Composition, composition production method, and molded body

Abstract

One aspect of the present disclosure provides a composition containing: a polymer of a hydrophobic polymerizable compound; PEDOT:PSS; and a surfactant.

Description

Composition, Method for Producing Composition, and Molded Body

[0001] The present disclosure relates to a composition, a method for producing the composition, and a molded body.

[0002] In recent years, polymer compositions having electrical conductivity have been used in packaging materials for electronic components, antistatic paints, parts of household appliances, and the like. As a method for imparting conductivity to a polymer, a method of mixing a polymer with a compound having conductivity can be mentioned.

[0003] For example, Patent Document 1 discloses a reaction product of a monomer having a cationic reactive group, a conductive polymer such as polyaniline, and a protonic acid dopant, and a thermosetting conductive polymer composition characterized in that the protonic acid dopant is heated to act as a cationic polymerization initiator, whereby the monomer is polymerized and cured.

[0004] Japanese Patent Application Laid-Open No. 2015-10202

[0005] One aspect of the present invention is to provide a novel composition having conductivity.

[0006] The inventors of the present invention considered imparting conductivity by combining a polymer of a hydrophobic polymerizable compound and PEDOT:PSS, but a composition having conductivity could not be obtained by simply adding PEDOT:PSS to the polymer, and it was found that a composition having conductivity could be obtained by further using a surfactant in combination.

[0007] The present invention includes the following aspects: [1] A composition comprising a polymer of a hydrophobic polymerizable compound, PEDOT:PSS, and a surfactant. [2] The composition according to [1], wherein the surfactant has a functional group capable of initiating polymerization of the polymerizable compound. [3] The composition according to [1] or [2], wherein the surfactant has a strongly acidic functional group. [4] The composition according to any one of [1] to [3], wherein the surfactant has a sulfo group. [5] The composition according to any one of [1] to [4], wherein the surfactant comprises dodecylbenzenesulfonic acid. [6] The composition according to any one of [1] to [5], wherein the polymerizable compound comprises a styrene-based compound. [7] The composition according to any one of [1] to [6], wherein the content of the polymer of the polymerizable compound is 30% by mass or more and 99% by mass or less based on the total amount of the composition. [8] The composition according to any one of [1] to [7], wherein the content of PEDOT:PSS is 0.01% by mass or more and 30% by mass or less based on the total amount of the composition. [9] The composition according to any one of [1] to [8], wherein the surfactant content is 0.01% by mass or more and 50% by mass or less based on the total amount of the composition.

[10] A method for producing a composition, comprising: step B1 of polymerizing a hydrophobic polymerizable compound in the presence of a surfactant to obtain a polymer; step B2 of mixing the polymer with a PEDOT:PSS solution containing PEDOT:PSS and a solvent to obtain a mixture; and step B3 of removing the solvent from the mixture.

[11] The method for producing a composition according to

[10] , wherein the PEDOT:PSS solution further comprises alkylene glycol.

[12] The method for producing a composition according to

[10] or

[11] , further comprising step C of melt-kneading the composition obtained in step B3 with the polymer.

[13] A molded article comprising the composition according to [1] to [9] and having a thickness of 0.1 mm or more.

[0008] According to one aspect of the present invention, a novel conductive composition can be provided.

[0009] The embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments described below.

[0010] One embodiment of the present invention is a composition (hereinafter also referred to as "Composition 1") containing a hydrophobic polymerizable compound (hereinafter also simply referred to as "polymerizable compound"), PEDOT:PSS, and a surfactant. In this specification, "hydrophobic" means that the solubility in 100 mL of water is 5 g or less at 20°C. The solubility of the hydrophobic polymerizable compound in 100 mL of water may be 3 g or less, or 1 g or less, at 20°C.

[0011] Polymerizable compounds may contain compounds having unsaturated bonds. Examples of compounds having unsaturated bonds include aromatic vinyl compounds, olefin compounds, and (meth)acrylic acid ester compounds. Polymerizable compounds may contain one or more of these compounds.

[0012] The polymerizable compound may contain aromatic vinyl compounds and may contain styrene compounds. Examples of styrene compounds include styrene, o-methylstyrene, β-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-β-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-β-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-chlorostyrene, β-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o- Examples include chlorostyrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-t-butylstyrene, m-t-butylstyrene, p-t-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, and styrene derivatives substituted with silyl groups. Polymerizable compounds preferably contain styrene.

[0013] Polymerizable compounds may include aromatic vinyl compounds other than styrene compounds. Examples of aromatic vinyl compounds other than styrene compounds include divinylbenzene compounds (1,2-divinylbenzene, 1,3-divinylbenzene, etc.), vinylnaphthalene compounds, vinylanthracene compounds, and the like.

