TWI423950B - Ammonium salt and antistatic composition containing same - Google Patents

Description

Ammonium salt and antistatic resin composition containing the same: AMMONIUM SALT AND ANTISTATIC COMPOSITION CONTAINING SAME

The present invention relates to a novel ammonium salt which is liquid at normal temperature, an antistatic agent for a resin using the ammonium salt, and an antistatic resin composition.

Japanese Laid-Open Patent Publication No. Hei 10-60322 discloses that a thiocyanate which can be used as an antistatic agent may be a metal thiocyanate such as sodium thiocyanate or potassium thiocyanate.

The present invention provides an antistatic agent for a resin, an antistatic resin composition containing the antistatic agent for the resin, and the like. The antistatic agent for a resin is characterized by containing an ammonium salt represented by the formula (1) (i.e., didecyldimethylammonium = thiocyanato) as an active ingredient.

Formula (1): R ¹ R ² R ³ R ⁴ N ⁺ SCN ^- (1) (wherein R ¹ and R ² each represent a fluorenyl group, and R ³ and R ⁴ each represent a methyl group).

In the present invention, "normal temperature" means 25 °C.

The ammonium salt represented by the formula (1) of the present invention (hereinafter referred to as ammonium salt (1)) can be, for example, an ammonium halide (hereinafter referred to as ammonium halide (2)) represented by the formula (2) using thiocyanate or An alkali metal salt (hereinafter referred to as thiocyanate) is produced by anion exchange.

Formula (2): R ¹ R ² R ³ R ⁴ N ⁺ X ^- (2) (wherein R ¹ to R ⁴ represent the same as defined above, and X represents a halogen atom).

A commercially available product can be used for the ammonium halide (2), for example, an amine represented by the formula (3) (hereinafter referred to as an amine (3)) and a halogenated alkane represented by the formula (4) (hereinafter referred to as a halogenated alkane). (4)) Manufactured by reaction.

R ¹ R ² R ³ N (3) (wherein R ¹ to R ³ represent the same as those described above.)

R ⁴ X (4) (wherein R ⁴ and X represent the same as those described above.)

Examples of the halogenated hydrocarbons (4) include methyl chloride, methyl bromide, methyl iodide and the like.

The amount of haloalkane (4) used is generally from 0.5 moles to 5 moles, preferably from 0.6 moles to 3 moles, and from 0.8 moles to 2 moles, relative to 1 mole of amine (3). Better.

The reaction of the amine (3) with the halogenated alkane (4) can be carried out without a solvent or in the presence of a solvent. Examples of the solvent in the case of carrying out the reaction in the presence of a solvent include alcohol solvents such as methanol, ethanol, and isopropanol; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate and butyl acetate; and tetrahydrofuran. 1, 4 - 2 An ether solvent such as an alkane; an aromatic hydrocarbon solvent such as toluene or xylene; an aliphatic or alicyclic hydrocarbon solvent such as hexane or cyclohexane; The amount of the solvent to be used is not particularly limited, but is usually 10 parts by weight or less, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 1 part by weight, per part by weight of the amine (3).

The reaction of the amine (3) with the halogenated alkane (4), for example, a mixture of the amine (3), the halogenated alkane (4) and the solvent, preferably at a temperature of 20 ° C or higher (preferably 60 ° C to 140 ° C) It is carried out by heating and stirring.

As described above, after the reaction mixture containing the ammonium halide (2) is obtained, the obtained reaction mixture can be used as it is in the reaction for producing the ammonium salt (1) of the present invention. And if necessary, the reaction mixture can be concentrated to obtain a residue containing ammonium halide (2) as a main component, and the residue can be used as it is in the reaction for producing the ammonium salt (1) of the present invention. Further, if necessary, the obtained residue may be mixed with an organic solvent, and an unreacted raw material or the like contained in the residue may be dissolved in an organic solvent, filtered, and the obtained purified ammonium halide (2) may be used in the production. In the reaction of the ammonium salt (1) of the present invention.

Examples of the thiocyanic acid include thiocyanic acid, sodium thiocyanate, potassium thiocyanate, and lithium thiocyanate. Among them, sodium thiocyanate or potassium thiocyanate is preferred. The amount of the thiocyanic acid used is generally 0.5 mol or more with respect to 1 mol of ammonium halide (2), and preferably 1 mol to 2 mol.

The anion exchange reaction is usually carried out in an aqueous solvent. The amount of water used is not particularly limited, but is usually 20 parts by weight or less, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 3 parts by weight, per part by weight of the ammonium halide (2).

