 1 to 6 and the inorganic filler (B).