JP2014062238A - Antistatic agent, and antistatic resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic agent capable of giving efficient permanent antistatic property to a molded article even with small amount addition without impairing exterior appearance and mechanical strength of the molded article, and to provide an antistatic resin composition containing the same.SOLUTION: There is provided an antistatic agent obtained by: copolymerizing ethylene with a vinyl compound (a) having 3 to 20 carbon atoms to obtain a copolymer (A); then adding an unsaturated acid anhydride (B) to the obtained copolymer (A) to obtain a polymer (C); and then ester bonding a monovalent hydroxyl group-containing compound (D) with a 1,3-dioxo-2-oxapropylene group of the obtained polymer (C). Here, the site where (B) is added is a carbon in (A), the carbon binding to at least two carbons and one hydrogen, a molar ratio of ethylene in (A) to (a) {a number of moles of the ethylene/a number of moles of (a)} is 95/5 to 70/30, and (D) is the hydroxyl group-containing compound containing a polyethylene oxide chain having a polymerization degree of 10 to 100.

Description

  The present invention relates to an antistatic agent and an antistatic resin composition containing the same.

  Conventionally, as a method for imparting antistatic properties to a highly insulating thermoplastic resin, a method of mixing a small amount of a surfactant with a thermoplastic resin is generally used. The antistatic property of a molded product obtained by molding a thermoplastic resin mixed with a surfactant is manifested by bleeding out of a low molecular weight surfactant on the surface of the molded product. Therefore, there is a problem that the antistatic effect is lost by washing or wiping the molded product, and it is difficult to maintain permanent antistatic properties. There is also a problem that the resin surface of the molded product is rough due to the bleed-out surfactant.

Known methods for imparting permanent antistatic properties to thermoplastic resins include (1) a method of mixing a conductive filler such as carbon black, and (2) a method of mixing a polymer type antistatic agent. However, in order to develop antistatic properties by the method (1), it is generally necessary to add a large amount of conductive filler, and the obtained thermoplastic resin composition does not have good processability, and the resin There is a problem that the molded article of the composition is inferior in mechanical strength such as impact resistance.
Moreover, as a method of (2), polyether polyamide (for example, patent document 1), polyether / polyolefin block polymer (for example, patent document 2), modified ethylene copolymer (for example, patent documents 3 and 4), etc. There is known a method of mixing a relatively small amount of a polymer type antistatic agent in a resin. However, when these antistatic agents are used, it is necessary to use more than 10% by weight in order to impart sufficient antistatic properties to the thermoplastic resin, and the physical properties of the molded product such as mechanical strength and heat resistance are reduced. There is a problem such as. Therefore, an antistatic agent that can impart permanent antistatic properties with a smaller amount of addition than before is desired.

Japanese Patent Laid-Open No. 08-12755 JP 2001-278985 A JP 2000-219738 A JP 09-111130 A

  The present invention relates to an antistatic agent capable of imparting sufficient permanent antistatic properties to a molded article even when added in a small amount without impairing the appearance and mechanical strength of the molded article, and an antistatic resin composition containing the same. The purpose is to provide.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention.
That is, the present invention relates to a polymer (C) obtained by adding an unsaturated acid anhydride (B) to a copolymer (A) of ethylene and a vinyl compound (a) having 3 to 20 carbon atoms. An antistatic agent in which a monovalent hydroxyl group-containing compound (D) is esterified to a dioxo-2-oxapropylene group, and the site to which (B) is added is carbon in (A), and at least carbon and It is carbon formed by two bonds and one bond with hydrogen, and the molar ratio of ethylene and (a) in (A) {number of moles of ethylene / number of moles of (a)} is 95/5 to 70. / 30 and (D) is an antistatic agent which is a hydroxyl group-containing compound having a polyethylene oxide chain with a degree of polymerization of 10 to 100; an antistatic resin composition containing this antistatic agent.

The antistatic agent and antistatic resin composition of the present invention have the following effects.
(1) The antistatic agent of the present invention can impart excellent permanent antistatic properties with a small amount of addition.
(2) A molded product obtained by molding the antistatic resin composition of the present invention is excellent in antistatic properties, appearance and mechanical strength.

  The antistatic agent of the present invention is a polymer (C) obtained by adding an unsaturated acid anhydride (B) to a copolymer (A) of ethylene and a vinyl compound (a) having 3 to 20 carbon atoms. , 3-dioxo-2-oxapropylene group is an antistatic agent obtained by esterifying a monovalent hydroxyl group-containing compound (D), and the site to which (B) is added is carbon in (A), Carbon having at least two bonds with carbon and one bond with hydrogen, and the molar ratio of ethylene and (a) in (A) {number of moles of ethylene / number of moles of (a)} is 95 / 5 to 70/30, and (D) is an antistatic agent that is a hydroxyl group-containing compound having a polyethylene oxide chain with a polymerization degree of 10 to 100.