The order of mixing the ammonium halide (2), the thiocyanate, and the water is not particularly limited, and the ammonium halide (2) may be mixed with water and then added with thiocyanate; or the thiocyanate may be mixed with water to form activated carbon. Decolorants (decolorants) After treatment, the filtrate obtained by filtration is used in an anion exchange reaction.

The reaction temperature is usually above 0 ° C, preferably from 10 to 80 ° C, and particularly preferably from 20 to 60 ° C.

After the completion of the reaction, the method for extracting the ammonium salt (1) of the present invention from the obtained reaction mixture may be, for example, separating the reaction liquid into an organic layer and an aqueous layer, and washing the organic layer as needed, followed by concentrating the organic layer. a method of obtaining the ammonium salt (1); adding an organic solvent insoluble in water (for example, toluene, ethyl acetate, dichloromethane, etc.) during or after the reaction, and extracting from an organic solvent insoluble in water The ammonium salt is washed with water as needed, and then the organic salt is distilled off to obtain the ammonium salt (1).

The antistatic agent for a resin of the present invention is composed of the ammonium salt (1) of the present invention as an active ingredient, and may be used alone as an antistatic agent for a resin, or may be an additive such as a stabilizer or a solvent as required. Mixed use. The antistatic agent for a resin containing the ammonium salt (1) imparts an excellent antistatic function to the resin without impairing the transparency of the resin.

According to the method of adding the antistatic agent for a resin to a resin or the like, a resin composition containing the antistatic agent for the resin can be produced. Further, the resin composition containing the antistatic agent for a resin has transparency and is an antistatic property which exhibits a low surface resistance value.

The resin to be used for the antistatic resin composition of the present invention is usually a thermoplastic resin, a thermosetting resin, and a photocurable resin (for example, an acrylic photocurable resin).

Examples of thermoplastic resins are: polyethylene, polypropylene, ethylene or propylene with, for example, ethyl acetate, alpha- Copolymers of other vinyl monomers such as olefins and (meth) acrylates, addition polymers of norbornenes, addition copolymers of norbornenes and α-olefins, ring-opening polymerization of norbornenes Hydrogenated polymer, cyclopentadiene ring-opening polymer hydrogenated polymer, cyclohexadiene ring-opening polymer hydrogenated polymer and other polyolefin; polyvinyl chloride, polyvinylidene chloride and other chlorine-containing resin; Styrene resin such as polystyrene, AS resin, ABS resin, MS resin, MBS resin; (meth)acrylic resin such as polyacrylic acid, polymethacrylic acid, polymethyl methacrylate, etc.; by aromatic dihydroxy compound (for example) : bisphenol A) polycarbonate such as aromatic polycarbonate produced by carbon chlorohydrin or diphenyl carbonate; polyamines such as nylon 4, nylon 6, nylon 8, nylon 11, nylon 12, nylon 66; Thermoplastic polyimine such as ether quinone; polyester such as polyethylene terephthalate or polybutylene terephthalate; and mixtures thereof.

Among these resins, a (meth)acrylic resin is preferred.

Examples of thermosetting resins are epoxy resins (for example, bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, phenolic epoxy resin, etc.); thermosetting Polyimine (for example, polycondensate of pyromellitic anhydride and bis(4-aminophenyl)ether); polyurethane; phenol resin; amine resin (for example: melamine resin, urea) Resin, etc.), of which epoxy resin is preferred.

In the resin composition of the present invention, the antistatic agent for the resin of the present invention is contained in an amount of 0.05 to 50% by weight, preferably 0.5 to 25% by weight, particularly preferably 2 to 10% by weight based on the resin.

[Examples]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the examples. Further, in the following examples, the surface resistance value was measured using an IrrestaHT-210 manufactured by Mitsubishi Chemical Corporation at an applied voltage of 500V.

[Example 1]

180.6 g (0.4 mol) of Arquad 210-80E [dichlorodimethylammonium chloride-containing aqueous solution of ethanol (concentration 80.2%), registered trademark; manufactured by LION AKZO Co., Ltd.], 48.6 g (0.6 Sodium thiocyanate and 115.4 g of ion-exchanged water were mixed and stirred at 25 ° C for 1 hour. After completion of the reaction, the organic layer was separated by a liquid separation operation and washed twice with 115.4 g of ion-exchanged water. The obtained organic layer was concentrated under reduced pressure to give 146.2 g (yield: 95.0%) of dimethyl thiocyanate (hereinafter referred to as DDDMA-SCN) which was liquid at normal temperature. The NMR data of DDDMA-SCN and the melting point data are presented below.