[0014] Examples of olefin compounds include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, and 1-hexene.

[0015] Examples of (meth)acrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and phenyl methacrylate. Other examples of (meth)acrylic acid ester compounds include n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, amyl acrylate, isoamyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, and phenyl acrylate. In this specification, "(meth)acrylic acid ester" includes either or both of acrylic acid esters and methacrylic acid esters.

[0016] The polymerizable compound content may be 10% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more, based on the total amount of composition 1, and may be 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less. The polymerizable compound content may be, for example, 10 to 90% by mass, based on the total amount of composition 1.

[0017] PEDOT:PSS is poly(3,4-ethylenedioxythiophene) doped with polystyrene sulfonic acid. By including PEDOT:PSS as a conductive polymer, a composition with excellent conductivity (composition 2 described later) can be obtained.

[0018] From the viewpoint of further enhancing the conductivity of composition 2, the PEDOT:PSS content may be 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, based on the total amount of composition 1. From the viewpoint of enhancing the transparency of composition 2, the PEDOT:PSS content may be 1% by mass or less, 0.8% by mass or less, or 0.6% by mass or less, based on the total amount of composition 1. From the viewpoint of further enhancing the conductivity of composition 2, the PEDOT:PSS content may be, for example, 0.01 to 0.8% by mass, based on the total amount of composition 1.

[0019] From the viewpoint of further enhancing the conductivity of composition 2, the content of PEDOT:PSS may be 0.1 parts by mass or more, 0.3 parts by mass or more, 0.5 parts by mass or more, 0.7 parts by mass or more, 0.9 parts by mass or more, 1 part by mass or more, 1.2 parts by mass or more, 1.3 parts by mass or more, 1.4 parts by mass or more, or 10 parts by mass or more, per 100 parts by mass of polymerizable compound. From the viewpoint of enhancing the transparency of composition 2, the content of PEDOT:PSS may be 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 6 parts by mass or less, 5 parts by mass or less, 4 parts by mass or less, 2 parts by mass or less, 1.3 parts by mass or less, 1 part by mass or less, 0.8 parts by mass or less, 0.6 parts by mass or less, 0.4 parts by mass or less, or 0.2 parts by mass or less, per 100 parts by mass of polymerizable compound. The PEDOT:PSS content may be, for example, 0.1 to 20 parts by mass per 100 parts by mass of polymerizable compound.

[0020] The PEDOT:PSS content may be 0.1 parts by mass or more, 0.2 parts by mass or more, 0.3 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 1.2 parts by mass or more, 1.4 parts by mass or more, 1.5 parts by mass or more, 1.6 parts by mass or more, 2 parts by mass or more, 2.5 parts by mass or more, 2.8 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, or 20 parts by mass or more, per 100 parts by mass of surfactant. The content of PEDOT:PSS may be 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 6 parts by mass or less, 5 parts by mass or less, 4 parts by mass or less, 3.5 parts by mass or less, 3 parts by mass or less, 2.5 parts by mass or less, 2 parts by mass or less, 1 part by mass or less, 0.8 parts by mass or less, 0.5 parts by mass or less, or 0.4 parts by mass or less, per 100 parts by mass of surfactant, from the viewpoint of enhancing the transparency of composition 2. The content of PEDOT:PSS may be, for example, 0.1 to 40 parts by mass per 100 parts by mass of surfactant.

[0021] Composition 1 according to this embodiment contains a surfactant from the viewpoint of enhancing the conductivity of composition 2. The inclusion of a surfactant in the composition improves the dispersibility of PEDOT:PSS in the hydrophobic polymerizable compound (or its polymer), thereby improving the uniformity of the composition. As a result, a composition 2 with excellent conductivity can be obtained, and furthermore, the transparency of composition 2 may also be improved.

[0022] The surfactant may be, for example, a nonionic surfactant, anionic surfactant, a cationic surfactant, or an amphoteric surfactant. The surfactant may consist of one or more types.

[0023] The surfactant is preferably an anionic surfactant. The surfactant (anionic surfactant) may have a strongly acidic functional group as its hydrophilic group. The strongly acidic functional group has the function of initiating the polymerization of polymerizable compounds. That is, the surfactant may have a functional group capable of initiating the polymerization of polymerizable compounds. Examples of strongly acidic functional groups include sulfo groups and sulfonic acid bases. The sulfonic acid base may be a sodium sulfonate base.