As the vinyl compound (a), a compound having a (meth) acryloyl group having 3 to 20 carbon atoms {(meth) acrylic acid etc.}, an aromatic vinyl compound having 3 to 20 carbon atoms {styrene, t-butylstyrene, α -Methylstyrene, p-methylslene, ethylstyrene, divinylbenzene, 1,1-diphenylstyrene, bromostyrene, fluorostyrene, etc.}, vinyl ester compounds having 3 to 20 carbon atoms {vinyl acetate, vinyl propionate, vinyl butyrate, Vinyl herbate, vinyl caproate, vinyl enanthate, vinyl caprylate, vinyl pelargonate and vinyl caprate}, isopropenyl acetate, acrylonitrile, vinyl chloride and the like.
Among these, from the viewpoint of the reactivity of the addition reaction of (B), kneadability with the thermoplastic resin (E) and antistatic properties, a vinyl ester compound having 3 to 20 carbon atoms is preferable, and vinyl acetate is more preferable. Vinyl propionate, vinyl butyrate, vinyl valerate, vinyl caproate, vinyl enanthate, vinyl caprylate, vinyl pelargonate and vinyl caprate, and more preferably vinyl acetate.

  (A) may be used alone or in combination of two or more. When using 2 or more types together, from the viewpoint of the reactivity of the addition reaction of (B), kneadability with the thermoplastic resin (E) and antistatic properties, an aromatic vinyl compound having 3 to 20 carbon atoms and 3 carbon atoms ~ 20 vinyl ester compounds are preferred.

  The molar ratio {number of moles of ethylene / number of moles of (a)} of ethylene and vinyl compound (a) as monomers constituting the copolymer (A) is 95/5 to 70/30, From the viewpoint of dispersibility of the antistatic agent, 95/5 to 75/25 is preferable, and 90/10 to 80/20 is more preferable.

  The number average molecular weight (hereinafter referred to as Mn) of the copolymer (A) is preferably 3,000 to 500,000, more preferably 10,000 to 150,000 from the viewpoint of antistatic properties.

  The copolymer (A) is a copolymer of ethylene and a vinyl compound (a), and includes a random copolymer and a block copolymer. From the viewpoint of antistatic properties, block copolymers are preferred.

When (A) is a block copolymer, the degree of polymerization of the ethylene block is preferably 50 to 10,000, more preferably 200 to 3,000, from the viewpoint of dispersibility of the antistatic agent. .
Further, the degree of polymerization of the vinyl compound (a) block is preferably 10 to 1,200, more preferably 100 to 700, per block from the viewpoint of antistatic properties.
In (A), the degree of polymerization of at least one block is preferably in the above range, and more preferably 20 to 100% of the total number of blocks constituting (A) is in the above range.

Examples of the unsaturated acid anhydride (B) include compounds having 4 to 9 carbon atoms having an unsaturated double bond and a 1,3-dioxo-2-oxapropylene (—CO—O—CO—) group, Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and tetrahydrophthalic anhydride.
Among (B), maleic anhydride is preferable from the viewpoint of the reactivity of the addition reaction to (A) and the antistatic property.

  The polymer (C) is a polymer obtained by adding an unsaturated acid anhydride (B) to carbon obtained by bonding at least two carbon atoms in the copolymer (A) and one hydrogen atom. . For the production of the polymer (C), a conventional method of adding an unsaturated compound to the polyolefin (graft polymerization) can be used. For example, (A) and (B) without solvent using an extruder or the like. And an organic peroxide (for example, dicumyl peroxide) and a copolymer (A) and an acid anhydride such as maleic anhydride. It can be produced by a method in which it is used as a catalyst and heated to react in a solvent.

  In the present invention, the weight ratio {weight of (A) / weight of (B)} of the copolymer (A) and the unsaturated acid anhydride (B) constituting the polymer (C) is determined by dispersibility and charging. From the viewpoint of prevention, it is 95/5 to 70/30, and from the viewpoint of dispersibility of the antistatic agent, 95/5 to 75/25 is preferable, and more preferably 90/10 to 80/20.

The acid value of the polymer (C) is preferably 10 to 100, more preferably 20 to 40, from the viewpoint of antistatic properties and surface roughness of the molded product.
In addition, the acid value of a polymer (C) is measured by the method according to JISK6751-2.

The antistatic agent of the present invention is obtained by esterifying a polymer (C) with a monovalent hydroxyl group-containing compound (D).
The monovalent hydroxyl group-containing compound (D) is a hydroxyl group-containing compound containing a polyethylene oxide chain having a degree of polymerization of 10 to 100 of ethylene oxide (hereinafter sometimes abbreviated as EO). EO adducts to -20 hydroxyl group-containing compounds.
Examples of the hydroxyl group-containing compound having 1 to 20 carbon atoms include aliphatic alcohols (such as methanol, ethanol, propanol, butanol and hexanol), aromatic alcohols (such as phenol), araliphatic alcohols (such as benzyl alcohol), and alicyclic alcohols. (Cyclopentanol, cyclohexanol, methylcyclohexanol, etc.) and the like.

