JP4451646B2 - Antistatic resin composition - Google Patents

Description

  The present invention relates to a thermoplastic resin composition for molded articles having excellent permanent antistatic properties. More specifically, the present invention relates to a thermoplastic resin composition for a molded article having transparency and excellent permanent antistatic properties and mechanical properties.

  Conventionally, as a method for imparting antistatic properties without impairing the transparency of a thermoplastic resin such as a transparent polyolefin resin or an acrylic resin, a method of applying or kneading a surfactant to the surface is widely known. However, in such a method, it is difficult for the surfactant to be easily removed by water washing or friction to impart permanent antistatic properties. Therefore, as a method for imparting permanent antistatic properties while maintaining transparency, [1] a method of adding a linear cationic copolymer having a polyolefin-acrylamide or acrylate structure to an acrylic resin (for example, patent document) 1), [2] A method of adding fatty acid diethanolamide and fatty acid diethanolamine to polyolefin (for example, see Patent Document 2) has been proposed.

Japanese Patent Laid-Open No. 9-328597 JP-A-11-140227

  However, in the above [1], although transparency is maintained, there is a problem that the compatibility between the antistatic agent and the resin is poor and the mechanical properties of the resin are deteriorated. On the other hand, in the above [2], although the transparency is similarly maintained, there is a problem that the antistatic agent hardly transfers to the resin surface and the antistatic property is insufficient. An object of the present invention is to provide an antistatic agent for a molded article which is excellent in transparency and excellent in permanent antistatic properties and mechanical properties, and a thermoplastic resin composition comprising the antistatic agent.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, in the present invention, a block of polyolefin (a) and a block of hydrophilic polymer (b) having a volume resistivity of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm are composed of an ester bond, an amide bond, and an ether. An antistatic agent composed of a block polymer (A) having a structure in which it is alternately and repeatedly bonded via at least one bond selected from the group consisting of a bond and an imide bond is selected from polyolefin resin (B1) and acrylic resin (B2). It is contained in at least one thermoplastic resin (B) selected from the group consisting of : (A) and (B) have a refractive index difference of 0.01 or less, and the (B) haze transparency is maintained. An antistatic resin composition for a molded body , wherein the haze difference between the molded body and the thermoplastic resin (B) is 3.3% or less ; a molded body formed by molding the composition ; Lined Furthermore, it is a molded article obtained by coating or printing the molded body.

The resin composition of the present invention is extremely useful because of the following effects.
(1) A molded body obtained by molding the composition is excellent in permanent antistatic properties and mechanical properties.
(2) A molded product obtained by molding the composition has excellent transparency that could not be achieved by conventional techniques.
(3) A molded body formed by molding the composition is excellent in paintability and printing.

  As the block of the polyolefin (a), a polyolefin (a1) having a carbonyl group (preferably a carboxyl group), a hydroxyl group and an amino group at both ends of the polymer can be used.

As (a1), both polyolefins (a0) having a polyolefin which can be modified at both ends as a main component (content 50% by weight or more, more preferably 75% by weight or more, particularly preferably 80 to 100% by weight) are used. Examples thereof include those having a carbonyl group introduced at the terminal.
(A0) is usually a mixture of a polyolefin that can be modified at both ends, a polyolefin that can be modified at one end, and a polyolefin that does not have a terminal group that can be modified. Those are preferred.

  (A0) is a polyolefin [polymerization method] obtained by (co) polymerization (meaning polymerization or copolymerization; the same applies hereinafter) of one or a mixture of two or more olefins having 2 to 30 carbon atoms; A low molecular weight polyolefin [thermal degradation method] obtained by a thermal degradation method of a molecular weight polyolefin (polyolefin obtained by polymerization of an olefin having 2 to 30 carbon atoms) can be used.

Examples of the olefin having 2 to 30 carbon atoms include ethylene, propylene, an α-olefin having 4 to 30 carbon atoms (preferably 4 to 12 and more preferably 4 to 10), and 4 to 30 carbon atoms (preferably 4 to 18). More preferable examples include 4-8) dienes.
Examples of the α-olefin include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene, and the diene includes butadiene, isoprene, 1,4- Examples include pentadiene, 1,6-hexadiene, cyclopentadiene, and 1,11-dodecadiene.
Of these, 2 to 12 carbon atoms (ethylene, propylene, α-olefin having 4 to 12 carbon atoms, butadiene and / or isoprene, etc.) are preferable, and 2 to 10 carbon atoms (ethylene, propylene, carbon) are more preferable. Among them, ethylene, propylene and / or butadiene are particularly preferable.

The low molecular weight polyolefin obtained by the thermal degradation method can be easily obtained by, for example, the method described in JP-A-3-62804.
The polyolefin obtained by the polymerization method can be produced by a known method, for example, easily obtained by (co) polymerizing the olefin in the presence of a radical catalyst, a metal oxide catalyst, a Ziegler catalyst, a Ziegler-Natta catalyst, or the like. be able to.
As the radical catalyst, known ones such as di-t-butyl peroxide, t-butyl benzoate, decanol peroxide, lauryl peroxide, peroxy-dicarbonate ester, azo compound, etc., and oxidized to a γ-alumina carrier For example, molybdenum is attached.
Examples of the metal oxide catalyst include those obtained by attaching chromium oxide to a silica-alumina support.
Examples of Ziegler catalysts and Ziegler-Natta catalysts include (C ₂ H ₅ ) ₃ Al—TiCl ₄ .
A low molecular weight polyolefin by a thermal degradation method is preferable from the viewpoint of easy introduction of a carbonyl group as a modifying group and availability.

The number average molecular weight (hereinafter abbreviated as Mn) of (a0) by gel permeation chromatography (GPC) is preferably 800 to 20,000, more preferably 1,000 to 10,000, from the viewpoint of antistatic properties. Particularly preferred is 1,200 to 6,000.
The amount of the double bond in (a0) 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 antistatic properties.
The average number of double bonds per molecule is preferably 1.1 to 5, more preferably 1.3 to 3, particularly preferably 1.5 from the viewpoints of repetitive structure formation and antistatic properties. ~ 2.5, most preferably 1.8-2.2.
In the thermal degradation method, a low molecular weight polyolefin having an average number of terminal double bonds per molecule of 1.5 to 2 in the range of 800 to 6,000 Mn can be easily obtained [for example, Katsuhide Murata, See Tadahiko Makino, Journal of the Chemical Society of Japan, page 192 (1975)].

The measurement conditions of Mn are as follows (hereinafter, Mn is measured under the same conditions).
Apparatus: High-temperature gel permeation chromatography Solvent: Orthodichlorobenzene Reference substance: Polystyrene Sample concentration: 3 mg / ml
Column stationary phase: PLgel MIXED-B
Column temperature: 135 ° C

  As the polyolefin (a1) having a carbonyl group at both ends of the polymer, both ends of (a0) are α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, carbon number 1 to 4), a polyolefin (a11) having a structure modified with (hereinafter the same), a polyolefin (a12) having a structure obtained by secondary modification of (a11) with a lactam or an aminocarboxylic acid, Polyolefin (a13) having a structure in which (a0) is oxidized or hydroformylated and modified, polyolefin (a14) having a structure in which (a13) is secondarily modified with lactam or aminocarboxylic acid, and a mixture of two or more of these It is done.

(A11) can be obtained by modifying (a0) with an α, β-unsaturated carboxylic acid (anhydride).
Examples of the α, β-unsaturated carboxylic acid (anhydride) include carboxylic acids having 3 to 12 carbon atoms such as monocarboxylic acid [(meth) acrylic acid and the like], dicarboxylic acid (maleic acid, fumaric acid, itaconic acid, citracone Acid), alkyl (1 to 4 carbon atoms) esters thereof [methyl (meth) acrylate, butyl (meth) acrylate, diethyl itaconate, etc.], and anhydrides thereof.
Of these, from the viewpoint of reactivity with (a0), dicarboxylic acids, their alkyl esters and their anhydrides are preferred, maleic acid (anhydride) and fumaric acid are more preferred, and maleic acid is particularly preferred. (Anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) used is preferably 0.5 to 40% by weight based on the weight of the polyolefin (a0), preferably from the viewpoint of the formation of a repeating structure and antistatic properties. Preferably it is 1-30 weight%, Most preferably, it is 2-20 weight%.
Modification of the polyolefin (a0) with an α, β-unsaturated carboxylic acid (anhydride) is carried out by a known method, for example, the terminal double bond of (a0) is subjected to α, It can be carried out by thermally adding (ene reaction) β-unsaturated carboxylic acid (anhydride).
As a solution method, α, β-unsaturated carboxylic acid (anhydride) is added to (a0) in the presence of a hydrocarbon solvent such as xylene and toluene, and the temperature is 170 to 230 ° C. in an inert gas atmosphere such as nitrogen. The method of making it react is mentioned.
Examples of the melting method include a method in which (a0) is heated and melted, and then α, β-unsaturated carboxylic acid (anhydride) is added and reacted at 170 to 230 ° C. in an inert gas atmosphere such as nitrogen.
Among these methods, the solution method is preferable from the viewpoint of reaction uniformity.

