Antistatic agent

Abstract

The object of the present invention is to provide an antistatic agent that imparts excellent antistatic properties to thermoplastic resins without impairing transparency and mechanical properties. [Solution] An antistatic agent (Z) comprising a block polymer (A) composed of blocks of at least one hydrophobic polymer (a) selected from the group consisting of polyamide (a1) and polyolefin (a2) and blocks of hydrophilic polymer (b), and inorganic particles (C) having a volume average particle diameter of 1 to 50 nm, and having a refractive index of 1.500 to 1.600.

Description

Technical Field

[0001] The present invention relates to an antistatic agent.

Background Art

[0002] Conventionally, it is common to use an antistatic agent as a method for imparting antistatic properties to a highly insulating thermoplastic resin. As a method for imparting antistatic properties using an antistatic agent, a method of kneading a small amount of polyether ester amide (for example, see Patent Document 1), which is a polymer type antistatic agent, into a resin is known. However, even in the method of kneading the above polymer type antistatic agent, it could not be said that the antistatic properties were sufficiently satisfactory.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide an antistatic agent that imparts excellent antistatic properties to a thermoplastic resin without impairing transparency and mechanical properties.

Means for Solving the Problems

[0005] As a result of studies to achieve the above object, the present inventors have reached the present invention. That is, the present invention contains a block polymer (A) having as structural units a block of at least one hydrophobic polymer (a) selected from the group consisting of polyamide (a1) and polyolefin (a2) and a block of a hydrophilic polymer (b), and inorganic particles (C) having a volume average particle diameter of 1 to 50 nm, and is an antistatic agent (Z) having a refractive index of 1.500 to 1.600.

Effects of the Invention

[0006] The antistatic agent (Z) of the present invention has the following effects. (1) It imparts antistatic properties to a thermoplastic resin without impairing transparency and mechanical properties. (2) Molded articles of the antistatic composition containing the antistatic agent (Z) are excellent in transparency, mechanical properties, and antistatic properties.

Mode for Carrying Out the Invention

[0007] <Hydrophobic polymer (a)> The hydrophobic polymer (a) in the present invention means a polymer having a volume resistivity exceeding 1×10 11 Ω·cm. The hydrophobic polymer (a) is at least one selected from the group consisting of polyamide (a1) and polyolefin (a2), and these may be used alone or in combination of two or more. Among the hydrophobic polymers (a), polyamide (a1) is preferable from the viewpoint of antistatic properties.

[0008] The volume resistivity in the present invention is a value obtained by measuring in an atmosphere of 23°C and 50%RH in accordance with ASTM D257 (1984).

[0009] Examples of the polyamide (a1) include those obtained by ring-opening polymerization or polycondensation of amide-forming monomers. Examples of the amide-forming monomers include lactam (a01), aminocarboxylic acid (a02), and combinations of diamine (a03) and dicarboxylic acid (a04). Examples of the lactam (a01) include lactams having 4 to 20 carbon atoms (hereinafter sometimes abbreviated as C) (such as caprolactam, enanthlactam, laurolactam, undecanolactam, etc.). Examples of the ring-opening polymer of lactam (a01) include nylon 4, nylon 5, nylon 6, nylon 8, and nylon 12.

[0010] Examples of aminocarboxylic acids (a02) include C6-12 compounds such as ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and mixtures thereof.

[0011] Examples of diamines (a03) include C2-40, such as aliphatic diamines, alicyclic diamines, and aromatic (ali) diamines, as well as mixtures thereof. Examples of aliphatic diamines include those with a C2-40 ratio, such as ethylenediamine, propylenediamine, hexamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, and 1,20-eicosanediamine. Examples of alicyclic diamines include C5-40, such as 1,3- and 1,4-cyclohexanediamine, isophoronediamine, 4,4'-diaminocyclohexylmethane, and 2,2-bis(4-aminocyclohexyl)propane. Examples of aromatic aliphatic diamines include C7-20, such as xylylenediamine, bis(aminoethyl)benzene, bis(aminopropyl)benzene, and bis(aminobutyl)benzene. Examples of aromatic diamines include C6-40, such as p-phenylenediamine 2,4- and 2,6-toluylenediamine and 2,2-bis(4,4'-diaminophenyl)propane.

[0012] Examples of dicarboxylic acids (a04) include C2-40 dicarboxylic acids, such as aliphatic dicarboxylic acids, aromatic ring-containing dicarboxylic acids, alicyclic dicarboxylic acids, derivatives of these dicarboxylic acids [e.g., acid anhydrides, lower (C1-4) alkyl esters and dicarboxylate salts [alkali metals (e.g., lithium, sodium, and potassium)]] and mixtures of two or more of these.

[0013] Examples of aliphatic dicarboxylic acids include C2-40 (preferably C4-20, more preferably C6-12, from the viewpoint of antistatic properties), such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, maleic acid, fumaric acid, and itaconic acid. Examples of aromatic ring-containing dicarboxylic acids include C8-40 (preferably 8-16, more preferably 8-14, from the viewpoint of antistatic properties), such as ortho-, iso- and terephthalic acid, 2,6- and 2,7-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, tolylenedicarboxylic acid, xylylenedicarboxylic acid, and alkali metal 5-sulfoisophthalate salts (same as above). Examples of alicyclic dicarboxylic acids include C5-40 (preferably C6-18, more preferably C8-14, from the viewpoint of antistatic properties), such as cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid, and camphoric acid.

[0014] Among the above amide-forming monomers, caprolactam, 12-aminododecanoic acid, and a combination of adipic acid and hexamethylenediamine are preferred from the viewpoint of antistatic properties.

[0015] A method for producing polyamide (a1) includes using one or more of the above-mentioned dicarboxylic acids (C2-40, preferably 4-20) or diamines (C2-40, preferably 4-20) as molecular weight modifiers, and performing ring-opening polymerization or polycondensation of the above-mentioned amide-forming monomers in their presence. Examples of the C2-40 diamines include those exemplified in the above-mentioned diamine (a03), of which aromatic (ali) group diamines are preferred from the viewpoint of refractive index, and aromatic diamines are even more preferred. Examples of the C2-40 dicarboxylic acids include those exemplified in the dicarbon (a04) above, of which aromatic ring-containing dicarboxylic acids are preferred from the viewpoint of refractive index, and more preferably terephthalic acid, isophthalic acid, 2,6- and 2,7-naphthalenedicarboxylic acid, and sodium 3-sulfoisophthalate.

[0016] The amount of molecular weight modifier used is preferably 2 to 80% by weight, and more preferably 4 to 75% by weight, based on the total weight of the amide-forming monomer and the molecular weight modifier, with the lower limit being from the viewpoint of the antistatic properties of the molded article described later, and the upper limit being from the viewpoint of the heat resistance of the molded article.

[0017] The number-average molecular weight of polyamide (a1) [hereinafter abbreviated as Mn; measured by gel permeation chromatography (GPC)] is preferably 200 to 5,000, more preferably 500 to 4,000, and especially preferably 800 to 3,000, with the lower limit being from the viewpoint of antistatic properties and the upper limit being from the viewpoint of refractive index.

[0018] Examples of polyolefins (a2) include polyolefins having carboxyl groups at both ends of the polymer (a2-1), polyolefins having hydroxyl groups at both ends of the polymer (a2-2), polyolefins having amino groups at both ends of the polymer (a2-3), and polyolefins having isocyanate groups at both ends of the polymer (a2-4), polyolefins having a carboxyl group at one end of the polymer (a2-5), polyolefins having a hydroxyl group at one end of the polymer (a2-6), polyolefins having an amino group at one end of the polymer (a2-7), and polyolefins having an isocyanate group at one end of the polymer (a2-8). Of these, the preferred types are polyolefins having carboxyl groups at both ends of the polymer (a2-1) and polyolefins having a carboxyl group at one end of the polymer (a2-5). In this invention, "end" refers to the terminal portion where the repeating structure of the monomer units constituting the polymer is interrupted. Furthermore, "both ends" refers to both ends of the polymer's main chain, while "one end" refers to either end of the polymer's main chain.