  The added mole number (polymerization degree) of EO is 10 to 100, but 20 to 70 is preferable and 20 to 60 is more preferable from the viewpoint of conductivity and strength.

  The Mn of the hydroxyl group-containing compound (D) is preferably 600 to 5,000, more preferably 800 to 3,000, from the viewpoint of conductivity.

  The weight ratio {the weight of (C) / the weight of (D)} of the polymer (C) and the monovalent hydroxyl group-containing compound (D) constituting the antistatic agent of the present invention is from the viewpoint of conductivity and strength. 90/10 to 20/80, more preferably 85/15 to 40/60.

  The antistatic agent of this invention can be obtained by esterifying a polymer (C) and a hydroxyl-containing compound (D) by a well-known method at 100 to 300 degreeC in the absence of a catalyst.

  The Mn of the antistatic agent is preferably from 2,000 to 1,000,000, more preferably from 4,000 to 500,000, from the viewpoint of mechanical properties and antistatic properties of the molded article of the antistatic resin composition described later. 000, particularly preferably 6,000 to 100,000.

The number average molecular weight (Mn) in the present invention can be measured under the following conditions using gel permeation chromatography (GPC).
Apparatus (example): “HLC-8120” [manufactured by Tosoh Corporation]
Column (example): “TSKgelGMHXL” (2 pieces)
"TSKgelMultiporeHXL-M" (1 pc.)
Sample solution: 0.3 wt% orthodichlorobenzene solution Solution injection amount: 100 μl
Flow rate: 1 ml / min Developing solvent: Orthodichlorobenzene Measurement temperature: 135 ° C
Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (Molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400) , 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

In the present invention, the acid value (mgKOH / g) of the antistatic agent is preferably 0 to 10, more preferably 0 to 5, and further preferably 0 to 2 from the viewpoint of antistatic properties.
When the acid value is within this range, the cation in the antistatic property improver (F) is not exchanged with the proton of the carboxyl group in the compound (C), and the antistatic property is good.
The acid value is measured by the following measurement method.

<Method for measuring acid value of antistatic agent>
About 2 g of sample (measured to 3 digits after the decimal point) is put into a 200 ml Erlenmeyer flask equipped with a cooling tube, 40 ml of xylene is added, and it is heated and dissolved with a hotting stirrer. After confirming complete dissolution, titration is quickly performed with a 0.1 mol / l potassium hydroxide / methyl alcohol titration solution using a phenolphthalein indicator.
A blank solution prepared in the same manner except that a measurement sample is not added is quickly titrated with a 0.1 mol / l potassium hydroxide / methyl alcohol titration solution using a phenolphthalein indicator.
The acid value is calculated by the following formula.
Acid value = (XY) × 5.61 / Z
X: The amount of 0.1 mol / l potassium hydroxide / methyl alcohol titration solution used for titration of the solution in which the measurement sample was dissolved (mL)
Y: Amount of 0.1 mol / l potassium hydroxide / methyl alcohol titration solution used for titration of blank solution (mL)
Z: Weight of measurement sample (g)

  The antistatic resin composition of the present invention is an antistatic resin composition containing the antistatic agent and the thermoplastic resin (E).

(E) includes polyphenylene ether resin (E1) (PPE); polyolefin resin (E2) [polypropylene (PP), polyethylene (PE), ethylene-vinyl acetate copolymer resin (EVA), and ethylene-ethyl acrylate copolymer resin Etc.]; poly (meth) acrylic resin (E3) [polymethyl methacrylate and the like]; polystyrene resin (E4) [vinyl group-containing aromatic hydrocarbons alone and vinyl group-containing aromatic hydrocarbons, and (meth) acrylic acid Copolymers comprising at least one selected from the group consisting of esters, (meth) acrylonitrile and butadiene; for example, polystyrene (PS), styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer Polymer (ABS resin), methyl methacrylate / butadi Polyester / styrene copolymer (MBS resin) and styrene / methyl methacrylate copolymer (MS resin)]; polyester resin (E5) [polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate and polyethylene Adipate]; polyamide resin (E6) [nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12, etc.]; polycarbonate resin (E7) [polycarbonate and Polycarbonate / ABS alloy resin (PC / ABS) and the like]; polyacetal resin (E8), and a mixture of two or more thereof.
Among these, (E1), (E2), (E3), (E4) and (E7) are preferable from the viewpoint of the mechanical properties of the molded product described later and the dispersibility of the antistatic agent in (E). is there.