(A12) can be obtained by secondary modification of (a11) with lactam or aminocarboxylic acid.
Examples of the lactam include lactams having 6 to 12 carbon atoms (preferably 6 to 8, more preferably 6), such as caprolactam, enantolactam, laurolactam, and undecanolactam.
Examples of aminocarboxylic acids include aminocarboxylic acids having 2 to 12 carbon atoms (preferably 4 to 12 and more preferably 6 to 12), such as amino acids (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.), ω- Examples include aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Of these, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred from the viewpoint of reactivity of secondary modification, and caprolactam is more preferred. Laurolactam, ω-aminocaprylic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, particularly preferred are caprolactam and 12-aminododecanoic acid.
The amount of the lactam or aminocarboxylic acid used can be arbitrarily selected as long as the difference in refractive index from the thermoplastic resin (B) described later is 0.01 or less. However, transparency and antistatic properties can be selected. In view of the above, preferably, 0.1 to 20 lactams or aminocarboxylic acids, more preferably 0.3 to 15, particularly preferably per residue obtained by removing the carboxyl group from the α, β-unsaturated carboxylic acid. Is 0.5-10.

(A13) can be obtained by oxidizing (a0) with oxygen and / or ozone or hydroformylating by an oxo method to introduce a carbonyl group.
The introduction of the carbonyl group by oxidation can be carried out by a known method, for example, the method described in US Pat. No. 3,692,877. The introduction of a carbonyl group by hydroformylation can be carried out by a known method, for example, Macromolecules, Vol. 31, 5943 page.

(A14) can be obtained by secondary modification of (a13) with lactam or aminocarboxylic acid.
Examples of the lactam and aminocarboxylic acid include those exemplified in (a12), and the amounts used are also the same.

Mn of the polyolefin (a1) having carbonyl groups at both ends of the polymer is preferably 800 to 25,000, more preferably 1,000 from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. ˜20,000, particularly preferably 2,500 to 10,000.
The acid value of (a1) is preferably 4 to 280 (mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with (b), more preferably 4 to 100, particularly preferably. Is 5-50.

  Polyether diol (b1) and polyether diamine (b2) can be used as the hydrophilic polymer (b).

The polyether diol (b1) has a structure obtained by addition reaction of an alkylene oxide (hereinafter abbreviated as AO) (2 to 12 carbon atoms) with the diol (b01) or dihydric phenol (b02), for example, the general _{^{formula: H (OA 1) m O}} -E 1 -O (A 1 O) m ' ones represented by H, and the like.
In the formula, E ¹ represents a residue obtained by removing a hydroxyl group from (b01) or (b02), and A ¹ has 2 to 12 carbon atoms (preferably 2 to 8, more preferably, may contain a halogen atom). Is an alkylene group of 2 to 4); m and m ′ represent an integer of 1 to 300, preferably 2 to 250, particularly preferably 10 to 100, and m and m ′ may be the same or different. In addition, m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and the bond form in the case where these are composed of two or more oxyalkylene groups is a block form. , Random or a combination thereof.

As the diol (b01), a dihydric alcohol (aliphatic, alicyclic and araliphatic dihydric alcohol) having 2 to 12 carbon atoms (preferably 2 to 10, more preferably 2 to 8 carbon atoms) and 1 to 1 carbon atoms are used. And 12 tertiary amino group-containing diols.
Examples of the aliphatic dihydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 1,12-dodecanediol.
Examples of the alicyclic dihydric alcohol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-cyclooctanediol, and 1,3-cyclopentanediol.
Examples of the araliphatic dihydric alcohol include xylylenediol, 1-phenyl-1,2-ethanediol and 1,4-bis (hydroxyethyl) benzene.

As the tertiary amino group-containing diol, an aliphatic or alicyclic primary monoamine (having 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms) bishydroxyalkyl (1 to 1 carbon atoms in the alkyl group). 12, preferably 2 to 10, more preferably 2 to 8) and bishydroxyalkyl (alkyl group having 1 to 12 carbon atoms) of aromatic (aliphatic) primary monoamine (carbon number 6 to 12). It is done.
The bishydroxyalkylated monoamine is a known method, for example, reacting monoamine with AO having 2 to 4 carbon atoms [ethylene oxide (hereinafter abbreviated as EO) propylene oxide (hereinafter abbreviated as PO), butylene oxide, etc.]. Or it can obtain easily by making monoamine and C1-C12 halogenated hydroxyalkyl (2-bromoethyl alcohol, 3-chloropropyl alcohol, etc.) react.

Aliphatic primary monoamines include methylamine, ethylamine, 1- and 2-propylamine, n- and i-amylamine, hexylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2- and 3- Examples include aminoheptane, heptylamine, nonylamine, decylamine, undecylamine, and dodecylamine.
Examples of the alicyclic primary monoamine include cyclopropylamine, cyclopentylamine, and cyclohexylamine.
Examples of the aromatic (aliphatic) primary monoamine include aniline and benzylamine.

  Examples of the dihydric phenol (b02) include 6 to 18 carbon atoms (preferably 8 to 18, more preferably 10 to 15), such as monocyclic dihydric phenol (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenol (bisphenol). A, bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-2,2-butane, dihydrokibiphenyl and the like) and condensed polycyclic divalent phenols (dihydroxynaphthalene, binaphthol and the like).

  Of (b01) and (b02), from the viewpoint of antistatic properties, preferred are dihydric alcohols and dihydric phenols, more preferred are aliphatic dihydric alcohols and bisphenols, and particularly preferred are ethylene glycol and bisphenol A. .

As AO to be subjected to addition reaction with diol (b01) or dihydric phenol (b02), AO having 2 to 12 carbon atoms (EO, PO, 1,2-, 1,4-, 2,3- and 1,3- Butylene oxide and a mixture of two or more thereof), and other AOs and substituted AOs may be used in combination.
Examples of other AO and substituted AO include epoxidized products of α-olefins having 5 to 12 carbon atoms, styrene oxide and epihalohydrin (such as epichlorohydrin and epibromohydrin). The amount of each of the other AO and substituted AO used is preferably 30% by weight or less, more preferably 0 or 25% by weight, particularly preferably 0 or 20% from the viewpoint of antistatic properties based on the weight of the total AO. % By weight or less.

When two or more kinds of AO are used in combination, the coupling form may be random and / or block.
Of AO, from the viewpoint of antistatic properties, EO alone and a combination of EO and AO other than EO (block and / or random addition) are more preferred, and EO alone and a combination of EO and PO are particularly preferred. Is EO alone.
The number of added moles of AO is preferably from the viewpoint of the volume resistivity value of the hydrophilic polymer (b), preferably from 1 to 300 moles, more preferably from 2 to 250 moles, particularly per hydroxyl group of (b01) or (b02). Preferably it is 10-100 mol.

The addition reaction of AO can be performed by a known method, for example, in the presence of an alkali catalyst (potassium hydroxide, sodium hydroxide, etc.) under the conditions of 100 to 200 ° C. and pressure of 0 to 0.5 MPaG.
The content of the oxyalkylene unit in the polyether diol (b1) is preferably from 5 to 99.8% by weight, more preferably from the viewpoint of the volume resistivity value of the hydrophilic polymer (b) based on the weight of (b1). Is 8 to 99.6% by weight, particularly preferably 10 to 98% by weight. Further, the content of the oxyethylene unit in the polyoxyalkylene chain is preferably 5 to 100% by weight, more preferably 10 to 100% from the viewpoint of the volume resistivity value of (b) based on the weight of the polyoxyalkylene chain. % By weight, particularly preferably 50 to 100% by weight, most preferably 60 to 100% by weight.

The polyether diamine (b2) has a structure in which the hydroxyl group of the polyether diol (b1) is modified to an amino group (primary or secondary amino group), for example, a general formula: RNH-A ^2- (OA ¹ ) those represented by ^{_{m O-E 1 -O (A}} 1 O) m '-A 2 -NHR the like.
The symbol E ¹ in the formula represents a residue obtained by removing a hydroxyl group from (b01) or (b02), and A ¹ has 2 to 12 carbon atoms (preferably 2 to 8, preferably 2 to 8 carbon atoms) which may contain a halogen atom. Preferably 2-4) alkylene group; m and m ′ represent an integer of 1 to 300, preferably 2 to 250, particularly preferably 10 to 100, and m and m ′ may be the same or different. A ² represents an alkylene group having 2 to 12 carbon atoms (preferably 2 to 8, more preferably 2 to 4) which may contain a halogen atom, and A ¹ and A ² may be the same or different. R represents H or an alkyl group having 1 to 4 carbon atoms (preferably 1 or 2).
(B2) can be easily obtained by changing both terminal hydroxyl groups of (b1) to amino groups by a known method.
As a method of changing a hydroxyl group to an amino group, a known method, for example, a method of reducing a terminal cyanoalkyl group obtained by cyanoalkylating a hydroxyl group of (b1) to form an amino group [for example, (b1) and acrylonitrile And a method of hydrogenating the resulting cyanoethylated product], a method of reacting (b1) with an aminocarboxylic acid or lactam, a method of reacting (b1) with a halogenated amine under alkaline conditions, and the like. .
What was mentioned above as (b) may use together 2 or more types arbitrarily, if the refractive index difference of a block polymer (A) and a thermoplastic resin (B) satisfy | fills 0.01 or less. The refractive indexes of (A) and (B) are calculated from theoretical formulas or the refractive indexes of resins obtained by polymerizing monomers constituting (A) or (B) in advance are given in JIS K7105 (1981). It is calculated | required by measuring according to it. The refractive index in the present invention is a value measured with an Abbe refractometer.

The volume resistivity value of the hydrophilic polymer (b) (value measured by the method described later in an atmosphere of 23 ° C. and 50% RH) is 10 ⁵ to 10 ¹¹ Ω · cm, preferably 10 ⁶ to 10 ¹⁰ Ω. · Cm, more preferably 10 ⁷ to 10 ⁹ Ω · cm. When the volume resistivity value is less than 10 ^{5, the} physical properties of the resin deteriorate, and when it exceeds 10 ¹¹ , the antistatic property deteriorates.
Mn of (b) is preferably 150 to 20,000, more preferably 300 to 18,000, particularly preferably 1,000 to 15,000, from the viewpoint of heat resistance and reactivity with polyolefin (a). Most preferably, it is 1,200 to 8,000.

