JP5538122B2 - Polymer and antistatic agent comprising the same - Google Patents

Description

  The present invention relates to a polymer and an antistatic agent comprising the same. Specifically, in addition to antistatic properties, the present invention relates to an antistatic agent that does not impair its transparency and appearance even when blended with a resin, a resin composition containing the same, and a film and sheet made of the resin composition.

  In general, synthetic resins are used in various applications such as molded products and films because of their excellent characteristics. However, synthetic resin products are very electrostatic due to their hydrophobicity, so if dust or dirt adheres to the product and the appearance is impaired, electrical failure appears during processing, or it is used in electronic equipment Has the major drawback of causing malfunctions.

  Conventionally, as a means for solving these drawbacks, there are methods of adding various surfactants such as anions, cations, and nonions, which have been put into practical use. However, although this method of adding a surfactant is excellent in antistatic properties in a short period after product molding, the surfactant bleeded out on the product surface is lost due to friction, water washing, etc. It is difficult to maintain performance. Further, since the temperature at the time of molding of the synthetic resin product is high, the surfactant partly causes thermal decomposition, which causes smoke generation at the time of molding or coloring of the product. In addition, in multilayer films and sheets of synthetic resin, it is necessary to add an antistatic agent not only to the surface layer but also to the core layer in order to exert antistatic performance. There are disadvantages.

  In recent years, as means for solving the disadvantages and problems caused by the use of these surfactants, a polyester ester amide as a main component and an acid-modified polyolefin or the like as a third component are blended (Patent Document 1) or a cationized maleimide structure is prepared. (Patent Document 2) Polymer type antistatic agents have been proposed, but these are still insufficient in performance. Further, a polymer type antistatic agent obtained by copolymerizing a modified polyolefin and a polyfunctional hydrophilic group (Patent Documents 3 and 4) has been proposed, but there is a problem that the performance is not stable in a film and a sheet even though it is effective in a molded product. there were. In particular, when the film is used as a member such as a touch panel or a deflection plate, high optical homogeneity is required, but its appearance and transparency are not sufficiently satisfactory, such as generation of streaks and fish eyes.

Patent Document 5 proposes an antistatic agent containing a compound obtained by reacting boric acid and polyalkylene glycol. However, since this compound is not sufficiently compatible with a resin such as polyolefin, transparency is improved. It cannot be used for required applications.
Japanese Patent Laid-Open No. 11-170456 (2 pages) Japanese Patent No. 3077847 (pages 1 to 2) JP 2001-278985 A (2-5 pages) JP 2002-284880 A (2-3 pages) Japanese Patent No. 3761502

  An object of the present invention is to provide an antistatic agent that maintains antistatic properties for a long period of time and does not impair the appearance and transparency even when kneaded into a resin, and a resin composition containing the same.

  As a result of intensive studies, the present inventor has found that an antistatic agent comprising a specific polymer can solve the above problems, and has completed the present invention.

That is, the present invention
(A) a diol having a polyoxyalkylene group,
The present invention relates to a polymer obtained by reacting (b) a boron compound and (c) a polyolefin whose terminal is acid-modified.

  Hereinafter, the present invention will be described in detail.

(A) A diol having a polyoxyalkylene group can be obtained, for example, by adding an alkylene oxide to the diol. Specifically, in addition to polyethylene glycol and polypropylene glycol, for example, those represented by the following general formula (1) can be mentioned.

_{H- (OA 1) m-O} -R 1 -O- (A 2 O) n-H (1)

In the formula, R ₁ is a residue obtained by removing a hydroxyl group from a diol, A ₁ and A ₂ are each independently an alkylene group having 2 to 4 carbon atoms, and m and n are the number of alkylene oxides added per hydroxyl group of the diol. Represent. m (OA ₁ ) and n (A ₂ O) may be the same or different, and the bond form in the case where they are composed of two or more oxyalkylene groups is block or random or Any of these combinations may be used. m and n are 1-100 normally, Preferably it is 2-30, Most preferably, it is an integer of 3-10. M and n may be the same or different.