The content (% by weight) of the antistatic agent in the antistatic resin composition of the present invention is 0.5% from the viewpoint of antistatic properties, based on the total weight of the antistatic agent and the thermoplastic resin (E). -30 is preferable, More preferably, it is 3-10.
The content (% by weight) of the thermoplastic resin (E) is preferably from 70 to 99.5, more preferably from the viewpoint of resin strength, based on the total weight of the antistatic agent and the thermoplastic resin (E). Is 90-97.

The antistatic resin composition of the present invention may further contain an antistatic agent (F). From the viewpoint of antistatic properties, it is preferable to contain (F).
The antistatic property improver (F) is selected from the group consisting of an alkali metal salt or alkaline earth metal salt (F1), a quaternary ammonium salt (F2), a surfactant (F3), and an ionic liquid (F4). At least one selected from the group consisting of

  Examples of the alkali metal salt or alkaline earth metal salt (F1) include alkali metals (lithium, sodium, potassium, etc.) or alkaline earth metals (magnesium, calcium, etc.) and organic acids [mono- or dicarboxylic acids having 1 to 7 carbon atoms]. Acids (formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.), sulfonic acids having 1 to 20 carbon atoms (methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, etc.) ) And thiocyanic acid], and organic and inorganic acids [hydrohalic acid (hydrochloric acid, hydrobromic acid, etc.), perchloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.] and alkaline earth metals Examples include salts.

  As the quaternary ammonium salt (F2), amidinium (1-ethyl-3-methylimidazolium or the like) or guanidinium (2-dimethylamino-1,3,4-trimethylimidazolinium or the like), the organic acid or the inorganic Examples include salts with acids.

  Examples of the surfactant (F3) include known nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

  The ionic liquid (F4) is a compound other than the above (F1) to (F3), has a melting point of 100 ° C. or lower, and at least one of the constituent cations or anions is an organic ion, and has an initial conductivity. Is 1 to 200 mS / cm (preferably 10 to 200 mS / cm), and specific examples include the molten salt exemplified in International Publication No. 95/15572.

  The antistatic property improver (F) is preferably a quaternary ammonium salt (F2) from the viewpoint of antistatic properties and moldability, more preferably a salt of amidinium and a sulfonic acid having 1 to 20 carbon atoms, Particularly preferred is 1-ethyl-3-methylimidazolium benzene sulfonate.

When the antistatic resin composition of the present invention contains the antistatic agent (F), the content (% by weight) of (F) is the antistatic agent, thermoplastic resin (E) and (F). From the viewpoint of giving a resin molded product having a good appearance without antistatic property and precipitation, based on the total weight of 0.01 to 29.01 is preferable, more preferably 0.05 to 7, particularly preferably. It is 0.1-5, Most preferably, it is 0.14-3.
Further, the content (% by weight) of the antistatic agent is based on the total weight of the antistatic agent and (E) and (F), from the viewpoint of giving a resin molded product having a good appearance without antistatic properties and precipitation. 0.99 to 29.99, more preferably 1 to 20, particularly preferably 1.5 to 15, and most preferably 2.5 to 10.
In addition, the content (% by weight) of (E) is based on the total weight of the antistatic agent and (E) and (F), from the viewpoint of giving a resin molded product having a good appearance without antistatic properties and precipitation. 70-99, more preferably 73-98.86, particularly preferably 82-98.36, and most preferably 87-97.36.

The weight ratio of the antistatic agent to the antistatic agent (F) {weight of antistatic agent / weight of (F)} is preferably 99/1 to 70/30 from the viewpoint of conductivity. Preferably it is 96/4 to 80/20, and next more preferably it is 96/4 to 90/10.
The ratio of the total weight of the antistatic agent and antistatic agent (F) to the weight of the thermoplastic resin (E) {total weight of antistatic agent and (F) / weight of (E)} From the viewpoint of properties and strength, 1/99 to 20/80 is preferable, and 3/97 to 10/90 is more preferable.

  The antistatic resin composition composition of the present invention may further contain an additive (G). (G) includes compatibilizer (G1), colorant (G2), mold release agent (G3), antioxidant (G4), flame retardant (G5), ultraviolet absorber (G6), antibacterial agent (G7 ) And a filler (G8). (G) may use 2 or more types together.

  As the compatibilizing agent (G1), a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group (for example, A polymer described in JP-A-3-258850, a modified vinyl polymer having a sulfonic acid group described in JP-A-6-345927, and a block polymer having a polyolefin part and an aromatic vinyl polymer part) Etc.

  Colorants (G2) include inorganic pigments (white pigments, cobalt compounds, iron compounds, sulfides, etc.), organic pigments (azo pigments, polycyclic pigments, etc.) and dyes (azo, indigoid, sulfide, alizarin). System, acridine system, thiazole system, nitro system, aniline system, etc.).

  As a mold release agent (G3), C12-18 fatty acid alkyl (C1-4) ester (butyl stearate, etc.), C2-18 fatty acid glycol (C2-8) ester (Ethylene glycol monostearate, etc.), polyhydric (trivalent or higher) alcohol esters (hardened castor oil, etc.) of fatty acids having 2 to 18 carbon atoms, liquid paraffin and the like.