[0024] Examples of hydrophobic groups in surfactants include alkyl groups, alkenyl groups, and aryl groups. Alkyl and alkenyl groups may be linear or branched.

[0025] The number of carbon atoms in the hydrophobic group of the surfactant may be 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may be 40 or less, 30 or less, 28 or less, 26 or less, 24 or less, 22 or less, 20 or less, or 18 or less. The number of carbon atoms in the hydrophobic group of the surfactant may be, for example, 4 to 40.

[0026] The surfactant may include at least one selected from the group consisting of alkylbenzenesulfonic acid, alkylsulfonic acid, and salts thereof. The salt may be a sodium salt. Examples of alkyl groups in alkylbenzenesulfonic acid and alkyl groups in alkylsulfonic acid include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, etc. From the viewpoint of further enhancing the transparency and conductivity of composition 2, the surfactant may include dodecylbenzenesulfonic acid or a salt thereof.

[0027] The surfactant content may be 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 32 parts by mass or more, 35 parts by mass or more, 37 parts by mass or more, 40 parts by mass or more, 42 parts by mass or more, 43 parts by mass or more, or 43.3 parts by mass or more, per 100 parts by mass of polymerizable compound, and may be 60 parts by mass or less, 55 parts by mass or less, 52 parts by mass or less, 48 ​​parts by mass or less, 45 parts by mass or less, 43.3 parts by mass or less, 43 parts by mass or less, or 30 parts by mass or less. The surfactant content may be, for example, 20 to 60 parts by mass per 100 parts by mass of polymerizable compound.

[0028] The surfactant content may be 1% by mass or more, 5% by mass or more, or 10% by mass or more, based on the total amount of composition 1, and may be 50% by mass or less, 40% by mass or less, 30% by mass or less, or 20% by mass or less. The surfactant content may be, for example, 1 to 50% by mass, based on the total amount of composition 1.

[0029] Composition 1 according to one embodiment may further contain a polymerization initiator capable of initiating the polymerization of a polymerizable compound. In this specification, a compound that is both a polymerization initiator and a surfactant will be classified as a surfactant. That is, in addition to the surfactant described above, composition 1 according to one embodiment may further contain a polymerization initiator that is not classified as a surfactant. The polymerization initiator may include at least one selected from the group consisting of radical polymerization initiators, cationic polymerization initiators, and anionic polymerization initiators, and may include a radical polymerization initiator.

[0030] Examples of radical polymerization initiators include organic peroxides, azo compounds, benzoin compounds, benzoin ether compounds, acetophenone compounds, and benzopinacol.

[0031] Examples of cationic polymerization initiators include sulfonium salts, phosphonium salts, quaternary ammonium salts, aryldiazonium salts, organometallic salts, allene-ion complexes, and boron trifluoride amine complexes.

[0032] Examples of anionic polymerization initiators include aliphatic amine compounds, aromatic amine compounds, secondary or tertiary amine compounds, imidazole compounds, polymercaptan compounds, boron trifluoride-amine complexes, dicyandiamides, and organic acid hydrazides.

[0033] Composition 1 according to one embodiment may contain a solvent. Examples of solvents include alcohols, alkylene glycols, sugars, alkoxides, etc. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, etc. The solvent content may be 50% by mass or more, 60% by mass or more, or 70% by mass or more, and 99.9% by mass or less, based on the total amount of PEDOT:PSS and the solvent. For example, the solvent content may be 50 to 99.9% by mass, based on the total amount of PEDOT:PSS and the solvent.

[0034] One embodiment of the present invention is a composition (hereinafter also referred to as "Composition 2" or "Masterbatch") containing a polymer of a hydrophobic polymerizable compound, PEDOT:PSS, and a surfactant. The details of the polymerizable compound and the surfactant in the polymer of the hydrophobic polymerizable compound are the same as those described above as the polymerizable compound and surfactant in Composition 1.

[0035] The polymer content of the polymerizable compound may be 30% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 67% by mass or more, 69% by mass or more, 69.3% by mass or more, 69.5% by mass or more, 69.7% by mass or more, 69.9% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, 88% by mass or more, 95% by mass or more, or 96% by mass or more, and may be 99% by mass or less, 98% by mass or less, 97% by mass or less, 92% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 73% by mass or less, 70% by mass or less, 69.7% by mass or less, 69.2% by mass or less, or 65% by mass or less, based on the total amount of composition 2. The content of polymerizable compound polymers may be, for example, 30 to 99% by mass based on the total amount of composition 2.