[0019] Polyolefins (a2-1) having carboxyl groups at both ends of the polymer include polyolefins (a2-01) in which carboxyl groups are introduced at both ends, with polyolefins (a2-01) having modifiable polyolefins at both ends as the main component (preferably in a content of 50% by weight or more, more preferably 75% by weight or more, and particularly preferably 80-100% by weight) as the main component; Polyolefins (a2-2) having hydroxyl groups at both ends of the polymer are obtained by introducing hydroxyl groups at both ends of polyolefins (a2-01), which are mainly composed of polyolefins whose ends are modifiable; Polyolefins (a2-3) having amino groups at both ends of the polymer include polyolefins (a2-01) whose main component is a polyolefin whose ends are modifiable, into which amino groups have been introduced at both ends; and As polyolefins (a2-4) having isocyanate groups at both ends of the polymer, polyolefins (a2-01) mainly composed of polyolefins whose ends are modifiable can be used, with isocyanate groups introduced at both ends.

[0020] For (a2-5) to (a2-8), instead of polyolefin (a2-01) whose main component is polyolefin with modifiable ends at both ends, a polyolefin (a2-02) whose main component is polyolefin with modifiable ends at one end (preferably in a content of 50% by weight or more, more preferably 75% by weight or more, and particularly preferably 80-100% by weight) can be used, in which a carboxyl group, a hydroxyl group, an amino group, or an isocyanate group can be introduced to one end.

[0021] Polyolefins (a2-01) whose main component is a polyolefin with modifiable ends include polyolefins obtained by (co)polymerization [(co)polymerization means polymerization or copolymerization. The same applies hereinafter.] of one or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10 carbon atoms) (polymerization method) and degraded polyolefins {high molecular weight [preferably number average molecular weight (hereinafter abbreviated as Mn) 50,000 to 150,000] polyolefins obtained by mechanical, thermal or chemical degradation (degradation method)}. Among polyolefins (a2-01) whose main component is a polyolefin whose ends are modifiable, demodified polyolefins are preferred from the viewpoint of ease of modification when introducing carboxyl groups, hydroxyl groups, amino groups, or isocyanate groups, and ease of availability, and thermally demodified polyolefins are preferred. With the thermally demodified polyolefin, as described below, low molecular weight polyolefins with an average of 1.5 to 2 terminal double bonds per molecule can be easily obtained, and these low molecular weight polyolefins can be easily modified by introducing carboxyl groups, hydroxyl groups, amino groups, or isocyanate groups.

[0022] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the polymer in this invention can be measured using gel permeation chromatography (GPC) under the following conditions. • Device (example): "HLC-8120" [Manufactured by Tosoh Corporation] • Columns (example): "TSKgelGMHXL" [manufactured by Tosoh Corporation] (2 pieces), "TSKgelMultiporeHXL-M" [manufactured by Tosoh Corporation] (1 piece) • Sample solution: 0.3% by weight orthodichlorobenzene solution ·Solution injection volume: 100μl ·Flow rate: 1ml / min ·Measurement temperature: 135℃ • Detection device: Refractive index detector • Reference material: Standard polystyrene (TSKstandardPOLYSTYRENE) 12 samples (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]

[0023] The thermally deconstituted polyolefins are not particularly limited, but examples include those obtained by heating high molecular weight polyolefins in an inert gas (at 300-450°C for 0.5-10 hours, for example, by the method described in Japanese Patent Publication No. 3-62804), and those thermally deconstituted by heating in air.

[0024] Examples of high molecular weight polyolefins used in the aforementioned thermal reduction method include (co)polymers of one 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; melt flow rate (hereinafter abbreviated as MFR; unit is g / 10min) is preferably 0.5 to 150, more preferably 1 to 100]. Here, MFR is a numerical value representing the melt viscosity of the resin; a higher value indicates lower melt viscosity. MFR is measured using an extrusion-type plastometer as defined in JIS K6760, and the measurement method conforms to the method specified 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 olefins having 2 to 30 carbon atoms include α-olefins with 2 to 30 carbon atoms and dienes with 4 to 30 carbon atoms. Examples of α-olefins having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-icosene, and 1-tetracosene. Examples of dienes with 4 to 30 carbon atoms include butadiene, isoprene, cyclopentadiene, and 1,11-dodecadiene. Among olefins having 2 to 30 carbon atoms, those preferred from the viewpoint of molecular weight control are ethylene, propylene, α-olefins having 4 to 12 carbon atoms, butadiene, isoprene, and mixtures thereof. More preferred are ethylene, propylene, α-olefins having 4 to 10 carbon atoms, butadiene, and mixtures thereof. Particularly preferred are ethylene, propylene, butadiene, and mixtures thereof.

[0025] The Mn content of the polyolefin (a2-01), which mainly consists of polyolefins with modifiable ends, is preferably 800 to 5,000, more preferably 1,000 to 4,000, and particularly preferably 1,200 to 3,000, with a lower limit from the viewpoint of antistatic properties and an upper limit from the viewpoint of refractive index. In polyolefin (a2-01) whose main component is polyolefin with modifiable ends, the number of terminal double bonds is preferably 1 to 40 per 1,000 carbon atoms, more preferably 2 to 30, and particularly preferably 4 to 20, from the viewpoint of the antistatic properties of the molded article.

[0026] The average number of terminal double bonds per molecule of polyolefin (a2-01), which mainly consists of polyolefins with modifiable ends, is preferably 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, from the viewpoint of ease of forming repeating structures in the molecule, antistatic properties of molded articles, and thermoplasticity of the block polymer (A) described later.

[0027] Using a method to obtain low molecular weight polyolefins by thermal degeneration, polyolefins (a2-01) mainly composed of polyolefins with Mn in the range of 800 to 6,000, an average number of terminal double bonds per molecule of 1.5 to 2, and denatureable at both ends can be easily obtained [Katsuhide Murata, Tadahiko Makino, Journal of the Chemical Society of Japan, p. 192 (1975)].

[0028] Polyolefin (a2-02) mainly composed of a polyolefin with modifiable ends can be obtained in the same manner as polyolefin (a2-01) mainly composed of polyolefins with modifiable ends. The Mn of polyolefin (a2-02) mainly composed of a polyolefin with modifiable ends is preferably 2,000 to 30,000 at the lower limit from the viewpoint of antistatic properties and preferably 2,500 to 20,000 at the upper limit from the viewpoint of refractive index, more preferably 2,500 to 20,000, and particularly preferably 3,000 to 10,000. The number of double bonds per 1,000 carbon atoms of polyolefin (a2-02), which mainly consists of a polyolefin with one end that can be modified, is preferably 0.3 to 20, more preferably 0.5 to 15, and particularly preferably 0.7 to 10, from the viewpoint of antistatic properties of the molded article and molecular weight control of the block polymer (A).

[0029] The average number of double bonds per molecule of polyolefin (a2-02), which mainly consists of a polyolefin with one end modifiable, is preferably 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, from the viewpoint of ease of forming repeating structures in the molecule, antistatic properties of molded articles, and thermoplasticity of the block polymer (A) described later. Among polyolefins (a2-02) whose main component is a polyolefin with one end that can be modified, low molecular weight polyolefins obtained by thermal reduction are preferred from the viewpoint of ease of modification, and even more preferred are polyethylene and / or polypropylene with a Mn of 3,000 to 10,000 obtained by thermal reduction. Using a method to obtain low molecular weight polyolefins by thermal degeneration, polyolefins (a2-02) can be obtained, mainly consisting of polyolefins with a Mn value in the range of 6,000 to 30,000, an average number of terminal double bonds per molecule of 1 to 1.5, and one end being denaturable. Since low molecular weight polyolefins obtained by the thermal reduction method have the average number of terminal double bonds, they can be easily modified by introducing carboxyl groups, hydroxyl groups, amino groups, or isocyanate groups.

[0030] Polyolefins (a2-01) mainly composed of polyolefins with modifiable ends and polyolefins (a2-02) mainly composed of polyolefins with modifiable ends can be obtained, for example, as mixtures thereof. These mixtures may be used as is or after purification and separation. Of these, the mixture is preferred from the viewpoint of manufacturing cost and other factors.

[0031] The following describes polyolefins (a2-1) to (a2-4) whose main component is a polyolefin with modifiable ends at both ends, and which have a carboxyl group, a hydroxyl group, an amino group, or an isocyanate group at both ends. However, polyolefins (a2-5) to (a2-8) whose main component is a polyolefin with modifiable ends at one end, and which have one of these groups at the other end, can be obtained in the same manner as (a2-1) to (a2-4) by replacing (a2-01) with (a2-02).