  In the block polymer (A), the block of the polyolefin (a) and the block of the hydrophilic polymer (b) have at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond and an imide bond. Among them, a polymer having a repeating unit represented by the following general formula (1) is preferable from the viewpoint of antistatic properties and transparency.

In the formula (1), n is an integer of 2 to 50 (preferably 3 to 40, more preferably 4 to 30, particularly preferably 4 to 30); ^one of R ¹ and R ² is H and the other is H or methyl group; y is an integer of from 15 to 800 (preferably 20 to 500, more preferably 30 to 400); E ¹ is the residue minus the hydroxyl groups from diol (b01) or the dihydric phenol (b02); a ¹ is An alkylene group having 2 to 4 carbon atoms; m and m ′ are integers of 1 to 300 (preferably 5 to 200, more preferably 8 to 150); X and X ′ are the following general formulas (2) and (3) And a corresponding group selected from (2 ′) and (3 ′), that is, when X is a group represented by the general formula (2), X ′ is a group represented by the general formula (2 ′) The same relationship applies to equations (3) and (3 ′).

In the general formulas (2) and (3) and the corresponding formulas (2 ′) and (3 ′), R is the same as described in the above (b2) and is H or having 1 to 4 carbon atoms (preferably 1 Or 2) an alkyl group, R ³ is a divalent hydrocarbon group having 1 to 11 carbon atoms (preferably 2 to 11, more preferably 5 to 11), and R ⁴ is H or 1 to 10 carbon atoms (preferably 1-8, more preferably 1-6) alkyl group; r is an integer of 1-20 (preferably 1-15, more preferably 1-10), u is 0 or 1; Q, Q ′, T and T ′ are groups represented by the following formulae

In the general formulas (4) and (5) and the corresponding (4 ′) and (5 ′), R ⁵ is H or a carbon number of 1 to 10 (preferably 1 to 8, more preferably 1 to 6). ), R ⁶ is H or a methyl group, t is 1 when R ⁶ is a methyl group, and 0 when H is H.

The polyether segment {(OA ¹ ) _m O—E ¹ —O (A ¹ O) _{m ′} } in {} in the repeating unit represented by the general formula (1) is the polyether diol (b1) or poly It is a structure derived from ether diamine (b2), and E ¹ , A ¹ , m and m ′ in the formula are the same as described above.

In the general formula (1), the block polymer in which X is a group represented by the general formula (2) and X ′ is a group represented by the general formula (2 ′) includes (a11) and / or (a12) and (A1) obtained by polymerizing (b1) and (A2) obtained by polymerizing (a11) and / or (a12) and (b2) are included.
(A1) includes (A11) in which (a11) and (b1) are combined, (A12) in which (a12) and (b1) are combined, and a mixture of (A11) and (A12). Similarly, (A2) includes (A21) in which (a11) and (b2) are combined, (A22) in which (a12) and (b2) are combined, and a mixture of (A21) and (A22). included.

(A1) is a known method, for example, a method in which (b1) is added to (a11) and / or (a12) and a polymerization (polycondensation) reaction is usually carried out at 200 to 250 ° C. under reduced pressure, or uniaxial or It can manufacture by the method of superposing | polymerizing normally with 160-250 degreeC and residence time 0.1-20 minutes using a biaxial extruder.
In the above polymerization reaction, known catalysts such as antimony catalyst (antimony trioxide, etc.); tin catalyst (monobutyltin oxide, etc.); titanium catalyst (tetrabutyl titanate, etc.); zirconium catalyst (tetrabutyl zirconate, etc.); organic acid Metal salt catalysts [zirconium organic acid salts (such as zirconyl acetate), zinc acetate, etc.]; and mixtures of two or more of these. Of these, preferred are zirconium catalyst and zirconium organic acid salt, and more preferred is zirconyl acetate.
The usage-amount of a catalyst is 0.001 to 5% normally with respect to the total weight of (a11) and / or (a12) and (b1), Preferably it is 0.01 to 3%.

Of (A1), (A12) may be reacted with (b1) after (a11) is secondarily modified with the above lactam or aminocarboxylic acid, or (a11) and lactam or aminocarboxylic acid may be reacted. The reaction may be carried out in the presence of (b1) followed by reaction with (b1).

(A2) is the same as (A1) except that the combination of (a11) and / or (a12) and (b1) in (A1) is replaced with the combination of (a11) and / or (a12) and (b2) It can be manufactured by the method.
Of (A2), (A22) may be produced by secondarily modifying (b2) with the lactam or aminocarboxylic acid and then reacting it with (a11).

In the general formula (1), the block polymer in which X is a group represented by the general formula (3) and X ′ is a group represented by the general formula (3 ′) includes (a13) (when r = 1) And / or (a14) (when r ≧ 2) and (b1) are subjected to a polymerization reaction (A3) and (a13) and / or (a14) and (b2) are subjected to a polymerization reaction (A4) obtained by the above.
(A3) includes (A31) in which (a13) and (b1) are combined, (A32) in which (a14) and (b1) are combined, and a mixture of (A31) and (A32). Similarly, (A4) includes (A41) in which (a13) and (b2) are combined, (A42) in which (a14) and (b2) are combined, and a mixture of (A41) and (A42). included.
(A3) and (A4) can be produced by the same method as (A1) and (A2).

  The amount of (b) constituting the block polymer (A) is selected in such a range that the difference in refractive index between (A) and the thermoplastic resin (B) is 0.01 or less, which is preferable from the viewpoint of antistatic properties. Is 20 to 90% by weight, more preferably 25 to 80% by weight, and particularly preferably 30 to 70% by weight based on the total weight of (a) and (b).

The Mn of the block polymer (A) is preferably 2,000 to 60,000, more preferably 5,000 to 40,000, and particularly preferably 8,000 to 30,000 from the viewpoint of antistatic properties.
The refractive index of (A) is preferably 1.42 to 1.55, and more preferably 1.45 to 1.53, from the viewpoint of the transparency of the molded body described later.

In the structure of (A), the average number of repeating units (Nn) of the repeating unit of the polyolefin (a) block and the hydrophilic polymer (b) block is preferably 2 to 50 from the viewpoint of antistatic properties, Preferably it is 2.3-30, Most preferably, it is 2.7-20, Most preferably, it is 3-10.
Nn can be determined by Mn and ¹ H-NMR analysis of (A).
For example, in the case of (A1) having a structure in which blocks of (a11) and (b1) are alternately and repeatedly bonded, 4.0 ^{1 to} 4.1 ppm ester bond {—C in ¹ H-NMR analysis Since the signal attributed to the proton of (C═O) —OCH ₂ —} and the signal attributed to the proton of polyethylene glycol of 3.2 to 3.7 ppm can be observed, the ratio of these proton integral values was determined. Thus, Nn can be obtained from this ratio and Mn.

  The terminal of (A) is the carbonyl group, amino group and / or unmodified polyolefin terminal derived from (a) (polyolefin terminal without any modification, ie, alkyl group or alkenyl group), or hydroxyl group derived from (b) And / or any amino group. Among these, a carbonyl group, an amino group, and a hydroxyl group are preferable as a terminal from the viewpoint of reactivity, and a carbonyl group and a hydroxyl group are more preferable.

  Examples of the thermoplastic resin (B) include vinyl resins [polyolefin resin (B1), acrylic resin (B2), polyvinyl chloride resin (B3), polystyrene resin (B4), etc.], polyamide resin (B5), and polyester resin. Examples thereof include transparent resins such as (B6) and polycarbonate resin (B7). Of these, from the viewpoint of the difference in refractive index from (A), preferred are vinyl resins such as polyolefin resin (B1), acrylic resin (B2), and polyvinyl chloride resin (B3), and more preferred are polyolefin resins (B1). ) And acrylic resin (B2).

The vinyl resins [(B1) to (B4)] are obtained by (co) polymerizing the following vinyl monomers by a known polymerization method (radical polymerization method, Ziegler catalyst polymerization method, metallocene catalyst polymerization method, etc.).
Vinyl monomers include hydrocarbon vinyl monomers (aliphatic hydrocarbons, aromatic hydrocarbons, etc.), acrylic monomers, other unsaturated mono- and dicarboxylic acids and their derivatives, carboxylic acid esters of unsaturated alcohols, unsaturated Examples include alkyl ethers of alcohols, halogen-containing vinyl monomers, and combinations (random and / or block) of two or more thereof.

Among the hydrocarbon vinyl monomers, examples of the aliphatic hydrocarbon include olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10) exemplified as raw materials for the polyolefin (a0).
The aromatic hydrocarbon includes 8 to 30 carbon atoms, such as styrene and derivatives thereof [o-, m- and p-alkyl (1 to 10 carbon atoms) styrene (vinyltoluene, etc.), α-alkyl (1 to 1 carbon atoms). 10) Styrene (α-methylstyrene, etc.), halogenated styrene (chlorostyrene, etc.), etc.].