¹ H-NMR (CDCl ₃ ) σ: 0.89 (t, 6H), 1.26-1.39 (m, 28H), 1.75-1.78 (m, 4H), 3.30 (s, 6H), 3.42-3.46 (m, 4H)

Melting point: 23 ° C

[Embodiment 2]

To 100 parts by weight of a two-liquid cross-linking type acrylic adhesive SK-DYNE 909A (registered trademark; manufactured by Soken Chemical Co., Ltd.), 5 parts by weight of DDDMA-SCN and 0.2 parts by weight of a hardener L-based for acrylic resin are added. 45 (manufactured by Soken Chemical Co., Ltd.) and 150 parts by weight of ethyl acetate/methyl ethyl ketone (50/50) as a diluent solvent to prepare an adhesive coating liquid. This adhesive coating liquid was applied onto a polyester film by a bar coater to have a film thickness of about 10 μm after drying, and then heated at 80 ° C for 2 minutes to be hardened to prepare a test film for evaluation. The test film thus prepared was kept in an environment of 15 to 20 ° C and 50% RH for 24 hours, and then the surface resistance value of the coated surface was measured at 20 ° C and 50% RH. In terms of transparency, it is visually observed that "○" when transparent, and "x" when it is opaque. The results are shown in Table 1.

[Comparative Example 1] and [Comparative Example 2]

A test film was produced in the same manner as in Example 2 except that the antistatic agent shown in Table 1 was used instead of the DDDMA-SCN described in Example 2, and the same surface resistance value as in Example 2 was measured for the test film. . The results are shown in Table 1. Meanwhile, DDDMA-NO ₃ and DDDMA-PTS in Table 1 represent (didecyldimethyl)ammonium nitrate and (didecyldimethyl)ammonium p-toluenesulfonate, respectively.

As is clear from the results of Table 1, the surface resistivity of the acrylic resin composition to which the antistatic agent for a resin of the present invention is added is a slight value compared with the case where an ammonium salt of an anion other than the thiocyanate ion is used. However, it is preferable in terms of transparency of the resin.

[Example 3]

100 parts by weight of bisphenol A type epoxy resin EPIKOTE 828 (epoxy equivalent: 186 g/eq, registered trademark; manufactured by Nippon Epoxy Co., Ltd.), 14.1 parts by weight of imino dipropylamine as a hardening agent, and 5.7 weight The DDDMA-SCN (5% by weight relative to the resin) was mixed to obtain an epoxy resin composition. This epoxy resin composition was poured into a circular mold having a diameter of 50 mm and a depth of 5 mm, and heated at 50 ° C for 1 hour, and further heated at 100 ° C for 6 hours to be thermally cured to prepare a test piece for evaluation. The prepared test piece was allowed to stand in an environment of 23 ° C and 50% RH for 6 hours, and then the surface resistance of the test piece was measured at 23 ° C and 50% RH. In terms of transparency, it is visually observed that "○" when transparent, and "x" when it is opaque. The results are shown in Table 2.

[Comparative Example 3] and [Comparative Example 4]

A test piece was produced in the same manner as in Example 3 except that the antistatic agent shown in Table 2 was used instead of the DDDMA-SCN described in Example 3, and the same surface resistance value as in Example 3 was measured for the test piece. . In terms of transparency, the same procedure as in Example 3 was also carried out, and the results of the results are shown in Table 2.

As is clear from the results of Table 2, the epoxy resin composition to which the antistatic agent for a resin of the present invention is added exhibits the same degree of transparency and low surface as compared with the case of using an ammonium salt other than thiocyanate ion as an anion. resistance.

[Industrial availability]

Since the ammonium salt of the present invention is a liquid at normal temperature, it is easy to handle and can be expected to be used in various fields. The antistatic agent for a resin containing the ammonium salt imparts an excellent antistatic function to the resin without impairing the transparency of the resin. Further, the resin composition containing the antistatic agent for a resin has transparency and is an antistatic property which exhibits a low surface resistance value.

Claims (3)

A compound which is (didecyldimethyl)ammonium thiocyanate. An antistatic agent for a resin characterized by containing (dimercaptodimethylammonium) thiocyanate as an active ingredient. An antistatic resin composition characterized by containing an antistatic agent for a resin as in the second aspect of the patent application.