[0032] As polyolefins (a2-1) having carboxyl groups at both ends of the polymer, the following can be used: polyolefins (a2-1-1) having a structure in which the ends of polyolefins (a2-01), which mainly consist of polyolefins whose ends are modifiable, are modified with α,β-unsaturated carboxylic acids (anhydrides) (meaning α,β-unsaturated carboxylic acids, their alkyl (1-4 carbon atoms) esters, or their anhydrides; the same applies hereinafter); polyolefins (a2-1-2) having a structure in which (a2-1-1) is secondarily modified with lactam or aminocarboxylic acid; polyolefins (a2-1-3) having a structure in which polyolefins (a2-01), which mainly consist of polyolefins whose ends are modifiable, are modified by oxidation or hydroformylation; polyolefins (a2-1-4) having a structure in which (a2-1-3) is secondarily modified with lactam or aminocarboxylic acid; and mixtures of two or more of these.

[0033] Polyolefin (a2-1-1), which has a structure in which the terminals of (a2-01) are modified with an α,β-unsaturated carboxylic acid (anhydride), can be obtained by modifying polyolefin (a2-01), which mainly consists of polyolefins whose terminals can be modified, with an α,β-unsaturated carboxylic acid (anhydride). Examples of α,β-unsaturated carboxylic acids (anhydrides) used for modification include monocarboxylic acids, dicarboxylic acids, alkyl (1-4 carbon atoms) esters of mono or dicarboxylic acids, and anhydrides of mono or dicarboxylic acids. Specifically, examples include (meth)acrylic acid [(meth)acrylic acid means acrylic acid or methacrylic acid; the same applies hereinafter], methyl (meth)acrylate, butyl (meth)acrylate, maleic acid (anhydride), dimethyl maleate, fumaric acid, itaconic acid (anhydride), diethyl itaconic acid, and citraconic acid (anhydride). Among the α,β-unsaturated carboxylic acids (anhydrides) used for modification, dicarboxylic acids, alkyl esters of mono- or dicarboxylic acids, and anhydrides of mono- or dicarboxylic acids are preferred from the viewpoint of ease of modification. More preferably are maleic acid (anhydride) and fumaric acid, with maleic acid (anhydride) being particularly preferred.

[0034] The amount of α,β-unsaturated carboxylic acid (anhydride) used for modification is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight, and particularly preferably 2 to 20% by weight, based on the weight of the polyolefin (a2-01) whose main component is a polyolefin whose ends can be modified. This is from the viewpoint of ease of forming repeating structures in the molecule, the antistatic properties of the molded product, and the dispersibility of the block polymer (A) in the antistatic resin composition described later. Modification with α,β-unsaturated carboxylic acid (anhydride) can be carried out, for example, by adding α,β-unsaturated carboxylic acid (anhydride) to the terminal double bond of a polyolefin (a2-01) whose terminals are mainly composed of polyolefins that can be modified, using either a solution method or a melting method, and the reaction temperature is preferably 170 to 230°C.

[0035] (a2-1-2) can be obtained by secondarily modifying a polyolefin (a2-1) having carboxyl groups at both ends of the polymer with a lactam or aminocarboxylic acid. Examples of lactams used for secondary modification include lactams having 6 to 12 carbon atoms (preferably 6 to 8, more preferably 6), specifically caprolactam, enantractam, laurolactam, and undecanolactam. Examples of aminocarboxylic acids used for secondary modification include aminocarboxylic acids having 2 to 12 carbon atoms (preferably 4 to 12, more preferably 6 to 12), specifically amino acids (glycine, alanine, valine, leucine, isoleucine, and phenylalanine, etc.), ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Among the lactams and aminocarboxylic acids used for secondary modification, preferred are caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid; more preferably caprolactam, laurolactam, ω-aminocaprylic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid; and particularly preferred are caprolactam and 12-aminododecanoic acid.

[0036] The amount of lactam or aminocarboxylic acid used for secondary modification is preferably 0.5 to 200% by weight, more preferably 1 to 150% by weight, and particularly preferably 2 to 100% by weight, based on the weight of the polyolefin (a2-1) having carboxyl groups at both ends of the polymer, which is the modified product, from the viewpoint of ease of forming repeating structures in the molecule, antistatic properties of the molded article, and thermoplasticity of the block polymer (A).

[0037] (a2-1-3) can be obtained by oxidizing a polyolefin (a2-01) whose main component is a polyolefin whose ends are modifiable with oxygen and / or ozone (oxidation method), or by introducing a carboxyl group by hydroformylation using the oxo method. The introduction of carboxyl groups by oxidation can be carried out by known methods, such as the method described in U.S. Patent No. 3,692,877. The introduction of carbonyl groups by hydroformylation can be carried out by various methods, including those known, such as the method described in Macromolecules, Vol. 31, p. 5943. (a2-1-4) can be obtained by secondarily modifying (a2-1-3) with a lactam or aminocarboxylic acid. Examples of lactams and aminocarboxylic acids used for secondary modification include those exemplified as lactams and aminocarboxylic acids used for secondary modification of polyolefins (a2-1) having carboxyl groups at both ends of the polymer, and the preferred range and amount used are also the same.

[0038] The manganese content of polyolefin (a2-1) having carboxyl groups at both ends of the polymer is preferably 800 to 5,000, more preferably 1,000 to 4,000, and especially preferably 1,500 to 3,000, with a lower limit from the viewpoint of antistatic properties and an upper limit from the viewpoint of refractive index. Furthermore, the acid value of the polyolefin (a2-1) having carboxyl groups at both ends of the polymer is preferably 4 to 280 mg KOH / g, more preferably 4 to 100 mg KOH / g, and particularly preferably 5 to 50 mg KOH / g, from the viewpoint of reactivity with the hydrophilic polymer (b) and the thermoplasticity of the block polymer (A).

[0039] As the polyolefin (a2-2) having hydroxyl groups at both ends of the polymer, the polyolefin (a2-1) having carboxyl groups at both ends of the polymer can be modified with an amine having hydroxyl groups to obtain a polyolefin having hydroxyl groups, or a mixture of two or more of these. Examples of hydroxyl group-containing amines that can be used for denaturation include amines having hydroxyl groups with 2 to 10 carbon atoms, specifically 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, and 3-aminomethyl-3,5,5-trimethylcyclohexanol. Of these, amines having hydroxyl groups with 2 to 6 carbon atoms (such as 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, and 6-aminohexanol) are preferred from the viewpoint of ease of modification, 2-aminoethanol and 4-aminobutanol are more preferred, and 2-aminoethanol is particularly preferred.

[0040] The amount of hydroxyl group-containing amine used for modification 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 the polyolefin (a2-1) having carboxyl groups at both ends of the polymer, which is the modified product, from the viewpoint of ease of forming repeating structures in the molecule, antistatic properties of the molded article, dispersibility of the block polymer (A) in the antistatic resin composition described later, and mechanical properties of the molded article. The Mn in (a2-2) is preferably 800 to 5,000, more preferably 1,000 to 4,000, and especially preferably 1,500 to 3,000, with the lower limit being from the viewpoint of antistatic properties and the upper limit being from the viewpoint of refractive index. The hydroxyl value of the polyolefin (a2-2) having hydroxyl groups at both ends of the polymer is preferably 4 to 280 mg KOH / g, more preferably 4 to 100 mg KOH / g, and particularly preferably 5 to 50 mg KOH / g, from the viewpoint of reactivity with the hydrophilic polymer (b) and the thermoplasticity of the block polymer (A).

[0041] As polyolefins (a2-3) having amino groups at both ends of the polymer, polyolefins having amino groups obtained by modifying the polyolefin (a2-1) having carboxyl groups at both ends of the polymer with the diamine (a03), and mixtures of two or more of these can be used. Of the aforementioned diamines (a03), aromatic (ali) diamines are preferred from the viewpoint of refractive index, and aromatic diamines are even more preferred.

[0042] The amount of diamine (a03) used to modify the polyolefin (a2-1) having carboxyl groups at both ends of the polymer 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), from the viewpoint of ease of forming repeating structures in the molecule, antistatic properties of the molded article, dispersibility of the block polymer (A) in the antistatic resin composition, and mechanical properties of the molded article. Furthermore, in order to prevent polyamidation (imide formation), the modification of polyolefin (a2-1) having carboxyl groups at both ends of the polymer with diamine (a03) is preferably carried out by using 0.5 to 1,000% by weight, more preferably 1 to 500% by weight, and particularly preferably 2 to 300% by weight of diamine (a03) based on the weight of polyolefin (a2-1) having carboxyl groups at both ends of the polymer, followed by removing the unreacted diamine (a03) under reduced pressure at 120 to 230°C.