  Examples of the diol include dihydric alcohols (for example, aliphatic, alicyclic or aromatic dihydric alcohols having 2 to 12 carbon atoms), dihydric phenols having 6 to 18 carbon atoms, and tertiary amino group-containing diols. Examples of the aliphatic dihydric alcohol include alkylene glycol (ethylene glycol, propylene glycol), 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,12-dodecanediol. Examples of the alicyclic dihydric alcohol include cyclohexane dimethanol and hydrogenated bisphenol, and examples of the aromatic dihydric alcohol include xylylene diol. Examples of the dihydric phenol include monocyclic dihydric phenol (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenol (bisphenol A, bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-2,2-butane, Dihydroxybiphenyl, etc.) and condensed polycyclic dihydric phenols (dihydroxynaphthalene, binaphthol, etc.).

  Examples of the tertiary amino group-containing diol include aliphatic or alicyclic primary monoamines having 1 to 30 carbon atoms (methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, amylamine, isoamylamine, Hexylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-aminoheptane, 3-aminoheptane, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine, dodecylamine, etc. ) And bishydroxyalkylated products of aromatic primary monoamines having 6 to 12 carbon atoms (aniline, benzylamine, etc.). Of these, preferred are aliphatic dihydric alcohols and bisphenols, and particularly preferred are ethylene glycol and bisphenol A.

  Examples of the oxyalkylene group constituting the polyoxyalkylene group include an oxyethylene group, an oxypropylene group, and an oxybutylene group. The polyoxyalkylene group is composed of one or more of these, and can be obtained, for example, by adding an alkylene oxide to a diol at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst.

  As the diol having a polyoxyalkylene group, polyethylene glycol having a molecular weight of 300 to 2,000, more preferably 500 to 1,000, and an ethylene oxide adduct of bisphenol A can be used.

  Moreover, in the range which does not impair the effect of this invention, you may use together the monool which has a polyoxyalkylene group, and the polyhydric alcohol which has a polyoxyalkylene group with (a) diol which has a polyoxyalkylene group. These can be obtained, for example, by adding alkylene oxide to monool or polyhydric alcohol.

  Examples of monools include monohydric alcohols (for example, aliphatic, alicyclic or aromatic monohydric alcohols having 1 to 24 carbon atoms) and monohydric phenols having 6 to 18 carbon atoms. Specific examples of the monohydric alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, phenethyl alcohol, and the like. Examples of the monohydric phenol include phenol, o-cresol, m-cresol, p-cresol and the like. Examples of the polyhydric alcohol include glycerin, diglycerin, trimethylolpropane, pentaerythritol, sorbitol, sorbitan and the like.

  As the oxyalkylene group constituting the polyoxyalkylene group, the same ones as described above can be preferably used. The number of moles of alkylene oxide added is usually in the range of 1 to 100 moles, preferably 2 to 30. In the case of two or more kinds of alkylene oxides, the bonding form may be block, random, or a combination thereof.

  The boron compound used in the present invention is not particularly limited, but specifically, boric anhydride (boron oxide), for example, various boric acids such as orthoboric acid, metaboric acid, tetraboric acid, for example, boric acid. Examples thereof include S-L, complex compounds of borate ester and alcohol, and precursors that generate boric anhydride by heating such as alkyl borate.

  (C) The polyolefin whose terminal is acid-modified can be obtained, for example, by modifying the terminal of the polyolefin with an α, β-unsaturated carboxylic acid or its anhydride.

  Examples of polyolefins include polyolefins (polymerization method) obtained by polymerizing one or a mixture of two or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10), and high molecular weight polyolefins. The low molecular weight polyolefin (thermal degradation method) obtained by the thermal degradation method can be used. The number average molecular weight Mn of the polyolefin is preferably 100 to 10,000, more preferably 300 to 3,000, and most preferably 500 to 1,500.

  Examples of the olefin having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 2-butene, isobutene, and α-olefin having 5 to 30 carbon atoms (preferably 5 to 12, more preferably 5 to 10). 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene, dienes having 4 to 30 carbon atoms (preferably 4 to 18, more preferably 4 to 8), such as butadiene , Isoprene, cyclopentadiene, 11-dodecadiene and the like.

  Examples of the α, β-unsaturated carboxylic acid or anhydride thereof used for acid modification include monocarboxylic acid, dicarboxylic acid and anhydrides thereof such as (meth) acrylic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous ) Itaconic acid and (anhydrous) citraconic acid. Of these, fumaric acid and in particular (maleic anhydride) are preferred.