As an acrylic monomer, C3-C30, for example, (meth) acrylic acid and its derivative (s) are mentioned.
Derivatives of (meth) acrylic acid include alkyl (C1-20) (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, n-, i- and t-butyl (meth) acrylate, hexyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, etc.], aliphatic ring (4 to 20 carbon atoms) -containing (meth) acrylate [cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (Meth) acrylate, cyclooctyl (meth) acrylate, etc.], aromatic ring (6 to 20 carbon atoms) -containing (meth) acrylate [phenyl (meth) acrylate, benzyl (meth) acrylate, etc.], [mono- and di-alkyl (C1-C4)] aminoalkyl (charcoal Number 2-4) (meth) acrylates [amino ethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc.], and (meth) acrylonitrile and (meth) acrylamide.

Other unsaturated mono- and dicarboxylic acids include unsaturated mono- and dicarboxylic acids having 2 to 30 carbon atoms (preferably 3 to 20, more preferably 4 to 15) such as crotonic acid and maleic acid. Examples thereof include acids, fumaric acid and itaconic acid, and derivatives thereof include 5 to 30 carbon atoms, such as mono- and di-alkyl (1 to 20 carbon atoms) esters, acid anhydrides (maleic anhydride, etc.) and acids. An imide (maleic acid imide etc.) etc. are mentioned.
Examples of the carboxylic acid ester of the unsaturated alcohol include carboxylic acid (carbon number 2 to 4) ester (vinyl acetate and the like) of an unsaturated alcohol [vinyl alcohol, (meth) allyl alcohol and the like] having 4 to 6 carbon atoms. Examples of the alkyl ether of unsaturated alcohol (same as above) include alkyl (carbon number of 1 to 20) ether of unsaturated alcohol (same as above).
Examples of the halogen-containing vinyl monomer include 2 to 12 carbon atoms such as vinyl chloride, vinylidene chloride and chloroprene.

  The polyolefin resin (B1) includes one or more (co) polymers of aliphatic hydrocarbon vinyl monomers and one or more vinyl monomers copolymerizable with one or more aliphatic hydrocarbon vinyl monomers (weight ratio is In general, a copolymer with 5/95 to 95/5, preferably 50/50 to 90/10) is included. Examples of the copolymerizable vinyl monomer include the vinyl monomers other than the aliphatic hydrocarbon vinyl monomer.

Specific examples of (B1) include polyethylene, polypropylene, ethylene / propylene copolymer (weight ratio 0.1 / 99.9 to 99.9 / 0.1), ethylene and / or propylene, and 4 to 12 carbon atoms. Copolymers (random or block) with one or more of α-olefins, ethylene / vinyl acetate copolymers (EVA, weight ratio 95 / 5-60 / 40), ethylene / ethyl acrylate copolymers (EEA, Weight ratio 95/5 to 60/40).
Of these, polyethylene, polypropylene, an ethylene / propylene copolymer, ethylene and / or propylene and one or more α-olefins having 4 to 12 carbon atoms are preferred from the viewpoints of transparency and antistatic properties. It is a coalescence (random or block, weight ratio of ethylene and / or propylene to α-olefin 9: 1 to 1: 9).

The melt flow rate (MFR) of (B1) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoints of resin physical properties and antistatic properties. The MFR is measured according to JIS K7210 (1976) (for example, in the case of polypropylene, the temperature is 230 ° C. and the load is 2.16 kgf; in the case of polyethylene, the temperature is 190 ° C. and the load is 2.16 kgf).
The crystallinity of (B1) is preferably 0 to 80%, more preferably 0 to 70%, particularly preferably 0 to 60% from the viewpoint of transparency. The degree of crystallinity is measured by methods such as X-ray diffraction and infrared absorption spectrum ["Polymer solid structure-Polymer Experimental Laboratory 2", Hatsugoro Nanshino, page 42, Kyoritsu Shuppan (1958)].

As the acrylic resin (B2), one or more (co) polymers of the acrylic monomer (polymethyl methacrylate, polybutyl acrylate, etc.) and one kind of vinyl monomer copolymerizable with one or more of the acrylic monomers. A copolymer with the above (weight ratio is usually 5/95 to 95/5, preferably 50/50 to 90/10). Examples of copolymerizable vinyl monomers include the vinyl monomers other than acrylic monomers.
The MFR of (B2) is preferably 0.5 to 150, more preferably 1 to 100, particularly preferably 2 to 80 from the viewpoints of resin physical properties and antistatic properties. The melt flow rate is measured in accordance with JIS K7210 (1976) (for example, temperature 230 ° C., load 1.2 kgf).

Examples of the polyvinyl chloride resin (B3) include one or more (co) polymers of the halogen-containing vinyl monomer and a copolymer of one or more vinyl monomers copolymerizable with the halogen-containing vinyl monomer. Examples of the copolymerizable vinyl monomer include the vinyl monomers other than the halogen-containing vinyl monomer.
The specific viscosity of (B3) is preferably from 0.1 to 0.8, more preferably from 0.2 to 0.8, particularly preferably from 0.3 to 0.7, from the viewpoints of resin physical properties and antistatic properties. . The specific viscosity is measured according to JIS K6721 (1977).

The Mn of the thermoplastic resin (B) is preferably 20,000 to 500,000, more preferably 25,000 to 450,000, and particularly preferably 30,000 to 400,000 from the viewpoint of resin physical properties.
The refractive index of (B) is preferably 1.42 to 1.55, and more preferably 1.45 to 1.53, from the viewpoint of the transparency of the molded body described later.

  The resin composition of the present invention comprises (A) in (B), and the content of (A) can be variously changed according to the required performance, but sufficient antistatic properties and mechanical properties are obtained. Preferably from the viewpoint of provision, it is 1 to 40% by weight, more preferably 1.5 to 30%, based on the total weight of (A) and (B).

In the resin composition of the present invention, an alkali metal or alkaline earth metal salt (C), a surfactant (D), an ionic liquid (E), a compatibilizing agent are necessary as long as the effects of the present invention are not impaired. You may contain the at least 1 sort (s) of additive chosen from the group which consists of an agent (F) and another additive for resins (G).
Among these, (C), (D) and (E) are added for the purpose of further improving the antistatic property.
Examples of the alkali metal and / or alkaline earth metal salt (C) include alkali acid (lithium, sodium, potassium, etc.) and / or alkaline earth metal (magnesium, calcium, etc.) organic acids [having 1 to 12 carbon atoms] Mono- and di-carboxylic acids (formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.), sulfonic acids having 1 to 20 carbon atoms (methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc.), thiocyanate Salts of inorganic acids [hydrohalic acid (hydrochloric acid, hydrobromic acid, etc.), perchloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.].

Specific examples of (C) include lithium acetate, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, magnesium bromide, lithium perchlorate, sodium perchlorate, potassium perchlorate, potassium sulfate, potassium phosphate. And potassium thiocyanate.
Of the above (C), from the viewpoint of antistatic properties, halide (more preferably lithium chloride, sodium chloride, potassium chloride), acetate (more preferably potassium acetate), and perchlorate (more preferable). Is potassium perchlorate).
The use amount of (C) is usually 5% by weight or less based on the weight of (A), preferably from 0.001 to 3% by weight from the viewpoint of giving a resin having a good appearance without depositing on the resin surface, More preferably, it is 0.01-2.5 weight%, Most preferably, it is 0.1-2 weight%, Most preferably, it is 0.15-1 weight%.
About the method of containing (C), in order not to impair the transparency of the resin composition, it is necessary to disperse in (A) in advance, and (C) is contained and dispersed and dissolved in the production of (A). The method of letting it leave is preferable. There is no particular limitation on the timing of adding (C) during the production of (A), and any of the timing before polymerization, during polymerization, and after polymerization may be used.

Surfactant (D) includes nonionic, anionic, cationic and amphoteric surfactants.
Nonionic surfactants include polyethylene glycol type [higher alcohol (8 to 18 carbon atoms such as stearyl alcohol, lauryl alcohol and myristyl alcohol, the same shall apply hereinafter) EO (2 to 50 mol) adduct, higher fatty acid (carbon 8 to 24, such as stearic acid, lauric acid and myristic acid, the same shall apply hereinafter) EO (2 to 50 mol) adduct, higher alkylamine (8 to 24 carbon atoms such as stearylamine, laurylamine and myristylamine, The same.) EO (2 to 50 mol) adduct, polypropylene glycol (Mn 800 to 4,000) EO (2 to 50 mol) adduct, etc.], and polyhydric alcohol type [polyoxyethylene (Mn 200 to 3,000) , Higher fatty acid ester of glycerin, higher grade of pentaerythrit Fatty acid esters, higher fatty acid esters of sorbit or sorbitan, alkyls of 3 to 60 polyhydric (2 to 5 or more) alcohols (3 to 60 carbon atoms, such as glycerin, pentaerythritol, sorbit, glucose) (3 to 3 carbon atoms) 60) ethers, alkanolamines (higher fatty acid amides of 2 to 24 carbon atoms, etc.)] and the like.

Examples of the anionic surfactant include compounds other than the above (C), such as carboxylates (alkali metal salts of higher fatty acids), sulfate esters [higher alcohol sulfate esters, higher alkyl ethers (8 to 24 carbon atoms). Sulfate esters, etc.], sulfonates [alkyl (carbon number 8-24) benzene sulfonate, alkyl (carbon numbers 8-18) sulfonate, paraffin (carbon numbers 25-60) sulfonate, etc.), phosphorus And acid ester salts (higher alcohol phosphate ester salts, etc.).
Examples of the cationic surfactant include quaternary ammonium salts [alkyl (carbon number 8 to 24) trimethylammonium salt and the like].
Examples of amphoteric surfactants include amino acid type [higher alkyl (carbon number 8-24) aminopropionate, etc.], betaine type [higher alkyl (carbon number 8-24) dimethylbetaine, higher alkyl (carbon number 8-24). Dihydroxyethyl betaine, etc.].
These surfactants may be used alone or in combination of two or more. Of these, anionic surfactants are preferred from the viewpoint of heat resistance and antistatic properties, more preferred are sulfonates, and particularly preferred are alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates. .