[0043] The manganese content of polyolefins (a2-3) having amino groups at both ends of the polymer is preferably 800 to 5,000, more preferably 1,000 to 4,000, and particularly preferably 1,500 to 3,000, with a lower limit from the viewpoint of antistatic properties and an upper limit from the viewpoint of refractive index. The amine value of polyolefins (a2-3) having amino groups at both ends of the polymer is preferably 4 to 280 mg KOH / g, more preferably 4 to 100 mg KOH / g, and particularly preferably 5 to 50 mg KOH / g, from the viewpoint of reactivity with hydrophilic polymer (b) and thermoplasticity of block polymer (A).

[0044] Examples of polyolefins (a2-4) having isocyanate groups at both ends include polyolefins (a2-2) having hydroxyl groups at both ends of the polymer, modified with poly(2-3 or more) isocyanate (hereinafter abbreviated as PI), and mixtures of two or more of these. PI includes aromatic PIs with 6 to 20 carbon atoms (excluding carbon atoms in the NCO group; the same applies hereinafter), aliphatic PIs with 2 to 18 carbon atoms, alicyclic PIs with 4 to 15 carbon atoms, aromatic aliphatic PIs with 8 to 15 carbon atoms, modified forms of these PIs, and mixtures of two or more of these.

[0045] Examples of aromatic PIs include 1,3- or 1,4-phenylenediisocyanate, 2,4- or 2,6-tolylenediisocyanate (TDI), crude TDI, 2,4'- or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, and 1,5-naphthylenediisocyanate.

[0046] Examples of aliphatic PIs include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

[0047] Examples of alicyclic PIs include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, and 2,5- or 2,6-norbornane diisocyanate.

[0048] Examples of aromatic aliphatic PIs include m- or p-xylylene diisocyanate (XDI) and α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI).

[0049] Modified forms of PI include urethane-modified forms, urea-modified forms, carbodiimide-modified forms, and uretdione-modified forms. Among PIs, aromatic PIs are preferred from the viewpoint of refractive index, and TDIs and MDIs are even more preferred.

[0050] The reaction between PI and polyolefin (a2-2) having hydroxyl groups at both ends of the polymer can be carried out, for example, in a manner similar to that of a urethane formation reaction. The molar equivalent ratio (NCO / OH) of PI and polyolefin (a2-2) having hydroxyl groups at both ends of the polymer is preferably 1.8 / 1 to 3 / 1, and more preferably 2 / 1. To accelerate the urethane reaction, known catalysts used in urethane reactions may be used as needed. Examples of catalysts include metal catalysts {tin catalysts [such as dibutyltin dilaurate and stanus octoate], lead catalysts [such as lead 2-ethylhexanoate and lead octoate], and other metal catalysts [such as naphthenate metal salts (such as cobalt naphthenate) and phenylmercury propionate]}; amine catalysts {triethylenediamine, diazabicycloalkenes [such as 1,8-diazabicyclo[5,4,0]undecene-7], dialkylaminoalkylamines (such as dimethylaminoethylamine and dimethylaminooctylamine), carbonates or organic acid (such as formic acid) salts of heterocyclic aminoalkylamines [such as 2-(1-aziridinyl)ethylamine and 4-(1-piperidinyl)-2-hexylamine], N-methyl or ethylmorpholine, triethylamine and diethyl- or dimethylethanolamine}; and combinations of two or more of these. The amount of catalyst used is preferably 3% by weight or less, and more preferably 0.001 to 2% by weight, based on the total weight of polyolefin (a2-2) having PI and hydroxyl groups at both ends of the polymer.

[0051] The Mn of the polyolefin (a2-4) having isocyanate groups at both ends is preferably 800 to 5,000, more preferably 1,000 to 4,000, and particularly preferably 1,500 to 3,000 from the viewpoint of antistatic properties and from the viewpoint of refractive index.

[0052] <Hydrophilic polymer (b)> The hydrophilic polymer (b) in the present invention means a polymer having a volume resistivity of 1×10 5 ~1×10 11 Ω·cm. The volume resistivity of the hydrophilic polymer (b) is preferably 1×10 6 ~1×10 9 Ω·cm, and more preferably 1×10 6 ~1×10 8 Ω·cm. When the volume resistivity is less than 1×10 5 Ω·cm, it is substantially difficult to obtain, and when it exceeds 1×10 11 Ω·cm, the antistatic property of the molded product described later deteriorates.

[0053] Examples of the hydrophilic polymer (b) include the hydrophilic polymers described in Patent No. 3488163, and specifically, polyether (b1), polyether-containing hydrophilic polymer (b2), etc.

[0054] Examples of the polyether (b1) include polyether diol (b1-1), polyether diamine (b1-2), and modified products thereof (b1-3). Examples of the polyether diol (b1-1) include those obtained by subjecting a diol (b0) to an addition reaction with an alkylene oxide (hereinafter abbreviated as AO), and specifically, those represented by the general formula (1). H-(OR 1 ...

[0055] ​​​​​​​​​ E in general formula (1) 1 This is a residue obtained by removing all hydroxyl groups from the diol (b0). Examples of diols (b0) include aliphatic dihydric alcohols with 2 to 12 carbon atoms, alicyclic dihydric alcohols with 5 to 12 carbon atoms, aromatic dihydric alcohols with 6 to 18 carbon atoms, and tertiary amino group-containing diols. Examples of aliphatic dihydric alcohols 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 abbreviated 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 alicyclic dihydric alcohols having 5 to 12 carbon atoms include 1,4-di(hydroxymethyl)cyclohexane and 1,5-di(hydroxymethyl)cycloheptane.

[0056] Examples of aromatic dihydric alcohols having 6 to 18 carbon atoms include monocyclic aromatic dihydric alcohols (such as xylylenediol, hydroquinone, catechol, resorcinol, and urushiol) and polycyclic aromatic dihydric alcohols (such as bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxydiphenyl-2,2-butane, dihydroxybiphenyldihydroxynaphthalene, and binaphthol). Examples of tertiary amino group-containing diols include bishydroxyalkylated compounds of aliphatic or alicyclic primary amines having 1 to 12 carbon atoms (such as methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, pentylamine, isopentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine, and dodecylamine) and bishydroxyalkylated compounds of aromatic primary amines having 6 to 12 carbon atoms (such as aniline and benzylamine). Among the diols (b0), polycyclic aromatic dihydric alcohols are preferred from the viewpoint of refractive index and the heat resistance of the molded articles described later, more preferably bisphenol compounds, and particularly preferably bisphenol S and bisphenol A.

[0057] R in general formula (1) 1 and R 2 These are each an alkylene group having 2 to 4 carbon atoms. Examples of alkylene groups having 2 to 4 carbon atoms include the ethylene group, the 1,2- or 1,3-propylene group, and the 1,2-, 1,3-, 1,4- or 2,3-butylene group. In general formula (1), m and n are each independently a number between 1 and 300, preferably between 2 and 250, and more preferably between 10 and 100. R when m and n are both 2 or greater in general formula (1) 1 , R 2 They may be the same or different, (OR 1 ) m , (R 2 O) n The parts can be either random joins or block joins.

[0058] Polyetherdiol (b1-1) can be produced by adding AO to diol (b0). As for AOs, carbon-2 to carbon-4 AOs [ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3-propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,3-, 1,4- or 2,3-butylene oxide (hereinafter abbreviated as BO), and combinations of two or more of these are used, but if necessary, other AOs [α-olefin oxides with 5 to 12 carbon atoms, styrene oxide, and epihalohydrins (epichlorohydrin, etc.)] can also be used in small proportions (30% by weight or less based on the total weight of AOs). When using two or more AOs in combination, the combination can be random or block. Preferred AOs are EO alone and EO in combination with other AOs, with EO alone being even more preferred.

[0059] The addition reaction of AO can be carried out by known methods, for example, in the presence of an alkaline catalyst at a temperature of 100-200°C. Based on the weight of polyetherdiol (b1-1) represented by general formula (1), (OR 1 ) m and (R 2 O) n The content is preferably 15 to 99.8% by weight, more preferably 25 to 99.6% by weight, and particularly preferably 35 to 98% by weight. (OR 1 ) m and (R 2 O) n The oxyethylene group content based on weight is preferably 5 to 100% by weight, more preferably 10 to 100% by weight, particularly preferably 50 to 100% by weight, and most preferably 60 to 100% by weight.