  Examples of the antioxidant (G4) include phenol compounds [monocyclic phenol (2,6-di-t-butyl-p-cresol, etc.), bisphenol [2,2′-methylenebis (4-methyl-6-t-butylphenol). And the like] and polycyclic phenols [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, etc.]], sulfur compounds (dilauryl- 3,3′-thiodipropionate etc.), phosphorus compounds (triphenyl phosphite etc.), amine compounds (octylated diphenylamine etc.) and the like.

  Examples of the flame retardant (G5) include halogen-containing flame retardants, nitrogen-containing flame retardants, sulfur-containing flame retardants, silicon-containing flame retardants and phosphorus-containing flame retardants.

  Examples of the ultraviolet absorber (G6) include benzotriazole [2- (2′-hydroxy-5′-methylphenyl) benzotriazole and the like], benzophenone (2-hydroxy-4-methoxybenzophenone and the like), salicylate (phenyl salicylate). Etc.) and acrylates (2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate etc.) and the like.

  Examples of the antibacterial agent (G7) include benzoic acid, sorbic acid, halogenated phenol, organic iodine, nitrile (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylene bisthocyanocyanate, etc.), N- Examples include haloalkylthioimides, copper agents (such as 8-oxyquinoline copper), benzimidazoles, benzothiazoles, trihaloallyls, triazoles, organic nitrogen sulfur compounds (such as Suraoff 39), quaternary ammonium compounds, and pyridine skeleton-containing compounds.

  Examples of the filler (G8) include inorganic fillers (such as calcium carbonate, talc, and clay) and organic fillers (such as urea and calcium stearate).

The addition amount of (G1) based on the total weight of the antistatic agent and (E) is preferably 0 to 20% by weight, more preferably 0.1 to 15% by weight, from the viewpoint of mechanical properties of the molded product. The amount is particularly preferably 1 to 10% by weight, particularly preferably 1.5 to 8% by weight.
The total amount of (G2) to (G8) based on the total weight of the antistatic agent and (E) is preferably 0 to 45% by weight, more preferably 0.001 from the viewpoint of the mechanical properties of the molded product. -40% by weight, particularly preferably 0.01-35% by weight, most preferably 0.05-30% by weight.

The antistatic resin composition of the present invention can be obtained by melt-mixing the antistatic agent and the thermoplastic resin (E) of the present invention and (F) and / or (G) if necessary. As a method of melt-mixing, generally, each component in the form of pellets or powder is mixed with an appropriate mixer (such as Henschel mixer (registered trademark)) and then melt-mixed with an extruder to form pellets. Can be applied.
There is no particular limitation on the order of addition of each component during melt mixing, for example,
[1] A method of melting and mixing (E) and, if necessary, (F) and / or (G) after melt-mixing the antistatic agent.
[2] After melt-mixing the antistatic agent, a part of (E) is melt-mixed in advance to prepare a high-concentration composition (masterbatch resin composition) of the antistatic agent, and then the remaining (E) and A method of melt-mixing (F) and / or (G) as necessary (master batch method or master pellet method).
Etc.
The concentration of the antistatic agent in the masterbatch resin composition in the method [2] is preferably 40 to 80% by weight, more preferably 50 to 70% by weight.
Of the methods [1] and [2], the method [2] is preferable from the viewpoint that the antistatic agent can be efficiently dispersed in (E).

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

The molded article of the present invention has excellent mechanical properties and permanent antistatic properties, as well as good paintability and printability, and a molded article can be obtained by coating and / or printing the molded article.
Examples of the method for coating a molded product include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, dip coating, roller coating, and brush coating.
As the paint, paints generally used for plastic coating can be used, and specific examples include polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint.
The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is preferably 10 to 50 μm from the viewpoint of antistatic properties.

As a method for printing on a molded product or a surface on which a molded product has been coated, any printing method generally used for plastic printing can be used. Gravure printing, flexographic printing, screen printing, pad printing And dry offset printing and offset printing.
As the printing ink, those usually used for plastic printing can be used, and examples include gravure ink, flexo ink, screen ink, pad ink, dry offset ink, and offset ink.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the part in an Example represents a weight part and% represents weight%.

<Production Example 1>
[Production of hydroxyl group-containing compound (D-1)]
In a pressure-resistant autoclave reaction kettle, 100 parts of triethylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.) and 0.1 part of sodium hydroxide (Wako Pure Chemical Industries, Ltd.) are placed. The pressure was reduced to 1 Mpa, and 997 parts of EO was added dropwise at a reaction temperature of 140 ° C. over 5 hours to obtain a hydroxyl group-containing compound (D-1) (EO 45 mol adduct, Mn 2,000). The product was identified by NMR (manufactured by BRUKER) and GPC (the following conditions).
Apparatus: HLC-8120 manufactured by Tosoh Corporation
Column: 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF (tetrahydrofuran) solution Solution injection amount: 100 μl
Detector: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (Molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

<Production Example 2>
[Production of hydroxyl group-containing compound (D-2)]
In Production Example 1, a hydroxyl group-containing compound (D-2) (EO 20 mol adduct, Mn900) was obtained in the same manner as in Production Example 1 except that 455 parts of EO was used instead of 997 parts of EO.