(C) It is preferable to use a polyolefin in which only one end is acid-modified as the polyolefin in which the terminal is acid-modified, because the viscosity characteristics of the resulting polymer can be easily controlled. Examples of the polyolefin in which only one terminal is acid-modified include poly (iso) butenyl succinic anhydride (PIBSA). PIBSA can be obtained by reacting isobutene homopolymer or poly (iso) butene, which is a copolymer of isobutene and n-butene, with maleic anhydride.

  The polymer of the present invention can also be obtained by reacting (a), (b) and (c) at a time, but (1) (a) and (b) in that the reaction is easy to control. (2) Production of reacting (b) with (b) after reacting (a) with (c) The method is preferred.

  In the production method (1), the reactions (a) and (b) proceed at 120 to 250 ° C. even without a catalyst. The reaction between the obtained reactant and (c) can be carried out at 150 to 250 ° C. in the presence of a catalyst. The catalyst may be an acid catalyst or an alkali catalyst, but an alkali catalyst is preferred because it can be used as it is for neutralizing acid groups derived from (c). The reaction molar ratio of (a) and (b) is not particularly limited, but by forming a crosslinked structure, a polymer having a viscosity characteristic close to that of a blank resin can be obtained. If (a) is 0.3-3 mol, it is preferable, and if it is 0.5-2 mol, it is more preferable. Subsequently, (c) is reacted so that the total mass of (a), (b) and (c) is 100%, so that it is 40 to 95 mass%, particularly 50 to 80 mass%, It is preferable in terms of compatibility between the obtained polymer and the resin.

  In the production method (2), the reactions (a) and (c) can be carried out at 150 to 250 ° C. in the presence of a catalyst. The catalyst may be an acid catalyst or an alkali catalyst, but an alkali catalyst is preferred because it can be used as it is for neutralizing acid groups derived from (c). The reaction between the obtained reactant and (b) proceeds at 120 to 250 ° C. even without a catalyst, but the catalyst of the previous reaction may remain. The reaction molar ratio of (a) and (c) is not particularly limited, but (a) is 0.1 to 2 with respect to 1 mol of (c) in terms of compatibility between the resulting polymer and the resin. If it is mol, it is preferable, and if it is 0.5-2 mol, it is more preferable. Furthermore, it is most preferable that the number of reactive groups in (b) is equal to the hydroxyl groups remaining in the reactants of (a) and (c) in that a polymer having a viscosity characteristic close to that of the blank resin can be obtained.

  When the acid group derived from (c) is present in the polymer, it is preferable that part or all of the acid group is neutralized with an alkaline substance. Examples of alkaline substances used for neutralization include hydroxides and carbonates of alkali metals such as lithium, potassium and sodium, hydroxides and carbonates of alkaline earth metals such as calcium and magnesium, ammonia, and organic amines. In view of antistatic properties, alkali metal hydroxides such as potassium are preferable. The ratio of the acid groups forming the salt is not necessarily all of the remaining acid groups, but is preferably 30 mol% or more, more preferably 50 mol% or more in terms of antistatic properties.

  The weight average molecular weight of the polymer according to the present invention is usually in the range of 2,000 to 1,000,000, but it is 5,000 to 300,000 in terms of both antistatic properties and compatibility with the resin. It is preferable if it is within the range. In the present invention, the “polymer” may be the polymer itself, or may be a polymer in a broad sense including components including unreacted components and side reaction products generated in each polymerization step.

  The polymer of the present invention can be suitably used particularly as an antistatic agent. The mechanism by which the polymer of the present invention imparts antistatic properties to the resin is not clear, but by incorporating a structural unit derived from boric acid into the polymer, the alkaline substance used to neutralize the remaining acid groups is separated. It is considered that an antistatic effect is exhibited. When using the polymer of this invention as an antistatic agent, 3-30 mass% is preferable in the thermoplastic resin, and 5-20 mass% is more preferable.