[0060] Examples of polyetherdiamines (b1-2) include those represented by general formula (2). H2N-R 3 -(OR 4 ) p -OE 2 -O-(R 5 O) q -R 6 -NH2(2) E in general formula (2) 2 This is a residue obtained by removing all hydroxyl groups from diol(b0). Examples of diol(b0) are the same as those mentioned above. R in general formula (2) 3 , R 4 , R 5 and R 6 These are each an alkylene group having 2 to 4 carbon atoms. As an alkylene group having 2 to 4 carbon atoms, R in general formula (1) 1 and R 2 Examples similar to those exemplified above can be cited, and the preferred range is also the same. In general formula (2), p and q are each independently a number between 1 and 300, preferably between 2 and 250, and more preferably between 10 and 100. R when p and q are both 2 or greater in general formula (2) 4 , R 5 They may be the same or different, (OR 4 ) p , (R 5 O) q The parts can be either random joins or block joins.

[0061] Polyetherdiamine (b1-2) can be obtained by converting all the hydroxyl groups of polyetherdiol (b1-1) to alkylamino groups. For example, it can be produced by reacting (b1-1) with acrylonitrile and hydrogenating the resulting cyanoethylated product.

[0062] Examples of modified products (b1-3) include aminocarboxylic acid modified products (terminal amino group), isocyanate modified products (terminal isocyanate group), and epoxy modified products (terminal epoxy group) of polyetherdiol (b1-1) or polyetherdiamine (b1-2). Aminocarboxylic acid modified products can be obtained by reacting (b1-1) or (b1-2) with an aminocarboxylic acid or lactam. Isocyanate-modified products can be obtained by reacting a polyetherdiol (b1-1) or polyetherdiamine (b1-2) with a polyisocyanate, or by reacting a polyetherdiamine (b1-2) with phosgene. Epoxy-modified products can be obtained by reacting a polyetherdiol (b1-1) or polyetherdiamine (b1-2) with a diepoxide (epoxy resin such as diglycidyl ether, diglycidyl ester, and alicyclic diepoxide: epoxy equivalent 85-600), or by reacting (b1-1) with an epihalohydrin (such as epichlorohydrin).

[0063] Of the polyethers (b1), alkylene oxide adducts of polycyclic aromatic dihydric alcohols are preferred from the viewpoint of refractive index and the heat resistance of the molded articles described later, alkylene oxide adducts of bisphenol compounds are preferred, and EO adducts of bisphenol A and dihydroxynaphthalene are particularly preferred. In the case of alkylene oxide adducts of bisphenol compounds, Mn is preferably 300 to 5,000, more preferably 600 to 3,000, and particularly preferably 1,000 to 2,500.

[0064] Examples of polyether-containing hydrophilic polymers (b2) include polyether ester amide (b2-1) having a polyetherdiol (b1-1) segment, polyetheramide imide (b2-2) having a polyetherdiol (b1-1) segment, polyether ester (b2-3) having a polyetherdiol (b1-1) segment, polyetheramide (b2-4) having a polyetherdiamine (b1-2) segment, and polyether urethane (b2-5) having a polyetherdiol (b1-1) or polyetherdiamine (b1-2) segment.

[0065] Polyether ester amide (b2-1) is composed of polyamide (a1') having carboxyl groups at both ends and polyether diol (b1-1) from polyamide (a1). Examples of polyamides (a1') having carboxyl groups at both ends include ring-opening polymers of the lactam (a01), polycondensates of the aminocarboxylic acid (a02), and polyamides of the diamine (a03) and dicarboxylic acid (a04). Among polyamides (a1') having carboxyl groups at both ends, preferred from the viewpoint of antistatic properties are ring-opened polymers of caprolactam, polycondensates of 12-aminododecanoic acid, and polyamides of adipic acid and hexamethylenediamine, with the ring-opened polymer of caprolactam being even more preferred.

[0066] The polyetheramide-imide (b2-2) is composed of a polyamide-imide (a3) ​​having at least one imide ring and a polyetherdiol (b1-1). Examples of polyamide-imides (a3) ​​having at least one imide ring include polymers consisting of lactam (a01) and a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring, polymers consisting of aminocarboxylic acid (a02) and a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring, polymers consisting of polyamide (a1') and a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring, and mixtures thereof.

[0067] Examples of polyether esters (b2-3) include those composed of polyester (Q) and polyetherdiol (b1-1). Examples of polyester (Q) include polyesters composed of a dicarboxylic acid (a04) and a diol (b0). The preferred dicarboxylic acid is the same as in the case of polyamide (a1) production. Examples of polyetheramides (b2-4) include those composed of polyamide (a1) and polyetherdiamine (a212). The polyether urethane (b2-5) is composed of a diisocyanate from the PI, a polyether diol (b1-1) or polyether diamine (b1-2), and optionally a chain extender [such as the diol (b0) and diamine (a03)]. The preferred diamine is the same as in the case of (a1) production.

[0068] From the viewpoint of moldability, the content of the polyether (b1) segment in the polyether-containing hydrophilic polymer (b2) is preferably 30 to 80% by weight, and more preferably 40 to 70% by weight, based on the weight of the polyether-containing hydrophilic polymer (b2). The oxyethylene group content in the polyether-containing hydrophilic polymer (b2) is preferably 30 to 80% by weight, and more preferably 40 to 70% by weight, based on the weight of the polyether-containing hydrophilic polymer (b2), from the viewpoint of antistatic properties and moldability. The lower limit of Mn in the polyether-containing hydrophilic polymer (b2) is preferably 800, and more preferably 1,000, from the viewpoint of heat resistance. The upper limit of Mn in (b2) is preferably 50,000, and more preferably 30,000, from the viewpoint of reactivity with the hydrophobic polymer (a).

[0069] <Block polymer (A)> The block polymer (A) in the present invention is composed of blocks of the hydrophobic polymer (a) and a hydrophilic polymer (b) as constituent units.

[0070] Of the block polymers (A), (A1) and / or (A2) below are preferred from the viewpoint of antistatic properties, and (A1) is more preferred. (A1): Polyether ester amides derived from polyamides and polyethers consisting of alkylene oxide adducts of bisphenol compounds (number average molecular weight 300-5,000) and / or polyalkylene glycols; (A2): A block polymer having a structure in which a block of polyolefin and a block of polyether are repeatedly bonded together via at least one type of bond selected from the group consisting of ester bonds, amide bonds, ether bonds, imide bonds, and urethane bonds;

[0071] The weight ratio of the blocks of hydrophobic polymer (a) and hydrophilic polymer (b) constituting the block polymer (A) is preferably 10 / 90 to 80 / 20, and more preferably 20 / 80 to 75 / 25, from the viewpoint of antistatic properties and water resistance.

[0072] The structures formed by the bonding of a block polymer (A) consisting of a hydrophobic polymer (a) and a block polymer (b) include the (a)-(b) type, (a)-(b)-(a) type, (b)-(a)-(b) type, and the [(a)-(b)]n type (where n represents the average number of repeats). As for the structure of the block polymer (A), a [(a)-(b)]n type is preferred from the viewpoint of antistatic properties, in which hydrophobic polymer (a) and hydrophilic polymer (b) are repeatedly and alternately bonded. In the [(a)-(b)]n type structure, n is preferably 2 to 50, more preferably 2.3 to 30, particularly preferably 2.7 to 20, and most preferably 3 to 10, from the viewpoint of antistatic properties and mechanical properties of the molded article. n is Mn of the block polymer (A) and 1 This can be determined by 1H-NMR analysis.

[0073] The Mn content of block polymer (A) is preferably 2,000 to 1,000,000, more preferably 4,000 to 500,000, and particularly preferably 6,000 to 100,000, from the viewpoint of the mechanical properties and antistatic properties of the molded article described later.

[0074] If the block polymer (A) has a structure in which a block of hydrophobic polymer (a) and a block of hydrophilic polymer (b) are linked via ester bonds, amide bonds, ether bonds, or imide bonds, it can be produced by the following method. One method involves placing a hydrophobic polymer (a) and a hydrophilic polymer (b) into a reaction vessel and reacting them for 1 to 50 hours under stirring at a reaction temperature of 100 to 250°C and a pressure of 0.003 to 0.1 MPa, while removing the water produced by the amidation, esterification, or imidation reaction (hereinafter abbreviated as "produced water") from the reaction system.