The amount of (D) used is usually 20% by weight or less based on the total weight of (A) and (D), and preferably 0.001 from the viewpoint of giving a resin having a good appearance without being deposited on the resin surface. -12% by weight, more preferably 0.01 to 10% by weight, particularly preferably 0.1 to 8 parts by weight.
Although there is no limitation in particular about the method of containing (D), in order to disperse | distribute effectively in a resin composition, it is preferable to make it disperse | distribute beforehand in (A). When (D) is dispersed in (A) in advance, it is particularly preferable to contain (D) in advance during the production (polymerization) of (A). There is no particular limitation on the timing at which (D) is contained during the production of (A), and any of the timing before polymerization, during polymerization, and after polymerization may be used.

  The ionic liquid (E) is a compound other than the above (C) and (D), has a melting point of room temperature or lower, and at least one of cations or anions constituting (E) is an organic ion, and has an initial conductivity. Is a room temperature molten salt of 1 to 200 ms / cm (preferably 10 to 200 ms / cm), for example, a room temperature molten salt described in WO95 / 15572.

  Examples of the cation constituting (E) include an amidinium cation, a guanidinium cation, and a tertiary ammonium cation.

  Examples of the amidinium cation include imidazolinium cation [1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazolinium. 1,3-dimethyl-2,4-diethylimidazolinium, etc.]; imidazolium cation [1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1, 2,3-trimethylimidazolium, etc.]; tetrahydropyrimidinium cation [1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6 -Tetrahydropyrimidinium, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 1,2 , 3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium and the like]; and dihydropyrimidinium cation [1,3-dimethyl-1,4- or -1,6-dihydropyrimidinium 1,2,3-trimethyl-1,4- or -1,6-dihydropyrimidinium, 1,2,3,4-tetramethyl-1,4- or -1,6-dihydropyrimidinium, etc. ].

  Examples of the guanidinium cation include a guanidinium cation having an imidazolinium skeleton [2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolinium, 2-dimethylamino-1-methyl-3,4-diethylimidazolinium, etc.]; guanidinium cation having an imidazolium skeleton [2-dimethyl Amino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolium, 2-dimethylamino-1-methyl -3,4-diethylimidazolium, etc.]; tetrahydropyrimidi Guanidinium cation having a skeleton [2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4 , 5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium, etc.]; and guanidinium having a dihydropyrimidinium skeleton Cation [2-dimethylamino-1,3,4-trimethyl-1,4- or -1,6-dihydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4- or -1, 6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4- or -1,6-dihydropyrimidinium Etc.], and the like.

  Examples of the tertiary ammonium cation include methyl dilauryl ammonium.

The amidinium cation, guanidinium cation and tertiary ammonium cation may be used alone or in combination of two or more.
Of these, from the viewpoint of initial conductivity, an amidinium cation is preferable, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.

In (E), examples of the organic acid and / or inorganic acid constituting the anion include the following.
Examples of the organic acid include carboxylic acid, sulfate ester, higher alkyl ether sulfate ester, sulfonic acid and phosphate ester.
Examples of the inorganic acid include super strong acids (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid and hexafluoroarsenic acid), phosphoric acid and boric acid. It is done.
The organic acid and inorganic acid may be used alone or in combination of two or more.
Among the above organic acids and inorganic acids, from the viewpoint of the initial conductivity of (E), a super strong acid or a super strong acid in which the Hammett acidity function (-H ₀ ) of the anion constituting (E) is 12 to 100 is preferable. These are acids that form anions other than the conjugated bases, and mixtures thereof.

  Examples of the anion other than the conjugate base of the super strong acid include halogen (for example, fluorine, chlorine and bromine) ions, alkyl (C1 to C12) benzenesulfonic acid (for example, p-toluenesulfonic acid) ions, and poly (n = 1). -25) Fluoroalkanesulfonic acid (for example, undecafluoropentanesulfonic acid) ion.

Super strong acids include those derived from protonic acids and combinations of protonic acids and Lewis acids, and mixtures thereof.
Examples of the protonic acid as the super strong acid include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkane (C1 -30) sulfonic acid [for example, methanesulfonic acid, dodecanesulfonic acid, etc.], poly (n = 1-30) fluoroalkane (C1-30) sulfonic acid (for example, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, hepta) Fluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and tetrafluoroboric acid.
Of these, borofluoric acid, trifluoromethanesulfonic acid and bis (pentafluoroethylsulfonyl) imidic acid are preferred from the viewpoint of ease of synthesis.

Examples of the protonic acid used in combination with the Lewis acid include hydrogen halide (for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid. , Pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof.
Of these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of (E).

Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, thallium pentafluoride, and mixtures thereof.
Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of (E).
The combination of the protonic acid and the Lewis acid is arbitrary, but as the super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorothalamic acid, hexafluoroantimonic acid, thallium hexafluoride Examples include sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride, and mixtures thereof.

  Among the above anions, (E) from the viewpoint of the initial conductivity, a super strong acid conjugate base (a super strong acid consisting of a proton acid and a super strong acid consisting of a combination of a proton acid and a Lewis acid), more preferably It is a conjugate base of a super strong acid consisting of a super strong acid consisting of a proton acid and a proton acid and boron trifluoride and / or phosphorus pentafluoride.

The amount of (E) used is preferably 10% or less based on the total weight of (A) and (B), preferably from the viewpoint of providing an antistatic effect and a good appearance without shifting to the surface of the molded body. 0.001 to 5%, more preferably 0.01 to 3%.
The method of adding (E) is not particularly limited, but from the viewpoint of effective dispersion in the resin, it is preferable to disperse in (A) in advance, and after the production (polymerization) of (A) More preferably, (E) is added and dispersed in advance.

Among the additives, the compatibilizer (F) is added for the purpose of further improving the compatibility of (A) and (B) in the resin composition of the present invention.
(F) is a modified vinyl polymer having at least one polar group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group (described in JP-A-3-258850). Etc.), modified vinyl polymers having a sulfonyl group (for example, those described in JP-A-6-345927), block polymers having a polyolefin portion and an aromatic vinyl polymer portion, and the like.
These (F) s may be used alone or in combination of two or more, but from the viewpoint of transparency, those having a refractive index difference from (A) or (B) of 0.01 or less are preferred.
The amount of (F) used is usually 20% by weight or less based on the total weight of (A) and (B), preferably 0.1 to 15% by weight, more preferably 1 to 15% from the viewpoint of compatibility and resin physical properties. It is 10% by weight, particularly preferably 1.5 to 8% by weight.

  Among the above additives, other resin additives (G) include nucleating agent (G1), lubricant (G2), plasticizer (G3), mold release agent (G4), antioxidant (G5), flame retardant There may be mentioned at least one selected from the group consisting of (G6), an ultraviolet absorber (G7) and an antibacterial agent (G8).

    Examples of the nucleating agent (G1) include polyvalent organic acids and metal salts thereof, metal salts of aryl phosphate compounds, polyvalent metal salts of cyclic aryl phosphate compounds, and dibenzylidene sorbitol compounds. Either may be used together.

  Examples of polyvalent organic acids and metal salts thereof include aliphatic carboxylic acids [having 3 to 18 carbon atoms such as malonic acid, succinic acid, adipic acid, maleic acid, azelaic acid, sebacic acid, dodecanedioic acid, citric acid, and butanetricarboxylic acid. And butanetetracarboxylic acid]; cycloaliphatic carboxylic acid [C7-18, such as cyclopentanedicarboxylic acid, 1-methylcyclopentanedicarboxylic acid, 2-methylcyclopentanedicarboxylic acid, cyclopentenedicarboxylic acid, cyclohexanedicarboxylic acid, 1 -Methylcyclohexanedicarboxylic acid, 4-methylcyclohexanedicarboxylic acid, 3,5-dimethylcyclohexanedicarboxylic acid, 4-butylcyclohexanedicarboxylic acid, 4-octylcyclohexanedicarboxylic acid and 4-cyclohexene-1,2-dicarboxylic acid] Aromatic (aliphatic) dicarboxylic acids [8 to 12 carbon atoms, such as phthalic acid, trimellitic acid and pyromellitic acid]; and their alkali metals (eg, lithium, sodium and potassium), alkaline earth metals (eg, magnesium, calcium) , Strontium and barium), zinc and aluminum salts.

  Examples of metal salts of aryl phosphate compounds include bis (4-t-butylphenyl) phosphate, bis (4-cumylphenyl) phosphate, and 2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate. 2,2′-methylene-bis (4-cumyl-6-tert-butylphenyl) phosphate, 2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate, 2,2′- Methylene-bis (4-ethyl-6-tert-butylphenyl) phosphate, 2,2′-methylene-bis (4,6-di-methylphenyl) phosphate, 2,2′-methylene-bis (4,6- Di-ethylphenyl) phosphate, 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, 2,2′-ethylidene- (4-i-propyl-6-t-butylphenyl) phosphate, 2,2′-ethylidene-bis (4-sec-butyl-6-t-butylphenyl) phosphate, 2,2′-butylidene-bis ( 4,6-di-methylphenyl) phosphate, 2,2′-butylidene-bis (4,6-di-t-butylphenyl) phosphate, 2,2′-t-octylmethylene-bis (4,6-di) -Methylphenyl) phosphate, 2,2'-t-octylmethylene-bis (4,6-di-t-butylphenyl) phosphate and 4,4'-dimethyl-6,6'-di-t-butyl-2 , 2′-biphenyl) phosphate alkali metal (eg lithium, sodium and potassium) salts, mono- and bis- (4-tert-butylphenyl) phosphates, dihydrides Oxy - (4-t- butylphenyl) phosphate, dihydroxy-- bis (4-t- butylphenyl) phosphate and tris (4-t- butylphenyl) phosphate aluminum, salts of calcium and zinc.