<Production Example 3>
[Production of hydroxyl group-containing compound (D-3)]
In Production Example 1, a hydroxyl group-containing compound (D-3) (EO 60 mol adduct, Mn 2,700) was obtained in the same manner as in Production Example 1 except that 1536 parts of EO was used instead of 997 parts of EO.

<Production Example 4>
[Production of hydroxyl group-containing compound (D-4)]
In Production Example 1, a hydroxyl group-containing compound (D-4) (EO 10 mol adduct, Mn485) was obtained in the same manner as in Production Example 1 except that 168 parts of EO was used instead of 997 parts of EO.

<Production Example 5>
[Production of hydroxyl group-containing compound (D-5)]
In Production Example 1, a hydroxyl group-containing compound (D-5) (EO 5 mol adduct, Mn 270) was obtained in the same manner as in Production Example 1 except that 52.6 parts of EO was used instead of 997 parts of EO.

<Production Example 6>
[Production of hydroxyl group-containing compound (D-6)]
In Production Example 1, a hydroxyl group-containing compound (D-6) (EO 100 mol adduct, Mn 4,600) was obtained in the same manner as in Production Example 1 except that 540 parts of EO was used instead of 997 parts of EO. .

<Production Example 7>
[Production of hydroxyl group-containing compound (D-7)]
In Production Example 1, a hydroxyl group-containing compound (D-7) (EO 130 mol adduct, Mn 5,900) was obtained in the same manner as in Production Example 1, except that 326 parts of EO was used instead of 997 parts of EO. .

<Production Example 8>
[Production of antistatic agent (F-1)]
In a pressure-resistant reaction vessel, 124 parts of benzenesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in 124 parts of methanol, and this is dissolved in 1-ethyl-3-methylimidazolium monomethyl carbonate (the synthesis method is disclosed in JP-A-2001-2001). 187 parts of a methanol solution (concentration 48%) of 316372 according to the method described in 316372. 1-ethyl-3-methylimidazolium benzene is removed by removing all of the solvent at 60-80 ° C. over about 5 hours under reduced pressure after the reaction is carried out while generating carbon dioxide by the reaction. The sulfonate was obtained.

<Production Example 9>
In a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introducing tube and pressure reducing device, an ethylene / vinyl acetate copolymer (Mn 15,000, product name “EVA400”) is used as the copolymer (A). Honeywell's 100 parts ethylene / vinyl acetate = 80/20) and 10.1 parts maleic anhydride as an unsaturated anhydride (B) were added with 68.8 parts xylene and dissolved uniformly. Substitution was performed, and after heating at 150 ° C. for 1 hour, a solution prepared by dissolving 0.053 part of dicumyl peroxide as an initiator in 7 parts of xylene was added dropwise over 2 hours to obtain the polymer (C-1). Obtained (acid number 29.4, Mn 100,000).

<Production Example 10>
In Production Example 9, instead of 100 parts of “ethylene / vinyl acetate copolymer (Mn 15,000, product name“ EVA400 ”, manufactured by Honeywell)”, “ethylene / vinyl acetate copolymer (MFR (melt flow rate)”) = 20, product name “Ultrasen 633”, manufactured by Tosoh Corporation, ethylene / vinyl acetate = 90/10) 100 parts ”,“ maleic anhydride 10.1 parts ”,“ maleic anhydride 12.2 A polymer (C-2) (acid value 35.5, Mn 99,000) was obtained in the same manner as in Example 1, except that “part” was used.

<Production Example 11>
In Production Example 9, instead of 100 parts of “ethylene / vinyl acetate copolymer (Mn 15,000, product name“ EVA400 ”, manufactured by Honeywell)”, “ethylene / vinyl acetate copolymer (MFR = 15, product name)” Instead of “UBE polyethylene V319”, Ube Maruzen Polyethylene Co., Ltd., 100 parts ethylene / vinyl acetate = 70/30), “10.1 parts maleic anhydride”, “17.5 parts maleic anhydride” Except having used, it carried out similarly to Example 1, and obtained the polymer (C-3) (The acid value of 48.5, Mn110,000).

<Example 1>
[Production of antistatic agent (1)]
After 40 parts of the hydroxyl group-containing compound (D-1) and 100 parts of the polymer (C-1) are esterified at a reaction temperature of 100 ° C. for 10 hours, xylene is distilled off under reduced pressure to prevent the antistatic property of the present invention. Agent (1) was obtained.