[0075] <Inorganic particles (C) with a volume-average particle diameter of 1-50 nm> The inorganic particles (C) in this invention have a volume-average particle diameter of 1 to 50 nm, preferably 5 to 40 nm. If the volume-average particle diameter of (C) is less than 1 nm, aggregation of particles due to van der Waals attraction is likely to occur, making it difficult to disperse them in a granular state. Furthermore, if the volume-average particle diameter of the inorganic particles (C) exceeds 50 nm, the effect of lowering the surface resistivity is not obtained, and transparency in the visible light region deteriorates. The inorganic particles (C) of the present invention may be untreated or surface-treated. If the inorganic particles (C) are surface-treated, their volume-average particle diameter refers to the volume-average particle diameter including the surface treatment agent. The volume-average particle diameter refers to the average value of the spherical equivalent diameter of the inorganic particles. Measurement methods include direct observation using an electron microscope, light or X-ray scattering, and dynamic light scattering. In this invention, the measurement was performed using dynamic light scattering. The shape of the inorganic particles (C) may be particulate, fibrous, or plate-like.

[0076] Examples of inorganic particles (C) used in the present invention include metal oxides such as silica, titanium oxide, barium titanate, zirconium oxide, aluminum oxide, zinc oxide, magnesium oxide, tin oxide, cerium oxide, iron(III) oxide, iron(II,III) oxide, tungsten oxide, yttrium oxide, iron titanate, manganese titanate, niobium pentoxide, and potassium tantalate; and clay minerals such as montmorillonite, saponite, and clay. From the viewpoint of antistatic performance and transparency, metal oxides are preferred, and zirconium oxide is even more preferred.

[0077] Furthermore, from the viewpoint of dispersibility, it is preferable to use an aqueous dispersion sol of the inorganic particles (C) or an organic solvent sol of the inorganic particles (C). That is, a sol (dispersion) in which the inorganic particles (C) are dispersed in water or an organic solvent. As the dispersion medium for inorganic particles (C), water or a general-purpose organic solvent can be used, such as water, methyl ethyl ketone (MEK), methanol, ethanol, isopropyl alcohol, ethyl acetate, toluene, and mixtures of two or more of these.

[0078] <Antistatic agent (Z)> The antistatic agent (Z) of the present invention contains the block polymer (A) and inorganic particles (C) having a volume-average particle diameter of 1 to 50 nm, and has a refractive index of 1.500 to 1.600. The refractive index is preferably 1.510 to 1.590, more preferably 1.520 to 1.580, and particularly preferably 1.530 to 1.570. If the refractive index is less than 1.500, the transparency of the molded product described later will be poor, and if it exceeds 1.600, it will be industrially difficult. The refractive index in this invention is a value obtained by measuring it using an Abbe refractometer in accordance with JIS K7142 (1996).

[0079] The weight ratio [(A) / (C)] of block polymer (A) to inorganic particles (C) having a volume-average particle diameter of 1 to 50 nm is preferably 30 / 70 to 65 / 35, and more preferably 35 / 65 to 60 / 40. If the inorganic particles (C) are surface-treated, the weight of the inorganic particles (C) refers to the weight including the surface treatment agent.

[0080] The antistatic agent (Z) can be manufactured, for example, by the following method. (1) Before and during the reaction between the hydrophobic polymer (a) and the hydrophilic polymer (b), an inorganic particle (C) or a sol containing dispersed inorganic particles (C) is added, and then the reaction is carried out. (2) Mix the block polymer (A) with inorganic particles (C) or a sol in which inorganic particles (C) are dispersed, and if necessary, remove the dispersion medium by distillation.

[0081] The refractive index of the antistatic agent (Z) can be appropriately adjusted depending on the type and weight of the hydrophobic polymer (a) and hydrophilic polymer (b), which are constituent units of the block polymer (A), the type and weight of the inorganic particles (C), and the type and weight of the antistatic enhancer (F) described later.

[0082] The antistatic agent (Z) of the present invention may optionally contain an antistatic enhancer (F) to the extent that it does not impair the effects of the present invention. Examples of antistatic agents (F) include alkali metal or alkaline earth metal salts (F1), quaternary ammonium salts (F2), surfactants (F3), and ionic liquids (F4). Two or more of (F1) to (F4) may be used in combination.

[0083] Examples of alkali metal or alkaline earth metal salts (F1) include salts of alkali metals (lithium, sodium, and potassium, etc.) or alkaline earth metals (magnesium and calcium, etc.) with organic acids [mono- or di-carboxylic acids having 1 to 7 carbon atoms (formic acid, acetic acid, propionic acid, oxalic acid, and succinic acid, etc.), sulfonic acids having 1 to 7 carbon atoms (methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid, etc.), and thiocyanic acid], and salts of the aforementioned organic acids with inorganic acids [(hydrohalogens (e.g., hydrochloric acid and hydrobromic acid, etc.), perchloric acid, sulfuric acid, nitric acid, and phosphoric acid, etc.)].

[0084] Examples of quaternary ammonium salts (F2) include salts of amidinium (such as 1-ethyl-3-methylimidazolium) or guanidium (such as 2-dimethylamino-1,3,4-trimethylimidazolinium) with the aforementioned organic or inorganic acid.

[0085] Examples of surfactants (F3) include known nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Two or more types of (F3) may be used in combination.

[0086] Examples of ionic liquids (F4) include room-temperature molten salts of compounds other than those described in (F1) to (F3) above, having a melting point of 25°C or lower, at least one of the constituent cations or anions being an organic ion, and an initial conductivity of 1 to 200 ms / cm (preferably 10 to 200 ms / cm). Specifically, examples of room-temperature molten salts are given in publication WO95 / 15572.

[0087] The respective weight-based content of the antistatic agent (Z) (F1) to (F4) is preferably 10% by weight or less, more preferably 0.01 to 8% by weight, and particularly preferably 0.1 to 6% by weight, from the viewpoint of providing a resin molded product with good appearance that does not precipitate on the resin surface and exhibits antistatic properties.

[0088] <Thermoplastic resin (E)> In the present invention, the thermoplastic resin (E) preferably has a refractive index of 1.540 or higher, more preferably 1.550 or higher, particularly preferably 1.560 or higher, with a preferred upper limit of 1.650 or lower, more preferably 1.630 or lower, and particularly preferably 1.600 or lower, from the viewpoint of transparency of the molded article of the antistatic resin composition described later.

[0089] Examples of thermoplastic resins (E) include polyester resin (E1), polycarbonate resin (E2), and polyacrylic resin (E3). The thermoplastic resin (E) may be used alone or in combination of two or more types. Of the thermoplastic resins (E), from the viewpoint of antistatic properties, transparency, and mechanical properties of the molded articles described later, at least one selected from the group consisting of polyester resin (E1), polycarbonate resin (E2), and polyacrylic resin (E3) is preferred, more preferably polycarbonate resin (E2) and polyacrylic resin (E3), and even more preferably polycarbonate resin (E2).

[0090] Polyester resins (E1) include polyethylene terephthalate (PET), polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene adipate, etc. Polycarbonate resin (E2) includes condensates of bisphenol A and phosgene, condensates of bisphenol A and carbonate esters obtained by transesterification, etc. Examples of polyacrylic resins (E3) include styrene / methyl methacrylate copolymer (MS) and methyl methacrylate / butadiene / styrene copolymer (MBS).

[0091] <Antistatic resin composition (Y)> The antistatic resin composition (Y) of the present invention comprises the antistatic agent (Z) and the thermoplastic resin (E). The weight ratio [(Z) / (E)] of the antistatic agent (Z) to the thermoplastic resin (E) is preferably 1 / 90 to 30 / 70, more preferably 3 / 97 to 25 / 80, and particularly preferably 5 / 95 to 20 / 90, from the viewpoint of the antistatic properties and mechanical properties of the molded product.

[0092] The composition may, as necessary and within the limits that do not impair the effects of the present invention, contain, in addition to the block polymer (A), inorganic particles (C), antistatic enhancer (F), and thermoplastic resin (E), at least one other additive (D) selected from the group consisting of colorants (white pigments, etc.), release agents (liquid paraffin, etc.), antioxidants (2,6-di-t-butyl-p-cresol, etc.), flame retardants (phosphorus-containing flame retardants, etc.), ultraviolet absorbers (phenyl salicylate, etc.), antibacterial agents (benzimidazole, etc.), compatibilizers (modified vinyl polymers having sulfonic acid groups as described in Japanese Patent Publication No. 6-345927, etc.), and fillers (calcium stearate, etc.). Each of the other additives (D) may be used individually or in combination of two or more.