  Examples of the polyvalent metal salt of the cyclic aryl phosphate compound include bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], bis [2,2′-methylene-bis (4 -Methyl-6-tert-butylphenyl) phosphate], bis [2,2′-thiobis (4-methyl-6-tert-butylphenyl) phosphate], bis [2,2′-thiobis (4-ethyl-6) -T-butylphenyl) phosphate], bis [2,2′-thiobis (4,6-di-t-butylphenyl) phosphate], bis [2,2′-thiobis (4-t-octylphenyl) phosphate] Bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], bis [(4,4′-dimethyl-6,6′-di-t-butyl-2,2 '-Bi Benzyl) phosphate], bis [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], tris [2,2′-ethylidene-bis (4,6-di-t-butyl) Phenyl) phosphate], tris [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], dihydroxy-2,2′-methylene-bis (4,6-di-t-) Butylphenyl) phosphate, dihydrooxy-2,2′-methylene-bis (4-cumyl-6-tert-butylphenyl) phosphate, dihydrooxy-bis [2,2′-methylene-bis (4,6-di-) t-butylphenyl) phosphate], dihydrooxy-2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate, dihydrooxy-2,2 ′ Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, hydroxy-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], hydroxy-bis [2, 2′-methylene-bis (4-cumyl-6-tert-butylphenyl) phosphate], bis [2,2′-methylene-bis (4,6-di-tert-butylphenyl) phosphate], hydroxy-bis [2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate] and hydroxy-bis [2,2′-ethylidene-bis (4,6-di-tert-butylphenyl) phosphate] Salts of alkaline earth metals (such as calcium and barium), aluminum, titanium, magnesium, zinc, oxyzirconium, etc. .

  Examples of the dibenzylidene sorbitol compound include 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, and 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol. 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidene Sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-bis (p-methylbenzylidene) sorbitol, 1,3,2,4-bis (p- Ethylbenzylidene) sorbitol, 1,3,2,4-bis (pn-propylbenzyl) Den) sorbitol, 1,3,2,4-bis (pi-propylbenzylidene) sorbitol, 1,3,2,4-bis (pn-butylbenzylidene) sorbitol, 1,3,2,4- Bis (p-sec-butylbenzylidene) sorbitol, 1,3,2,4-bis (pt-butylbenzylidene) sorbitol, 1,3- (2 ′, 4′-dimethylbenzylidene) -2,4-benzylidene Sorbitol, 1,3-benzylidene-2,4- (2 ′, 4′-dimethylbenzylidene) sorbitol, 1,3,2,4-bis (2 ′, 4′-dimethylbenzylidene) sorbitol, 1,3,2 4-bis (3 ′, 4′-dimethylbenzylidene) sorbitol, 1,3,2,4-bis (p-methoxybenzylidene) sorbitol, 1,3,2,4-bis p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-p-chlorobenzylidene-2, 4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2, 4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2, 4-p-chlorobenzylidene sorbitol, 1,3- Examples thereof include p-ethylbenzylidene-2 · 4-p-chlorobenzylidene sorbitol and 1,3,2,4-bis (p-chlorobenzylidene) sorbitol.

  Examples of the lubricant (G2) include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), higher fatty acid amides (such as stearic acid amide), and the like.

As the plasticizer (G3), aromatic carboxylic acid ester type [phthalic acid ester (dioctyl phthalate, dibutyl phthalate, etc.)], aliphatic monocarboxylic acid ester type [methyl acetyl ricinolate, triethylene glycol dibenzoate, etc.], Aliphatic dicarboxylic acid ester type [di (2-ethylhexyl) adipate, adipic acid-propylene glycol type polyester, etc.], aliphatic tricarboxylic acid ester type [citric acid esters (such as triethyl citrate), etc.], phosphoric acid triester type [Triphenyl phosphate etc.], petroleum resin and the like.
Examples of the release agent (G4) include lower alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters of fatty acids (such as hardened castor oil), glycol esters of fatty acids (such as ethylene glycol monostearate), and liquid paraffin. Etc.

  Examples of the antioxidant (G5) include phenolic [monocyclic phenol [2,6-di-t-butyl-p-cresol, butylated hydroxyanisole and the like], bisphenol [2,2′-methylenebis (4-methyl- 6-t-butylphenol), 4,4′-butylidenebis (3-methyl) -6-t-butylphenol, 4,4′-thiobis (3-methyl) -6-t-butylphenol, etc.], polycyclic phenol [1 , 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5- t-butylphenyl) butane and the like]; sulfur-based [dilauryl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, lauryl stearyl 3, '-Thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl β, β'-thiodibutyrate, dilauryl sulfide, etc.]; phosphorous [triphenyl phosphite, triisodecyl phosphite, diphenyl Isodecyl phosphite, phenyl diisodecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4 '-Butylidene-bis (3-methyl-6-t-butylphenylditridecyl) phosphite, cyclic neopentanetetrayl bis (octadecyl phosphite), cyclic neopentanetetrayl bis (2,6-di-t -Butyl-4-methylphenyl) phosphite, cyclic Neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, etc.]; amine-based [octylated diphenylamine, Nn-butyl-p-aminophenol, N, N -Diisopropyl-p-phenylenediamine, N, N-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N-diphenyl-p-phenylenediamine, N-phenyl-α-naphthylamine, phenyl- β-naphthylamine, phenothiazine, etc.].

  Examples of the flame retardant (G6) include organic flame retardants (such as nitrogen-containing [urea compounds, guanidine compounds, triazine compounds (melamine, guanamine, etc.) salts (inorganic acid salts, cyanuric acid salts, isocyanuric acid salts, etc.), etc.) ], Sulfur-containing [sulfuric acid ester, organic sulfonic acid, sulfamic acid, organic sulfamic acid and their salts, esters, amides, etc.], silicon-containing (polyorganosiloxane, etc.), phosphorus-containing [phosphoric acid ester (tri Inorganic flame retardants (such as antimony trioxide, magnesium hydroxide, zinc borate, barium metaborate, aluminum hydroxide, red phosphorus, ammonium polyphosphate) and the like.

  Examples of the ultraviolet absorber (G7) include benzotriazole series [2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, etc.], Benzophenone [2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, etc.], salicylate [phenyl salicylate, ethylene glycol monosalicylate, etc.], acrylate [2-ethylhexyl- 2-cyano-3,3′1-diphenyl acrylate, etc.].

  Antibacterial agents (G8) include benzoic acid, paraoxybenzoic acid ester, sorbic acid, halogenated phenol (2,4,6-tribromophenol sodium salt, etc.), organic iodine (4-chlorophenyl-3-iodopropargyl formal) ), Nitrile (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylene bisthocyanocyanate, etc.), N-haloalkylthioimide (N-tetrachloroethyl-thio-tetrahydrophthalimide, etc.), copper agent (Such as 8-oxyquinoline copper), benzimidazole (such as 2-4-thiazolylbenzimidazole), benzothiazole (such as 2-thiocyanomethylthiobenzothiazole), trihaloallyl (3-bromo-2,3-diiodo-2 -Propenyl ethyl carbonate, etc. , Triazole (such as azaconazole), organic nitrogen sulfur compound (such as suraoff 39), quaternary ammonium compound (such as trimethoxysilyl-propyloctadecyl ammonium chloride), pyridine compound [2,3,5,6-cytochloro-4- ( Methylsulfonyl) -pyridine] and the like.

  The amount used of (G) is based on the total weight of (A) and (B), (G1) is usually 20% by weight or less, preferably 1-10% by weight; (G2) is usually 20% by weight or less, Preferably 1 to 10% by weight; (G3) is usually 20% by weight or less, preferably 1 to 10% by weight; (G4) is usually 10% by weight or less, preferably 0.1 to 5% by weight; (G5) is Usually 5 wt% or less, preferably 0.1-3 wt%; (G6) is usually 20 wt% or less, preferably 1-10 wt%; (G7) is usually 5 wt% or less, preferably 0.1 3% by weight; (G8) is usually 3% by weight or less, preferably 0.05 to 1% by weight.

As the method for producing the resin composition of the present invention, (A) and (B), or (C), (D), (E), (F) and / or (G) are added to these as necessary. [(C) and (D) may be previously contained in (A) from the viewpoint of effective dispersion as described above. The method of melt-mixing is mentioned.
As a method of melt-mixing, a normal method, for example, pellets or powdery components are mixed with an appropriate mixer (Henschel mixer, etc.) and then melt-mixed with an extruder (temperature 150 to 260 ° C.) to form pellets. The method of making it.
There are no particular restrictions on the order of addition of each component during mixing, but for example, (1) (A) and (B), or (C), (D), (E), (F) as necessary. ) And / or (G) and blending and kneading, (2) part of (A) and (B), or if necessary, (C), (D), (E), ( F) and / or (G) is blended and kneaded, and then the remaining (B) is blended and kneaded. (3) (A) and (C) and a part of (B) as necessary. Examples include a method of blending and kneading (D), (E), (F) and / or (G), and then blending and kneading the remaining (B).
Among these methods, the methods (2) and (3) are called a master batch method or a master pellet method, and a small amount of (C), (D), (E), (F) and / or (G) is uniformly distributed. This is a preferable method from the viewpoint of dispersing in a resin.