  The antistatic agent of the present invention can exhibit a sufficient effect even if it is used alone, but as long as it does not impair the object of the present invention, known anionic surfactants, cationic surfactants, nonionic interfaces other than the present invention are necessary. Activators and amphoteric surfactants may be used alone or in combination of two or more. In addition, polymer type antistatic agents such as alkali metal and alkaline earth metal salts, polyether ester amides, antioxidants, lubricants, colorants, ultraviolet absorbers and various additives usually added to resin products A filler can also be added as an additional component.

  Examples of the alkali metal or alkaline earth metal salt include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, hydrochloric acid, hydrobromic acid, hydroiodic acid and perchloric acid. And salts with inorganic acids such as sulfuric acid and phosphoric acid, and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid.

  Examples of the thermoplastic resin include polyolefin resin, polystyrene resin, acrylic resin, vinyl resin, polyamide resin, polyester resin, polyacetal resin, polycarbonate resin, thermoplastic polyurethane resin, fluororesin, and a mixture of two or more thereof. .

  Examples of the polyolefin resin include homopolymers of α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 4-methyl-1-pentene, copolymers of the α-olefins, Examples include a copolymer of a monomer other than an α-olefin copolymerizable with the α-olefin and an α-olefin, and a mixture thereof. Examples of the monomer other than the α-olefin copolymerizable with the α-olefin include vinyl acetate, maleic acid, methacrylic acid, methyl methacrylate, and ethyl methacrylate.

  Examples of the polystyrene resin include homopolymers of styrenes and copolymers of styrenes with monomers copolymerizable with styrenes. Specific examples include polystyrene, acrylonitrile-styrene resin (AS), and acrylonitrile-butadiene-styrene resin (ABS). Examples of the vinyl resin include diene polymers such as butadiene resin and polyisoprene resin. Examples of the polyamide resin include nylon. Polyester resins include aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene adipate, polyethylene succinate, polybutylene succinate, polyethylene succinate, polybutylene succinate adipate, polyethylene succinate adipate, poly Examples thereof include aliphatic polyesters such as caprolactone and polylactic acid. Examples of the polyacetal resin include a polymer of formaldehyde or trioxane. Examples of the polycarbonate resin include a condensate of bisphenol A and phosgene and a condensate of bisphenol A and carbonic acid diester. Examples of the thermoplastic polyurethane resin include a reaction product of an organic diisocyanate and a polymer diol. Examples of the fluororesin include polymers of fluorine-containing monomers.

  The thermoplastic resin to which the antistatic agent according to the present invention is added is a suitable material that can be applied to known publicly-known molding methods, and the molded product obtained is not particularly limited. For example, a film / sheet, monofilament, fiber, Thermoformed bodies such as multifilaments such as nonwoven fabrics, injection molded bodies, blow molded bodies, laminates, foams, and vacuum molded bodies can be mentioned. In addition, the resin composition to which the antistatic agent according to the present invention is added has good moldability when stretch-oriented and crystallizes, and the effects of the present invention are remarkably exhibited. Films / sheets, tape yarns, stretch blows obtained by stretching It is suitable for the production of molded articles and (mono, multi) filaments.

  As a molding method of a molded body obtained from the resin composition to which the antistatic agent according to the present invention is added, an injection molding method, a blow molding method (injection stretch blow, extrusion stretch blow, direct blow), a balloon method, inflation molding, Co-extrusion method, calendar method, hot press method, solvent casting method, (stretching) extrusion molding, extrusion lamination method with paper and aluminum, profile extrusion molding, thermoforming such as vacuum (pressure air) molding, melt spinning (monofilament, multi-filament) Filament, spunbond method, melt blown method, defibrating yarn method, etc.), foam molding method, compression molding method, etc., and any method can be applied.

  In particular, in the case of a molding method capable of taking a step of orientation orientation crystallization such as extrusion molding, melt spinning, etc., it is possible to improve the practical strength and appearance such as strength, heat resistance, impact resistance and transparency of the obtained molded body. It can be used more preferably. The molded product obtained from the resin composition to which the block polymer according to the present invention is added includes, for example, a molded product obtained by a publicly known / official molding method, and there are no restrictions on its shape, size, thickness, design, etc. There is no.