[0093] The total content of other additives (D) based on the weight of the thermoplastic resin (E) is, for example, 45% by weight or less, preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight, from the viewpoint of the effect of each additive and the mechanical properties of the molded article.

[0094] The antistatic resin composition (Y) of the present invention can be obtained by melt-mixing the antistatic agent (Z) of the present invention, a thermoplastic resin (E), and optionally other additives (D). Generally, a method of melt-mixing can be applied in which each component, in pellet or powder form, is mixed in a suitable mixer (such as a Henschel mixer), and then melt-mixed in an extruder to form pellets.

[0095] There are no particular restrictions on the order in which each component is added during melt mixing, but for example, [1] A method in which an antistatic resin composition (Z) is melted and mixed, and then a thermoplastic resin (E) and, if necessary, other additives (D) are added and melted together; [2] A method in which an antistatic resin composition (Z) is melt-mixed, and then a portion of the thermoplastic resin (E) is pre-melted and mixed to produce a high-concentration composition of the antistatic resin composition (Z) (masterbatch resin composition), and then the remaining thermoplastic resin (E) and, if necessary, other additives (D) are melt-mixed (masterbatch method or master pellet method); These are some examples. In the method of [2], the concentration of the antistatic resin composition (Z) in the masterbatch resin composition is preferably 40 to 80% by weight, and more preferably 50 to 70% by weight. Of the methods [1] and [2], method [2] is preferred from the viewpoint that the antistatic resin composition (Z) can be efficiently dispersed in the thermoplastic resin (E).

[0096] <Molded products> The molded article of the present invention is a molded article of the antistatic resin composition (Y). That is, it is obtained by molding the antistatic composition (Y). The molding methods include injection molding, compression molding, calendering, slush molding, rotational molding, extrusion molding, blow molding, and film molding (casting method, tenter method, and inflation method, etc.). Depending on the purpose, the product can be molded using any method that incorporates means such as single-layer molding, multi-layer molding, or foam molding.

[0097] The haze of the molded article of the present invention is preferably 30% or less, more preferably 20% or less, and particularly preferably 10% or less, from the viewpoint of transparency. The haze value is obtained by measurement in accordance with JIS K7105 (1981). An example of the device used for this measurement is the ND-300A manufactured by Nippon Denshoku Industries Co., Ltd.

[0098] The molded articles of the present invention have excellent transparency, mechanical properties, and antistatic properties, as well as good paintability and printability, and molded articles can be obtained by painting and / or printing on the molded articles. [Examples]

[0099] The following describes embodiments of the present invention, but the present invention is not limited thereto. In the following, parts and % refer to parts by weight and weight percent, respectively.

[0100] <Manufacturing Example 1> [Production of polyamide (a1-1)] In a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube, and depressurization device, 77.2 parts of ε-caprolactam, 16.5 parts of terephthalic acid, 0.3 parts of antioxidant ["Irganox 1010", manufactured by BASF Japan Ltd.], and 6 parts of water were added. After purging with nitrogen, the mixture was heated to 220°C under a sealed container while stirring, and stirred at the same temperature (pressure: 0.2~0.3 MPa) for 4 hours to obtain polyamide (a1-1) having carboxyl groups at both ends. The acid value of (a1-1) was 120 and the Mn value was 900.

[0101] <Manufacturing Example 2> [Production of polyamide (a1-2)] Polyamide (a1-2) having carboxyl groups at both ends was obtained in the same manner as in Production Example 1, except that 82.5 parts of ε-caprolactam and 11.1 parts of terephthalic acid were used instead of 77.2 parts of ε-caprolactam and 16.5 parts of terephthalic acid in Production Example 1. The acid value of (a1-2) was 75 and the Mn was 1,300.

[0102] <Manufacturing Example 3> [Production of polyolefin (a2-1-1α) having carboxyl groups at both ends] In a pressure-resistant reaction vessel similar to that used in Production Example 1, 90 parts of low molecular weight polypropylene obtained by thermal degeneration [polypropylene (MFR: 10 g / 10 min) was thermally degenerated at 410 ± 0.1 °C under nitrogen aeration (80 mL / min) for 16 minutes. Mn: 3,400, number of double bonds per 1,000 carbon atoms: 7.0, average number of double bonds per molecule: 1.8, content of polyolefins that can be modified at both ends: 90% by weight], 10 parts of maleic anhydride, and 30 parts by weight of xylene were added and uniformly mixed. After purging with nitrogen, the mixture was sealed and heated to 200 °C while stirring to melt it, and the mixture was reacted at the same temperature for 10 hours. Then, the excess maleic anhydride and xylene were removed by distillation under reduced pressure (0.013 MPa or less) at 200 °C over 3 hours to obtain polyolefin (a2-1-1α) having carboxyl groups at both ends of the polymer. The acid value of (a2-1-1α) was 27.5, and the Mn value was 3,600.

[0103] <Manufacturing Example 4> [Production of polyolefin (a2-1-2α) obtained by secondary modification of (a2-1-1α)] In a pressure-resistant reaction vessel similar to that used in Production Example 1, 88 parts of (a2-1-1α) and 12 parts of 12-aminododecanoic acid were added and uniformly mixed. The mixture was then heated to 200°C under a nitrogen gas atmosphere with stirring, and reacted at the same temperature under reduced pressure (0.013 MPa or less) for 3 hours to obtain polyolefin (a2-1-2α) through secondary modification of (a2-1-1α). The acid value of (a2-1-2α) was 24.8, and the Mn value was 4,000.

[0104] <Manufacturing Example 5> [Production of block polymer mixture (A1-1C1)] In a reaction vessel equipped with a stirrer, thermometer, and heating / cooling device, 54 parts of (a1-1) and an EO adduct of bisphenol A (Mn: 1,800, volume resistivity: 2 × 10⁻¹⁰) were added. 7 (Ω·cm) 33 parts, EO adduct of bisphenol A (Mn: 310, volume resistivity: 1 × 10⁻¹⁰) 12 12 parts of (Ω·cm), 0.7 parts by weight of zirconyl acetate, and 189 parts of a dispersion of zirconia nanoparticles [Zircostar ZP-153, manufactured by Nippon Shokubai Co., Ltd., dispersion: MEK, refractive index approximately 1.8, volume average particle size 11 nm (dynamic light scattering method), solid content 70 wt%] (C-1) were added, the mixture was heated to 240°C while stirring, and polymerized under reduced pressure (0.013 MPa or less) at the same temperature for 6 hours to obtain a block polymer mixture (A1-1C1) containing a viscous block polymer (A1-1) and inorganic particles (C-1). The Mn content of (A1-1) was 27,000.

[0105] <Manufacturing Example 6> [Production of block polymer mixture (A1-1C2)] In Production Example 5, a block polymer mixture (A1-1C2) containing a viscous block polymer (A1-1) and inorganic particles (C-1) was obtained in the same manner as in Production Example 5, except that 189 parts of the dispersion of (C-1) were replaced with 117 parts of the dispersion of (C-1). The Mn content of (A1-1) was 27,000.

[0106] <Manufacturing Example 7> [Production of block polymer mixture (A1-1C3)] In Production Example 5, a block polymer mixture (A1-1C3) containing a viscous block polymer (A1-1) and inorganic particles (C-1) was obtained in the same manner as in Production Example 5, except that 189 parts of the dispersion of (C-1) were replaced with 127 parts of the dispersion of (C-1). The Mn content of (A1-1) was 27,000.

[0107] <Manufacturing Example 8> [Production of block polymer mixture (A1-2C1)] In a pressure-resistant reaction vessel similar to that in Manufacturing Example 5, 39 parts of (a1-2) and an EO adduct of bisphenol A (Mn: 1,800, volume resistivity: 2 × 10) were added. 7 (Ω·cm) 18 parts, EO adduct of bisphenol A (Mn: 2,900, volume resistivity: 1 × 10⁻⁶) 7 43 parts of (Ω·cm), 0.7 parts of zirconyl acetate, and 182 parts of a dispersion of (C-1) were added, and the temperature was raised to 240°C while stirring. Polymerization was carried out under reduced pressure (0.013 MPa or less) at the same temperature for 6 hours to obtain a block polymer mixture (A1-2C1) containing a viscous block polymer (A1-2) and inorganic particles (C-1). The Mn content of (A1-2) was 40,000.