Examples of the molding method of the resin composition of the present invention include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.) and the like. Depending on the purpose, it can be molded by any method.
The molded body formed by molding the resin composition of the present invention can be further coated and / or printed to form a molded article.
Examples of the coating method for the molded body include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, dip coating, roller coating, and brush coating.

Examples of the paint include paints generally used for painting plastics such as polyester melamine paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint.
The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is usually 10 to 50 μm, and preferably 15 to 40 μm from the viewpoint of physical properties of the coating film.
Examples of the method for printing on the molded article or the coated molded article include printing methods generally used for plastic printing, such as gravure printing, flexographic printing, screen printing, and offset printing.
Examples of the printing ink include those usually used for plastic printing.
Furthermore, the resin composition of the present invention can be added to a known paint or used as an antistatic paint by adding a solvent (for example, xylene or toluene).
Examples of the known paint include the paints described above.
The proportion in the case of adding the resin composition of the present invention to a known paint is preferably 5 to 60% by weight, more preferably 10 to 50% by weight from the viewpoint of antistatic properties based on the solid content weight of the known paint. Particularly preferably, it is 15 to 40% by weight.
Further, the concentration of the resin composition when a solvent is added to the resin composition of the present invention to form a coating is preferably 20 to 60% by weight, more preferably 25 to 55% by weight, particularly preferably from the viewpoint of antistatic properties. Is 30 to 50% by weight.

  A molded product formed by molding the resin composition of the present invention has excellent permanent antistatic properties, mechanical properties, and transparency, as well as excellent paintability and printability. Therefore, the resin composition of the present invention can be used for various moldings such as injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, and film molding (casting method, tenter method, inflation method, etc.). Housing products such as home appliances / OA equipment, game equipment and office equipment, various plastic containers such as IC trays, various packaging films, flooring sheets, artificial turf, mats, automobile parts, etc. Widely used as a material for various molded products.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In addition, a part shows a weight part below.
Production Example 1
Thermal degradation method [Thermal degradation of ethylene / propylene copolymer (ethylene content 2%) at a density of 0.90 at 23 ° C. and a melt flow rate of 6.0 g / 10 min at 410 ± 0.1 ° C.] The resulting low molecular weight ethylene / propylene random copolymer (Mn 3,500, density 0.89, 7.1 double bonds per 1,000 carbon atoms, average number of double bonds per molecule 1) .8, 95% by weight of polyolefin capable of modification at both ends), 10 parts of maleic anhydride and 30 parts of xylene were melted at 200 ° C. in a nitrogen gas atmosphere (sealed). Time reaction was performed.
Thereafter, excess maleic anhydride and xylene were distilled off at 200 ° C. under reduced pressure for 3 hours to obtain acid-modified polypropylene a111. The acid value of a111 was 27.2, and Mn was 3,700.

Production Example 2
Low molecular weight polypropylene (Mn 10,000) obtained by the thermal degradation method [polypropylene having a density of 0.90 at 23 ° C. and a melt flow rate of 10 (g / 10 min) at 410 ± 0.1 ° C.] , Density 0.89, 1.3 double bonds per 1,000 carbon atoms, average number of double bonds per molecule 1.80, content of polyolefin capable of modification at both ends 90% by weight) 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were melted at 200 ° C. in a nitrogen gas atmosphere (sealed) and reacted at 200 ° C. for 20 hours.
Then, excess maleic anhydride and xylene were distilled off under reduced pressure at 200 ° C. for 3 hours to obtain acid-modified polypropylene a112. The acid value of a112 was 5.0, and Mn was 10,000.

Production Example 3
Low molecular weight polypropylene (Mn 1,500) obtained by the thermal degradation method [polypropylene having a density of 0.90 at 23 ° C. and a melt flow rate of 10 (g / 10 min) at 410 ± 0.1 ° C.] , Density 0.89, 13.9 double bonds per 1,000 carbon atoms, average number of double bonds per molecule 1.95, content of polyolefin which can be modified at both ends 98% by weight) 80 parts, maleic anhydride 20 parts and xylene 30 parts were melted at 200 ° C. in a nitrogen gas atmosphere (sealed) and reacted at 200 ° C. for 20 hours.
Thereafter, excess maleic anhydride and xylene were distilled off at 200 ° C. under reduced pressure for 3 hours to obtain acid-modified polypropylene a113. The acid value of a113 was 55.3, and Mn was 1,600.

Production Example 4
66 parts of acid-modified polypropylene a111 obtained in Production Example 1 and 34 parts of 12-aminododecanoic acid were melted at 200 ° C. under a nitrogen gas atmosphere, and reacted at 200 ° C. for 3 hours under a reduced pressure of 10 mmHg or less. Acid-modified polypropylene a121 was obtained.
The acid value of a121 was 17.7, and Mn was 5,700.

Production Example 5
47 parts of acid-modified polypropylene a113 obtained in Production Example 3, 53 parts of ε-caprolactam and 3 parts of water were melted at 200 ° C. in a nitrogen gas atmosphere and reacted at 200 ° C. for 2 hours to obtain acid-modified polypropylene a122. Obtained.
The acid value of a122 was 26.1, and Mn was 3,700.

Production Example 6
90 parts of low molecular weight polypropylene and 0.5 part of cobalt hydroxide used in Production Example 2 are placed in a pressure resistant reactor, melted at 150 ° C., and a mixed gas of hydrogen and carbon monoxide 1: 1 is blown to 100 atm. And reacted at 150 ° C. for 5 hours. Thereafter, the pressure was returned to normal pressure, Tollen reagent was added, and the mixture was reacted at 150 ° C. for 3 hours to obtain acid-modified polypropylene a131. The acid value of a131 was 41.6, and Mn was 2,600.

Production Example 7
In a stainless steel autoclave, 60 parts of the acid-modified polypropylene a121 obtained in Production Example 4, 33 parts of polyethylene glycol (b11) (Mn 3,200, volume resistivity 3 × 10 ⁸ Ω · cm), sodium dodecylbenzenesulfonate 7 parts, 0.3 parts of antioxidant [Irganox 1010, manufactured by Ciba Specialty Chemicals Co., Ltd.] and 0.5 parts of zirconyl acetate were added and polymerized for 4 hours under reduced pressure at 230 ° C. and 1 mmHg or less. A thick polymer was obtained.
The polymer was taken out in a strand form on a belt and pelletized to obtain a block polymer A11.
The Mn of A11 was 28,000. Moreover, from this Mn and ¹ H-NMR analysis, the average number of repetitions Nn of A11 was 3.4. The refractive index measured by an Abbe refractometer based on JIS K7105 (1981) (hereinafter the same) was 1.497.

Production Example 8
In a stainless steel autoclave, 71 parts of acid-modified polypropylene a112 obtained in Production Example 2 and 2 parts of 12-aminododecanoic acid, α, ω-diaminopolyethylene glycol b21 (Mn 8,000, volume specific resistance 3 × 10 ⁷ Ω) Cm) 25 parts, lithium chloride 0.5 part, antioxidant (same as above) 0.3 part and zirconyl acetate 0.5 part were added and polymerized for 5 hours under conditions of 230 ° C. and 1 mmHg or less under reduced pressure. A viscous polymer was obtained. Thereafter, the same operation as in Production Example 7 was performed to obtain block polymer A21.
The Mn of A21 was 36,000. Moreover, from this Mn and ¹ H-NMR analysis, the average number of repetitions Nn of A21 was 2.0. The refractive index was 1.484.

Production Example 9
In a stainless steel autoclave, 31 parts of the acid-modified polypropylene a131 obtained in Production Example 6, 69 parts of polyethylene glycol b12 (Mn 6,000, volume resistivity 2 × 10 ⁵ Ω · cm), antioxidant (same as above) ) 0.3 parts and 0.5 parts of zirconyl acetate were added and polymerized for 4 hours under conditions of 230 ° C. and reduced pressure of 1 mmHg or less to obtain a viscous polymer. Thereafter, the same operation as in Production Example 7 was performed to obtain block polymer A31.
The Mn of A31 was 17,000. Moreover, from this Mn and ¹ H-NMR analysis, the average number of repetitions Nn of A31 was 2.1. The refractive index was 1.485.

Production Example 10
In a stainless steel autoclave, 47 parts of acid-modified polypropylene a111 obtained in Production Example 1, 3 parts of 12-aminododecanoic acid, polytetramethylene glycol (b13) (Mn 3,000, volume resistivity 8 × 10 ¹¹ Ω · cm) 50 parts, 0.3 parts of an antioxidant (same as above), 2 parts of sodium dodecylbenzenesulfonate and 0.5 parts of zinc acetate are added and polymerized for 5 hours at 230 ° C. under reduced pressure of 1 mmHg or less. A viscous polymer was obtained. Thereafter, the same operation as in Production Example 7 was performed to obtain block polymer A41.
The Mn of A41 was 28,000. Further, from this Mn and ¹ H-NMR analysis, the average repeating number Nn of A41 was 3.8. The refractive index was 1.490.