  A bottle, film or sheet, hollow tube, laminate, vacuum (compressed air) molded container, (mono, multi) filament, non-woven fabric, obtained from the above molding method by adding the resin composition to which the block polymer according to the present invention is added. Molded products such as foams include, for example, shopping bags, paper bags, shrink films, garbage bags, compost bags, lunch boxes, prepared food containers, food / confectionery packaging films, food wrap films, cosmetic / cosmetic wrap films. , Diapers, sanitary napkins, pharmaceutical wrap films, pharmaceutical wrap films, wrap films for surgical patches applied to stiff shoulders and sprains, agricultural and horticultural films, wrap films for agricultural products, greenhouse films, fertilizers Bags, packaging bands, magnetic tape cassettes for video and audio, etc. Disc packaging film, plate-making film, adhesive tape, tape, yarn, seedling pot, waterproof sheet, sandbag bag, architectural film, weed prevention sheet, vegetation net, etc., food, electronic, medical, pharmaceutical, cosmetics, etc. Films for packaging, films for electronic parts, electrical insulation films, films for laminating metal plates, films for glass displays, prism lens sheets for liquid crystal display components, base films for touch panels, backlights, polarizing plates, optics Lenses, covers for various instruments, antireflection films used on window glass for automobiles, trains, etc .; base films for display explosion-proof films, substrates for liquid crystal displays, organic EL display element substrates, substrates for color filters, substrates for touch panels, Optical sheets such as solar cell substrates; optical lenses, screens Lens sheet used for the emission and the like, electronics and automobile manufacturing industry, can be suitably used as various materials in a wide range of materials such as used in agriculture, civil engineering and fishery areas.

  Next, based on an Example, this invention is demonstrated in detail. However, the present invention is not limited to this embodiment.

[Production Example 1]
A stainless steel autoclave with a nitrogen inlet tube, a stirrer, and a thermometer (hereinafter simply referred to as “stainless steel autoclave”) was charged with 37.1 g of boric acid and 180 g of polyethylene glycol (hydroxyl value 374 mgKOH / g). Then, the temperature was raised to 220 ° C., and the mixture was reacted for 3 hours under a reduced pressure condition of trace nitrogen bubbling. The obtained product was a gel-like viscous polymer.

[Production Example 2]
A stainless steel autoclave was charged with 77.6 g of polybutenyl succinic acid (saponification value 90 mg KOH / g), 77.6 g of the product obtained in Production Example 1, and 0.7 g of an antioxidant (Irganox 1010). After sufficiently purging with nitrogen and raising the temperature to 80 ° C., 6.7 g of 48% KOH was added. Furthermore, after sufficient nitrogen substitution was performed and the temperature was raised to 220 ° C., the temperature was maintained at 220 ° C., 0.2 kPa or less, under a reduced pressure condition of trace nitrogen bubbling for 3 hours. The obtained product (referred to as Polymer 1) was a viscous polymer.

[Production Example 3]
A stainless steel autoclave was charged with 12.9 g of boric anhydride and 187.1 g of polyethylene glycol (hydroxyl value 374 mgKOH / g), sufficiently purged with nitrogen, heated to 220 ° C., and then subjected to reduced pressure conditions of trace nitrogen bubbling For 3 hours. The resulting product was a liquid polymer.

[Production Example 4]
A stainless steel autoclave was charged with 121.0 g of polybutenyl succinic acid (saponification value 90 mg KOH / g), 30.0 g of the product obtained in Production Example 3, and 0.7 g of an antioxidant (Irganox 1010). After sufficiently purging with nitrogen and raising the temperature to 80 ° C., 11.6 g of 48% KOH was added. Furthermore, after sufficient nitrogen substitution was performed and the temperature was raised to 220 ° C., the temperature was maintained at 220 ° C., 0.2 kPa or less, under a reduced pressure condition of trace nitrogen bubbling for 3 hours. The obtained product (referred to as polymer 2) was a viscous polymer.

[Production Example 5]
A stainless steel autoclave was charged with 24.7 g of boric acid, 120 g of polyethylene glycol (hydroxyl value 374 mgKOH / g), and 8.0 g of lithium iodide, sufficiently purged with nitrogen and heated to 220 ° C. The reaction was carried out for 3 hours under reduced pressure conditions of bubbling. The obtained product was a gel-like viscous polymer.