[0108] <Manufacturing Example 9> [Production of block polymer mixture (A2-1C1)] In a pressure-resistant reaction vessel similar to that in Manufacturing Example 5, add 50.4 parts of (a2-1-2α) and polyetherdiol (b1-1α)[PEG(Mn: 2,000, volume resistivity: 1 × 10⁻¹⁰). 7 49.2 parts of (Ω·cm), 0.7 parts of zirconyl acetate, and 155 parts of a dispersion of (C-1) were added, and the mixture was heated to 220°C while stirring. Polymerization was carried out under reduced pressure (0.013 MPa or less) at the same temperature for 3 hours to obtain a block polymer mixture (A2-1C1) containing a viscous block polymer (A2-1) and inorganic particles (C). The Mn content of (A2-1) was 50,000.

[0109] <Manufacturing Example 10> [Production of block polymer mixture (A1-1C4)] In Production Example 5, a block polymer mixture (A1-1C4) containing a viscous block polymer (A1-1) and inorganic particles (C-2) was obtained in the same manner as in Production Example 5, except that 189 parts of the dispersion of (C-1) were replaced with 78 parts of titanium dioxide nanoparticles [TTO-51(C), manufactured by Ishihara Sangyo Co., Ltd., average particle size 10-30 nm] (C-2). The Mn content of (A1-1) was 27,000.

[0110] <Manufacturing Example 11> [Manufacturing of block polymer (A1-1)] In a pressure-resistant reaction vessel similar to that in Manufacturing Example 5, 54 parts of (a1-1) and an EO adduct of bisphenol A (Mn: 1,800, volume resistivity: 2 × 10) were added. 7 (Ω·cm) 33 parts, EO adduct of bisphenol A (Mn: 310, volume resistivity: 1 × 10⁻¹⁰) 12 Twelve parts of (Ω·cm) and 0.7 parts of zirconyl acetate were added, and the mixture was heated to 240°C while stirring. Polymerization was carried out under reduced pressure (0.013 MPa or less) at the same temperature for 6 hours to obtain block polymer (A1-1). The manganese content of (A1-1) was 27,000.

[0111] <Manufacturing Example 12> [Manufacturing of block polymer (A2-1)] In a pressure-resistant reaction vessel similar to that in Manufacturing Example 5, add 50.4 parts of (a2-1-2α) and polyetherdiol (b1-1α)[PEG(Mn: 2,000, volume resistivity: 1 × 10⁻¹⁰). 7 49.2 parts of (Ω·cm) and 0.7 parts of zirconyl acetate were added, and the mixture was heated to 220°C while stirring. Polymerization was carried out under reduced pressure (0.013 MPa or less) at the same temperature for 3 hours to obtain block polymer (A2-1). The Mn content of (A2-1) was 50,000.

[0112] <Manufacturing Example 13> [Production of block polymer mixture (A1-2C2)] In Production Example 8, a block polymer mixture (A1-2C2) containing a viscous block polymer (A1-2) and inorganic particles (C-1) was obtained in the same manner as in Production Example 8, except that 182 parts of the dispersion of (C-1) were replaced with 411 parts of the dispersion of (C-1). The Mn content of (A1-2) was 40,000.

[0113] <Example 1> In a reaction vessel equipped with a stirrer, thermometer, and heating / cooling device, 100 parts of a block polymer mixture (A1-1C1) and 0 parts of sodium dodecylbenzenesulfonate (F-1) were charged. The mixture was mixed and stirred at 220°C for 1 hour, then removed in strand form on a belt, pelletized, and an antistatic agent (Z-1) was obtained.

[0114] <Examples 2-7, Comparative Examples 1-3> Each antistatic agent (Z) was obtained in the same manner as in Example 1, except that the compounding composition (parts) was as shown in Table 1. The results are shown in Table 1.

[0115] [Table 1]

[0116] <Examples 11-17, Comparative Examples 11-17> According to the formulation composition (parts) shown in Table 2, the components were blended in a Henschel mixer for 3 minutes, and then melt-kneaded in a vented twin-screw extruder at 100 rpm, 200°C, and residence time of 5 minutes to obtain each antistatic resin composition (Y). Each obtained antistatic resin composition (Y) was used to produce molded test specimens using the injection molding machine "PS40E5ASE" [manufactured by Nissei Plastic Industrial Co., Ltd.] at a cylinder temperature of 220°C [when using (E-2) to (E-5)] or 250°C [when using (E-1)], and a mold temperature of 50°C [when using (E-2) to (E-5)] or 80°C [when using (E-1)]. These specimens were then evaluated by the performance tests described below. The results are shown in Table 2.

[0117] (1) Surface resistivity [compliant with ASTM D257] For the test specimen (100 × 100 × 2 mm), after being left standing for 48 hours under conditions of 23°C and 50% RH humidity, the insulation was measured using the super-insulation meter "DSM-8103" [manufactured by HIOKI E.E. CORPORATION] under the same atmospheric conditions.

[0118] (2) Hayes A test specimen (40 × 40 × 2 mm) was used, and a cloudiness meter was employed to measure the cloudiness in accordance with JIS K7105 (1981).

[0119] (3) Izod impact strength (unit: kJ / m 2 ) Measurements were taken in accordance with ASTM D256 Method A (with notch, 3.2 mm thickness).

[0120] [Table 2]

[0121] The results in Tables 1 and 2 show that the antistatic agent (Z) of the present invention imparts antistatic properties to thermoplastic resins without impairing transparency or mechanical properties, compared to comparative agents. Furthermore, it can be seen that molded articles of antistatic compositions containing the antistatic agent (Z) exhibit excellent transparency, mechanical properties, and antistatic properties. [Industrial applicability]

[0122] The antistatic agent (Z) of the present invention imparts antistatic properties to thermoplastic resins without impairing their transparency and mechanical properties. Furthermore, molded articles of antistatic compositions containing the antistatic agent (Z) exhibit excellent transparency, mechanical properties, and antistatic properties. Therefore, it can be widely used as a material for housing products [for home appliances, office equipment, game consoles, and office equipment, etc.] molded by various molding methods [injection molding, compression molding, calendering, slush molding, rotational molding, extrusion molding, blow molding, foam molding, and film molding (e.g., casting method, tenter method, and inflation method)], plastic container materials [trays used in clean rooms (IC trays, etc.), other containers, etc.], various cushioning materials, covering materials (packaging films, protective films, etc.), flooring sheets, artificial turf, mats, tape substrates (for semiconductor manufacturing processes, etc.), and various molded products (automobile parts, etc.), making it extremely useful.

Claims

1. An antistatic agent (Z) comprising a block polymer (A) composed of blocks of at least one hydrophobic polymer (a) selected from the group consisting of polyamide (a1) and polyolefin (a2) and blocks of hydrophilic polymer (b), and inorganic particles (C) having a volume-average particle diameter of 1 to 50 nm, and having a refractive index of 1,500 to 1,600.

2. The antistatic agent according to claim 1, wherein the block polymer (A) is (A1) and / or (A2) below. (A1): Polyether ester amides derived from polyamides and polyethers consisting of alkylene oxide adducts of bisphenol compounds (number average molecular weight 300 to 5,000) and / or polyalkylene glycols; (A2): A block polymer having a structure in which blocks of polyolefin and blocks of polyether are repeatedly bonded together via at least one type of bond selected from the group consisting of ester bonds, amide bonds, ether bonds, imide bonds, and urethane bonds;

3. The antistatic agent (Z) according to claim 1, wherein (C) is a metal oxide.

4. The antistatic agent according to claim 1, wherein the weight ratio of (A) to (C) [(A) / (C)] is 30 / 70 to 65 / 35.

5. Furthermore, the antistatic agent (Z) according to claim 1 further contains at least one antistatic enhancer (F) selected from the group consisting of alkali metal or alkaline earth metal salts (F1), quaternary ammonium salts (F2), surfactants (F3), and ionic liquids (F4).

6. An antistatic resin composition (Y) comprising an antistatic agent (Z) according to any one of claims 1 to 5 and a thermoplastic resin (E).

7. The antistatic resin composition (Y) according to claim 6, wherein the thermoplastic resin (E) is at least one selected from the group consisting of polycarbonate resin (E1), polyester resin (E2), and polyacrylic resin (E3).

8. A molded article obtained by molding the antistatic resin composition (Y) described in claim 7.

Images