<Examples 2 to 6>
In Example 1, in place of (D-1) and (C-1), antistatic agents (2) to (6) were similarly used except that (C) and (D) shown in Table 1 were used, respectively. )

<Examples 7 to 10>
In Example 1, instead of (D-1) and (C-1), (C) and (D) shown in Table 1 were used respectively, and “reaction temperature was changed to 100 ° C.” instead of “reaction temperature” Was set at 130 ° C., and in the esterification reaction, antistatic agents (7) to (10) were obtained in the same manner except that “by-product water was removed by Dean Stark”.

<Comparative Example 1>
[Production of Comparative Antistatic Agent (1 ′)]
A comparative antistatic agent (1 ′) was prepared according to Production Example 6 of JP-A-2001-278985.

<Comparative Examples 2-3>
In Example 1, in place of (D-1) and (C-1), except that (C) and (D) shown in Table 1 were used, respectively, antistatic agents (2 ′) to ( 3 ′) was obtained.

About the antistatic agent obtained in Examples 1-10 and Comparative Examples 2-3, the acid value was measured with the following measuring method. The results are shown in Table 1.
<Method for measuring acid value of antistatic agent>
About 2 g of the sample (measured to 3 digits after the decimal point) was put into a 200 ml Erlenmeyer flask equipped with a cooling tube, 40 ml of xylene was added, and the mixture was heated and dissolved with a hotting stirrer. After confirming complete dissolution, before the sample was precipitated, titration was quickly performed with a 0.1 mol / l potassium hydroxide / methyl alcohol titration solution using a phenolphthalein indicator.
A blank solution prepared in the same manner except that the measurement sample was not added was quickly titrated with a 0.1 mol / l potassium hydroxide / methyl alcohol titration solution using a phenolphthalein indicator.
The acid value was calculated by the following formula.
Acid value = (XY) × 5.61 / Z
X: The amount of 0.1 mol / l potassium hydroxide / methyl alcohol titration solution used for titration of the solution in which the measurement sample was dissolved (mL)
Y: Amount of 0.1 mol / l potassium hydroxide / methyl alcohol titration solution used for titration of blank solution (mL)
Z: Weight of measurement sample (g)

<Example 11>
[Production of antistatic resin composition]
Plastoyl (Toyo Seiki Co., Ltd.) 2.86 parts of antistatic agent (1) and 0.14 part of 1-ethyl-3-methylimidazolium salt (F-1) of benzenesulfonic acid as antistatic agent (F) (Made by company) (180 degreeC, 40 rpm). 3 parts of this kneaded product and 97 parts of PP resin (product name “PM771M”, manufactured by Sun Allomer Co., Ltd.) as (E) were kneaded in a plastmill (200 ° C., 40 rpm) for 5 minutes. Furthermore, this was cut into pellets using a pelletizer (manufactured by Horai Co., Ltd.), blended for 3 minutes with a Henschel mixer (manufactured by Nihon Coke Kogyo Co., Ltd.), and then 900 rpm, The mixture was melt-kneaded at a melting temperature of 200 ° C. for a residence time of 5 minutes to obtain an antistatic resin composition (1) of the present invention.

<Examples 12 to 27>
The antistatic resin compositions (2) to (17) of the present invention were obtained by kneading in the compositions and blending ratios shown in Table 2 instead of the components in Example 10.

<Comparative Examples 4-6>
Instead of each component of Example 10, the compositions and blending ratios shown in Table 2 were kneaded to obtain comparative antistatic resin compositions (H1) to (H3).

In addition, the following were used for each component in Table 2.
E-1: PP resin [trade name “PM771M”, manufactured by Sun Allomer Co., Ltd.]
E-2: HIPS resin (impact polystyrene resin) [trade name “HIPS 433”, manufactured by PS Japan Ltd.]
E-3: ABS resin [trade name “Cebian 680SF”, manufactured by Daicel Polymer Co., Ltd.]
E-4: PC / ABS resin [trade name “Psycoloy C6600”, manufactured by SABIC Innovative Plastics Japan LLC]

  Antistatic resin compositions (1) to (17) obtained in Examples 11 to 27 and antistatic resin compositions (H1) to (H3) obtained in Comparative Examples 4 to 6 were injected into an injection molding machine [ Model number “PS40E5ASE”, manufactured by Nissei Plastic Industry Co., Ltd. The same shall apply hereinafter, and a molded product (100 × 100 × 2 mm) was produced under conditions of a cylinder temperature of 220 ° C. and a mold temperature of 50 ° C., and performance evaluation of the following items was performed. The results are shown in Table 2.

<Performance test items>
(1) Surface resistivity (unit: Ω)
In accordance with ASTM D257, the surface resistivity of a test piece (100 × 100 × 2 mm) was measured at 23 ° C. and a humidity of 50% RH using a superinsulator “DSM-8103” (manufactured by Toa DKK). The value was measured.