Production Example 11
Thermal degradation method with a Mn of 12,000 and a density of 0.89 [A polypropylene with a density of 0.90 at 23 ° C and a melt flow rate of 10 (g / 10 min) is thermally reduced at 400 ± 0.1 ° C. 95 parts of low molecular weight polypropylene and 5 parts of maleic anhydride obtained in the above were melted at 180 ° C. in a nitrogen atmosphere, and then a 50% xylene solution containing 1.5 parts of dicumyl peroxide was dissolved in 15 minutes. Then, the reaction was carried out for 1 hour. Thereafter, the solvent was distilled off to obtain a modified vinyl polymer F1 as a compatibilizer.
The acid value of F1 was 25.7, and Mn was 15,000. The refractive index was 1.501.

Examples 1-5, Comparative Examples 1-4
According to the formulation (parts) shown in Table 1, block polymer (A11, A21, A31, A41) or a linear cationic copolymer (A ratio 1) described later and a thermoplastic resin (B1, B2 described below) The resin composition of the present invention is optionally blended with a compatibilizer (F1) for 3 minutes in a Henschel mixer and then melt-kneaded in a twin-screw extruder with a vent at 220 ° C., 100 rpm, and a residence time of 3 minutes. Products (Examples 1 to 5) and comparative resin compositions (Comparative Examples 1 to 4) were obtained.

A ratio 1: linear cationic copolymer {trade name: ROLEX AS-170, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., refractive index 1.383}
B1: Polypropylene {Product name: Sun Allomer PM863V, manufactured by Sun Allomer Co., Ltd., refractive index 1.498}
B2: Polymethyl methacrylate {Brand name: ACRYPET VH, manufactured by Mitsubishi Rayon Co., Ltd., refractive index 1.489}

Performance Test About the resin composition of the present invention obtained in Examples 1 to 5 and the comparative resin composition obtained in Comparative Examples 1 to 4, respectively, using an injection molding machine [PS40E5ASE, manufactured by Nissei Plastic Industry Co., Ltd.] Each molding test piece is prepared at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C., and using these, transparency (total light transmittance, haze), mechanical properties (impact strength, flexural modulus and compatibility), Evaluation of water resistance, antistatic property (surface specific resistance value and surface specific resistance value after washing with water) and paintability (primary adhesion, water resistance and coating efficiency of the coating film) of the resin were performed according to the following methods. The results are shown in Table 2.

(1) Transparency 1) Total light transmittance A 2 mm thick, 40 mm square test plate was used, and a haze meter [manufactured by Nippon Denshoku Industries Co., Ltd.] was used and measured according to JIS K7105 (1981). .
2) Haze Using a 2 mm thick, 40 mm square test plate, a haze meter was used, and the haze was measured in accordance with JIS K7105 (1981).

(2) Mechanical properties 1) Impact strength Measured according to ASTM D256 (with notch, 3.2 mm thickness) Method A.
2) Flexural modulus Using a test piece (10 × 4 × 100 mm), it was measured according to ASTM D790 (distance between fulcrums 60 mm).
3) Compatibility The test piece (100 × 100 × 2 mm) is bent at 23 ± 5 ° C. (If it does not break once, the bending operation is repeated until it breaks), and the fracture surface is observed by the following criteria. evaluated.
Evaluation criteria ○ Good
X Defect [layered peeling with poor compatibility with (A) or (B)]

(3) Antistatic property 1) Surface specific resistance value Using a test piece (100 × 100 × 2 mm), it was measured in an atmosphere of 23 ° C. and humidity 50% RH with a super insulation meter (manufactured by Advantest Co., Ltd.) (ASTM D257).
2) Surface resistivity after washing with water The test piece (100 × 100 × 2 mm) leaning diagonally was washed with running water of 100 ml of ion-exchanged water (23 ° C.) at 23 ° C. and a flow rate of 100 ml / min. Dry at 80 ° C. for 3 hours. The operation of washing and drying was repeated 10 times, and the measurement was performed in an atmosphere of 23 ° C. and humidity 50% RH with a super insulation meter (manufactured by Advantest Co., Ltd.) (according to ASTM D257).

(4) Water resistance of the resin Tap water to a depth of 15 cm in a polypropylene lidded container with a diameter of 15 cm and a height of 20 cm is adjusted to a temperature of 40 ° C., and a test piece (100 × 100 × 2 mm) is about 5 cm below the surface of the water. In the state where the surface was sunk horizontally, the surface condition was evaluated by immersing for 120 hours and evaluated according to the following criteria.
Evaluation criteria ○ No change before and after evaluation
× Ward-shaped blisters or rough surface

(5) Coating test Using a grounding test piece (100 x 100 x 2 mm) and an electrostatic atomization electrostatic coating machine combined with air flow [Turbonea G minibell type automatic electrostatic coating device manufactured by Japan Landsburg Co., Ltd.] The test piece was electrostatically coated (applied voltage = -90 KV, discharge amount = 100 cc / min, rotation speed = 24,000 rpm, atomization head diameter = 70 mm, two-component urethane paint is Nippon Oil & Fats Co., Ltd. High Urethane # 5000 use). The coated plate was baked at 80 ° C. for 2 hours, and then the following test was performed. For the resin compositions obtained in Examples 1 and 2 and the resin compositions obtained in Comparative Examples 1 and 2 using the thermoplastic resin (B1), a corona treatment apparatus [HFS-202 manufactured by Kasuga Denki Co., Ltd.] After performing corona discharge treatment (30V × 10A = 300W, treatment for 1 second) using, electrostatic coating was performed.
1) Primary adhesion The coating surface of the coated plate was subjected to an adhesion test in accordance with JIS K5400 (1990) 8.5.2 cross-cut tape method.
2) Water resistance of coating film State of tap water in a polypropylene lidded container with a diameter of 15cm and a height of 20cm up to a depth of 15cm, temperature adjusted to 40 ° C, and a coating test piece submerged horizontally about 5cm below the surface of the water After 240 hours, the adhesion (primary adhesion) test was conducted as in 1).
3) Coating efficiency It calculated | required according to the following formula | equation.
Coating efficiency (%) = (weight after painting of test piece−weight before painting of test piece) × 100
÷ (absolute dry weight of discharged paint)

The absolute dry weight of the discharged paint was determined by the following method.
10 g of the paint was placed in a petri dish having a diameter of 15 cm and a depth of 1 cm, dried at 80 ° C. for 2 hours with a circulating dryer, and the weight (W1) of the paint after drying was measured and calculated according to the following formula.

Absolute dry weight of discharged paint = weight of paint discharged in coating test × (W1) / 10

  As is apparent from Table 2, the molded product formed by molding the resin composition of the present invention maintains transparency as compared with the molded product formed by molding the resin compositions of Comparative Examples 1 to 4, Excellent antistatic properties.

A molded product formed by molding the resin composition of the present invention has excellent permanent antistatic properties, mechanical properties, and transparency, as well as excellent paintability and printability. Therefore, the resin composition of the present invention can be used for various moldings such as injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, and film molding (casting method, tenter method, inflation method, etc.). Housing products such as home appliances / OA equipment, game equipment and office equipment, various plastic containers such as IC trays, various packaging films, flooring sheets, artificial turf, mats, automobile parts, etc. Widely used as a material for various molded products.

Claims (8)

The block of the polyolefin (a) and the block of the hydrophilic polymer (b) having a volume resistivity value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm are composed of an ester bond, an amide bond, an ether bond and an imide bond. An antistatic agent comprising a block polymer (A) having a structure in which the structure is repeatedly and alternately bonded through at least one bond selected from the group, and at least selected from the group consisting of a polyolefin resin (B1) and an acrylic resin (B2) In a molded article that is contained in one type of thermoplastic resin (B), the difference in refractive index between (A) and (B) is 0.01 or less, and the haze transparency of (B) is maintained . The antistatic resin composition for molded bodies , wherein the haze difference between the molded body and the thermoplastic resin (B) is 3.3% or less . The number average molecular weight of (A) is 2,000-60,000. The composition as described. The composition according to claim 1 or 2 , wherein (a) is an acid-modified polyolefin (a1). The composition according to any one of claims 1 to 3, wherein (A) is a block polymer comprising (A1) having a repeating unit represented by the following general formula (1).
[In the formula (1), n is an integer of 2 to 50, ^one of R ¹ and R ² is H and the other is H or a methyl group, y is an integer of 15 to 800, E ¹ is a hydroxyl group from a diol or a dihydric phenol. A ¹ is an alkylene group having 2 to 4 carbon atoms, m and m ′ are integers of 1 to 300, X and X ′ are general formulas (2), (3) and corresponding (2 ′) , (3 ′) (where X ′ is a symmetric group corresponding to X); (2), (3) and corresponding (2 ′), (3 ′), wherein R is H Or an alkyl group having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 11 carbon atoms, R ⁴ is H or an alkyl group having 1 to 10 carbon atoms, A ² is an alkylene having 2 to 4 carbon atoms in groups may be the same or different and a ¹ and a ^2, r is an integer from 1 to 20, u is 0 or 1, Q, T, Q 'and T' is the general formula (4), (5 And the corresponding (4 '), (5') a group represented by; general formula (4), (5) and the corresponding (4 '), (5') wherein, R ⁵ is H or a carbon number 1 to 10 alkyl groups, R ⁶ is H or a methyl group, t is 1 when R ⁶ is a methyl group, and 0 when H is H. ]
The composition according to any one of claims 1 to 4 , wherein the proportion of (A) based on the weight of (B) is 1 to 40% by weight. Further, selected from the group consisting of an alkali metal or alkaline earth metal salt (C), a surfactant (D), an ionic liquid (E), a compatibilizer (F), and other additives for resin (G). The composition according to any one of claims 1 to 5 , which contains at least one additive. The molded object formed by shape | molding the composition in any one of Claims 1-6 . A molded article obtained by coating or printing the molded body according to claim 7 .