[Production Example 6]
A stainless steel autoclave was charged with 77.6 g of polybutenyl succinic acid (saponification value 90 mg KOH / g), 77.6 g of the product obtained in Production Example 5, and 0.7 g of an antioxidant (Irganox 1010). After sufficiently purging with nitrogen and raising the temperature to 220 ° C., the temperature was maintained at 220 ° C., 0.2 kPa or less, under reduced pressure conditions of trace nitrogen bubbling for 3 hours. The obtained product (referred to as polymer 3) was a viscous polymer.

[Production Example 7]
Stainless steel autoclave with polybutenyl succinic acid (saponification value 90 mgKOH / g) 100.1 g and polyethylene glycol (hydroxyl value 374 mgKOH / g) 49.5, antioxidant (Irganox 1010) 0.7 g, sodium hydroxide Was charged in an amount of 0.3 g. After sufficiently purging with nitrogen and raising the temperature to 220 ° C., the temperature was maintained at 220 ° C., 0.2 kPa or less, under a reduced pressure condition of trace nitrogen bubbling for 6 hours. The product obtained was a viscous polymer.

[Production Example 8]
A stainless steel autoclave was charged with 50.0 g of the product obtained in Production Example 7, 82.9 g of polyethylene glycol (hydroxyl value 374 mg KOH / g), and 17.1 g of boric acid. After sufficiently purging with nitrogen and raising the temperature to 220 ° C., the temperature was maintained at 220 ° C., 0.2 kPa or less, under reduced pressure conditions of trace nitrogen bubbling for 5 hours. The obtained product (referred to as polymer 4) was a gel polymer.

[Production Example 9]
A stainless steel autoclave was charged with 16.45 g of boric acid, 39.9 g of polyethylene glycol (hydroxyl value of 374 mgKOH / g), and 47.5 g of ethylene oxide adduct of stearyldiethanolamine (hydroxyl value of 314 mgKOH / g). Then, the temperature was raised to 220 ° C., and the mixture was reacted for 3 hours under a reduced pressure condition of trace nitrogen bubbling. The product was a gel-like viscous polymer.

[Production Example 10]
77.6 g of polybutenyl succinic acid (saponification value 90 mg KOH / g), 77.6 g of the product obtained in Production Example 9 and 0.7 g of an antioxidant (Irganox 1010) were charged. After sufficiently purging with nitrogen and raising the temperature to 80 ° C., 6.7 g of 48% KOH was added. Furthermore, after sufficient nitrogen substitution was performed and the temperature was raised to 220 ° C., the temperature was maintained at 220 ° C., 0.2 kPa or less, under a reduced pressure condition of trace nitrogen bubbling for 3 hours. The obtained product (referred to as polymer 5) was a viscous polymer.

[Production Example 13]
A stainless steel autoclave was charged with 2.1 g of boric anhydride and 187.1 g of bisphenol A-18EO adduct (Bisol 18EN manufactured by Toho Chemical Industry; hydroxyl value 111 mgKOH / g), sufficiently purged with nitrogen, and heated to 220 ° C. Then, the reaction was allowed to proceed for 3 hours under a reduced pressure condition of trace nitrogen bubbling. The product was a liquid polymer.

[Production Example 14]
121.0 g of polybutenyl succinic acid (saponification value 90 mgKOH / g), 99.3 g of the product obtained in Production Example 13 and 1.1 g of an antioxidant (Irganox 1010) were charged. After sufficiently purging with nitrogen and raising the temperature to 80 ° C., 11.3 g of 48% KOH was added. Furthermore, after sufficient nitrogen substitution was performed and the temperature was raised to 220 ° C., the temperature was maintained at 220 ° C., 0.2 kPa or less, under a reduced pressure condition of trace nitrogen bubbling for 3 hours. The obtained product (referred to as polymer 6) was a viscous polymer.

[Production Example 15]
A stainless steel autoclave was charged with 3.4 g of boric acid and 180.0 g of polyoxyethylene glycol (hydroxyl value 112 mgKOH / g), sufficiently purged with nitrogen, heated to 220 ° C., and reduced pressure conditions for trace nitrogen bubbling The reaction was allowed to proceed for 3 hours. The product was a liquid polymer.