(2) Izod impact strength (Unit: J / m)
Measured according to ASTM D256 Method A (notched, 3.2 mm thickness).

(3) Appearance (3-1) Surface appearance The appearance of the front and back surfaces of an injection molded product (100 × 100 × 2 mm) was observed and evaluated according to the following criteria.
(Evaluation criteria)
○ Good with no abnormalities (equivalent to thermoplastic resin containing no antistatic agent)
× Surface roughness, swelling, etc. are observed

(3-2) Cross-sectional appearance It cut | disconnected with the cutter perpendicularly | vertically to the surface so that it might pass through the surface center part of a test piece (100x100x2mm), the cross section was observed, and the following reference | standard evaluated.
(Evaluation criteria)
○ Cross section is uniform and good (equivalent to thermoplastic resin containing no antistatic agent)
× Cross section is non-uniform

  As is apparent from Table 2, it can be seen that the antistatic property of the present invention can be imparted by adding a small amount. In addition, the antistatic resin composition containing the antistatic agent of the present invention gives a molded article having excellent permanent antistatic properties and is excellent in appearance and mechanical strength.

  The antistatic agent of the present invention can impart excellent permanent antistatic properties to a molded product and is excellent in appearance and mechanical strength, so various molding methods [injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding. , Blow molding, foam molding and film molding (cast method, tenter method and inflation method)], housing products (for home appliances / OA equipment, game machines, office equipment, etc.), plastic container materials [used in clean rooms Trays (IC trays, etc.) and other containers], various cushioning materials, covering materials (wrapping film, protective film, etc.), flooring sheets, artificial grass, mats, tape base materials (for semiconductor manufacturing processes, etc.) And it is suitable as a material for various molded products (automobile parts etc.).

Claims (13)

1,3-Dioxo-2-oxa of a polymer (C) formed by adding an unsaturated acid anhydride (B) to a copolymer (A) of ethylene and a vinyl compound (a) having 3 to 20 carbon atoms An antistatic agent obtained by esterifying a monovalent hydroxyl group-containing compound (D) into a propylene group,
The site to which (B) is added is the carbon in (A), which is a carbon that is bonded to at least two carbons and bonded to one hydrogen.
The molar ratio of ethylene in (A) to (a) {number of moles of ethylene / number of moles of (a)} is 95/5 to 70/30,
An antistatic agent in which (D) is a hydroxyl group-containing compound having a polyethylene oxide chain with a degree of polymerization of 10 to 100. The weight ratio {weight of (A) / weight of (B)} of the copolymer (A) and the unsaturated acid anhydride (B) constituting the polymer (C) is 95/5 to 30/70. The antistatic agent according to claim 1. The weight ratio {weight of (C) / weight of (D)} between the polymer (C) and the monovalent hydroxyl group-containing compound (D) is 90/10 to 20/80. Antistatic agent. The antistatic agent according to any one of claims 1 to 3, wherein the monovalent hydroxyl group-containing compound (D) has a number average molecular weight of 600 to 5,000. The antistatic agent according to any one of claims 1 to 4, wherein the copolymer (A) is a block copolymer of ethylene and a vinyl compound (a) having 3 to 20 carbon atoms. The copolymer (A) is a block copolymer of ethylene and a vinyl compound (a) having 3 to 20 carbon atoms, the degree of polymerization of ethylene in at least one block is 50 to 10,000, and at least one The antistatic agent according to any one of claims 1 to 5, wherein the degree of polymerization of the block (a) is 10 to 1,200. The antistatic resin composition containing the antistatic agent in any one of Claims 1-6, and a thermoplastic resin (E). The content of the antistatic agent is 0.5 to 30% by weight and the content of (E) is 70 to 99.5% by weight based on the total weight of the antistatic agent and the thermoplastic resin (E). 8. The antistatic resin composition according to 7. Further, at least one antistatic agent selected from the group consisting of alkali metal salts or alkaline earth metal salts (F1), quaternary ammonium salts (F2), surfactants (F3) and ionic liquids (F4). The antistatic resin composition according to claim 7 or 8, comprising (F). Based on the total weight of the antistatic agent, the thermoplastic resin (E) and the antistatic property improving agent (F), the content of the antistatic agent is 0.99 to 29.9% by weight, and the content of (E) is The antistatic resin composition according to claim 9, wherein the content of (F) is 70 to 99% by weight and 0.01 to 29.01% by weight. The antistatic property according to claim 9 or 10, wherein the weight ratio of the antistatic agent to the antistatic property improver (F) {weight of the antistatic agent / weight of (F)} is 99/1 to 70/30. Resin composition. The ratio of the total weight of antistatic agent and antistatic agent (F) to the weight of thermoplastic resin (E) {total weight of antistatic agent and (F) / weight of (E)} is 1 / 99- It is 20/80, The antistatic resin composition in any one of Claims 9-11. A molded article obtained by molding the antistatic resin composition according to any one of claims 7 to 12.