[Production Example 16]
120.0 g of polybutenyl succinic acid (saponification value 62 mg KOH / g), 66.5 g of the product obtained in Production Example 15 and 1.1 g of an antioxidant (Irganox 1010) were charged. After sufficiently purging with nitrogen and raising the temperature to 80 ° C., 7.7 g of 48% KOH was added. Furthermore, after sufficient nitrogen substitution was performed and the temperature was raised to 220 ° C., the temperature was maintained at 220 ° C., 0.2 kPa or less, under a reduced pressure condition of trace nitrogen bubbling for 3 hours. The obtained product (referred to as polymer 7) was a viscous polymer.

[Production Example 17]
A stainless steel autoclave was charged with 8.0 g of boric anhydride, 92.0 g of polyoxyethylene glycol (hydroxyl value 374 mgKOH / g), and 69.0 g of methoxypolyethylene glycol (hydroxyl value 140 mgKOH / g), and sufficiently substituted with nitrogen. The mixture was heated to 220 ° C. and then reacted for 3 hours under a reduced pressure condition of a slight nitrogen bubbling. The product was a liquid polymer.

[Production Example 18]
77.6 g of polybutenyl succinic acid (saponification value 90 mg KOH / g), 19.4 g of the product obtained in Production Example 17 and 0.7 g of antioxidant (Irganox 1010) were charged. After sufficiently purging with nitrogen and raising the temperature to 80 ° C., 6.7 g of 48% KOH was added. Furthermore, after sufficient nitrogen substitution was performed and the temperature was raised to 220 ° C., the temperature was maintained at 220 ° C., 0.2 kPa or less, under a reduced pressure condition of trace nitrogen bubbling for 3 hours. The obtained product (referred to as polymer 8) was a viscous polymer.

[Comparative Production Example 1]
A stainless steel autoclave was charged with 62.3 g of cyclohexanetricarboxylic acid, 87.7 g of polyethylene glycol (hydroxyl value 374 mgKOH / g), and 0.3 g of paratoluenesulfonic acid as a catalyst. Then, the reaction was allowed to proceed for 2 hours under a reduced pressure condition of trace nitrogen bubbling. The obtained product (referred to as comparative polymer 1) was a viscous polymer in which a gel and solid were present.

[Comparative Production Example 2]
77.6 g of polybutenyl succinic acid (saponification value 90 mg KOH / g), 77.6 g of Comparative Production Example 1 and 0.7 g of antioxidant (Irganox 1010) were charged. After sufficiently purging with nitrogen and raising the temperature to 80 ° C., 6.7 g of 48% KOH was added, further replacing with nitrogen, raising the temperature to 220 ° C., then 220 ° C., 0.2 kPa or less, The conditions were maintained for 3 hours under reduced pressure with a slight amount of nitrogen bubbling. The obtained product (referred to as comparative polymer 2) was a viscous polymer.

[Comparative Production Example 3]
A stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer, and a thermometer was charged with 68.0 g of pentaerythritol, 22.0 g of ethylene oxide, and 0.1 g of KOH, followed by nitrogen substitution, and the temperature was gradually raised. After confirming the progress of the reaction by reducing the internal pressure of the autoclave, the temperature was raised to 120 ° C., and ethylene oxide was gradually introduced into the autoclave from a separate tank to carry out an addition reaction. The amount of ethylene oxide added was 594 g. The obtained product (referred to as comparative polymer 3) was a liquid polymer.

Preparation of test piece 1 The polymer of the present invention described above was blended in the blending amount shown in Table 1 with respect to polypropylene [Novatech PP FL6H (trade name: sold by Nippon Polypro Co., Ltd.)] as a thermoplastic resin, and Laboplast After being melt-mixed at 200 ° C. with a mill and a roller mixer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the mixed resin was molded into a sheet having a thickness of 0.5 mm, a length of 60 mm, and a width of 60 mm with a press. Next, this sheet was heated in an oven, and then stretched 5.0 times in length and 5.0 times in width to obtain a film having a thickness of 20 μm.

Preparation of test piece 2 The above-mentioned polymer of the present invention was blended in the blending amount shown in Table 1 with respect to polypropylene [Prime Polypro F-300SP (trade name: Prime Polymer Co., Ltd.)] as a thermoplastic resin. A 200 μm sheet was formed at a melting temperature of 200-240 ° C. using a T-die extruder.

Preparation of Specimen 3 The above-mentioned polymer of the present invention was blended in the blending amount shown in Table 1 with respect to polyethylene [Sumikasen F-102 (trade name: sold by Sumitomo Chemical Co., Ltd.)] as a thermoplastic resin. A 200 μm sheet was formed at a melting temperature of 200 to 220 ° C. using a die extruder.

Preparation of Test Piece 4 The above-mentioned polymer of the present invention was blended in the blending amount shown in Table 1 with respect to polylactic acid [Lacia H-400 (trade name: sold by Mitsui Chemicals, Inc.)] as a thermoplastic resin. After being dissolved and mixed at 200 ° C. with a lab plast mill and a roller mixer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the mixed resin was molded into a sheet having a thickness of 0.2 mm, a length of 60 mm, and a width of 60 mm using a press. . Next, this sheet was heated in an oven and then stretched 3.0 times in length and 3.0 times in width to obtain a film having a thickness of 20 μm.

<Evaluation method>
(1) Antistatic property After standing for 1 day in an environment with a temperature of 23 ° C. and a relative humidity of 50%, a super insulation meter P-616 manufactured by Kawaguchi Electric Co., Ltd. was used in accordance with JIS-K6911 under the same conditions. The surface resistivity of the test piece prepared in this way was measured. Further, the test piece was immersed in hot water at 80 ° C. for 30 minutes, and the surface was wiped with a clean cloth, and then the surface resistivity was measured. The smaller the value, the better the antistatic property. The target surface resistivity (LogΩ / □) is 13 or less.
(2) Appearance A test piece containing no antistatic agent was visually compared with a test piece containing the antistatic agent of the present invention. Those having an appearance equivalent to that of the unblended material and being compatible with the resin were evaluated as “Good”, and those having a bad appearance due to the occurrence of streaks, voids, fish eyes and the like were evaluated.
(3) Transparency Measure the HAZE value of the film and sheet prepared with a HAZE measuring device (HAZEMETER TC-HIIIDPK manufactured by Tokyo Denshoku Co., Ltd.), and the antistatic agent-free test piece and the antistatic agent of the present invention The difference ΔHAZE from the blended test piece was comparatively evaluated. The smaller ΔHAZE is, the closer the transparency is to a test piece containing no antistatic agent. The target for ΔHAZE is 10 or less.

From the above results, it was confirmed that the polymer according to the present invention was excellent in antistatic properties and durability, and did not impair the appearance and transparency even when kneaded into a resin.

Claims (7)

(A) a diol having a polyoxyalkylene group,
(B) a polymer obtained by reacting a boron compound and (c) poly (iso) butenyl succinic anhydride, obtained by the following production method (1) or (2), An antistatic agent comprising a polymer having a weight average molecular weight of 2,000 to 300,000.
Production method (1);
(A) and (b) are reacted so that (a) is 0.3 to 3 mol per mol of (b), and then the obtained reaction product and (c) are combined with (a), ( When the total mass of b) and (c) is 100%, the production method of obtaining the polymer by reacting (c) to be 40 to 95 mass%.
Production method (2);
(A) and (c) are reacted so that (a) is 0.1 to 2 mol per 1 mol of (c), and then the resulting reaction product and (b) are reacted to form the polymer. Manufacturing method. The antistatic agent according to claim 1, wherein (a) the diol having a polyoxyalkylene group is a compound represented by the following general formula (1).

_{H- (OA 1) m -O-} R 1 -O- (A 2 O) n -H (1)
(A ₁ and A ₂ each independently represents an alkylene group having 2 to 4 carbon atoms. R ₁ is a residue obtained by removing a hydroxyl group from a diol. M and n each independently represents an integer of 1 to 100. m (OA ₁ ) and n (A ₂ O) may be the same or different, and the bond form in the case where they are composed of two or more oxyalkylene groups is block or random or Any of these combinations may be used.) The antistatic agent according to claim 1 or 2, wherein the (b) boron compound is one or more selected from the group consisting of boric acid, boric anhydride, and alkyl borate. A thermoplastic resin composition comprising the antistatic agent according to claim 3 . The resin composition according to claim 4 , wherein the thermoplastic resin is a polyolefin resin. A film comprising the resin composition according to claim 4 or 5 . A sheet comprising the resin composition according to claim 4 or 5 .