[0036] The PEDOT:PSS content may be 0.01% by mass or more, 0.02% by mass or more, 0.03% by mass or more, 0.04% by mass or more, 0.05% by mass or more, 0.06% by mass or more, 0.07% by mass or more, 0.08% by mass or more, 0.1% by mass or more, 0.2% by mass or more, 0.4% by mass or more, 0.5% by mass or more, 0.7% by mass or more, 0.8% by mass or more, 0.9% by mass or more, 1% by mass or more, 5% by mass or more, or 8% by mass or more, based on the total amount of composition 2, from the viewpoint of further enhancing the conductivity of composition 2. From the viewpoint of enhancing the transparency of composition 2, the PEDOT:PSS content may be 30% by mass or less, 20% by mass or less, 15% by mass or less, 12% by mass or less, 10% by mass or less, 9% by mass or less, 8% by mass or less, 7% by mass or less, 6% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.7% by mass or less, 0.6% by mass or less, 0.5% by mass or less, 0.4% by mass or less, 0.3% by mass or less, 0.2% by mass or less, or 0.1% by mass or less, based on the total amount of composition 2. The PEDOT:PSS content may be, for example, 0.01 to 30% by mass, based on the total amount of composition 2.

[0037] The PEDOT:PSS content may be 0.01 parts by mass or more, 0.03 parts by mass or more, 0.05 parts by mass or more, 0.07 parts by mass or more, 0.08 parts by mass or more, 0.09 parts by mass or more, 0.1 parts by mass or more, 0.3 parts by mass or more, 0.5 parts by mass or more, 0.7 parts by mass or more, 0.9 parts by mass or more, 1 part by mass or more, 1.2 parts by mass or more, 1.4 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, or 15 parts by mass or more, per 100 parts by mass of the polymerizable compound. The content of PEDOT:PSS may be 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, 4 parts by mass or less, 2 parts by mass or less, 1.3 parts by mass or less, 1 part by mass or less, 0.8 parts by mass or less, 0.4 parts by mass or less, 0.3 parts by mass or less, 0.2 parts by mass or less, 0.18 parts by mass or less, 0.16 parts by mass or less, or 0.12 parts by mass or less, per 100 parts by mass of polymerizable compound polymer. The content of PEDOT:PSS may be, for example, 0.01 to 30 parts by mass per 100 parts by mass of polymerizable compound polymer.

[0038] The content of PEDOT:PSS in Composition 2, relative to 100 parts by mass of surfactant, is the same as that described for the content of PEDOT:PSS in Composition 1.

[0039] In composition 2, PEDOT:PSS may be dispersed in particulate form. That is, in one embodiment, composition 2 may contain PEDOT:PSS particles. The maximum length of PEDOT:PSS particles observed by an optical microscope under conditions of 100x magnification and a field of view of 0.9 mm × 0.6 mm may be 0.1 μm or more, 0.8 μm or more, 1 μm or more, greater than 1 μm, 8 μm or more, 10 μm or more, or greater than 10 μm, and may be 100 μm or less, 50 μm or less, 20 μm or less, 12 μm or less, 10 μm or less, 2 μm or less, or 1 μm or less. The above maximum length of PEDOT:PSS particles may be, for example, 0.1 to 100 μm.

[0040] The surfactant content may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.8% by mass or more, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 2.5% by mass or more, 2.8% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, 25% by mass or more, or 28% by mass or more, and may be 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 32% by mass or less, 30% by mass or less, 25% by mass or less, 22% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, 5% by mass or less, or 4% by mass or less, based on the total amount of composition 2. The surfactant content may be, for example, 0.01 to 50% by mass, based on the total amount of composition 2.

[0041] The surfactant content may be 0.1 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 1.5 parts by mass or more, 2 parts by mass or more, 2.5 parts by mass or more, 3 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 37 parts by mass or more, 40 parts by mass or more, 42 parts by mass or more, 43.4 parts by mass or more, or 47 parts by mass or more, per 100 parts by mass of the polymerizable compound.

[0042] Next, a method for producing Composition 2 described above will be explained. One embodiment of the present invention is a method for producing a composition (production method A) comprising: step A1 of mixing a hydrophobic polymerizable compound, PEDOT:PSS, a surfactant, and a solvent to obtain a solution; and step A2 of heating the solution to polymerize the polymerizable compound and remove the solvent. Another embodiment of the present invention is a method for producing a composition (production method B) comprising: step B1 of polymerizing a hydrophobic polymerizable compound in the presence of a surfactant to obtain a polymer; step B2 of mixing the polymer with a PEDOT:PSS solution containing PEDOT:PSS and a solvent to obtain a mixture; and step B3 of removing the solvent from the mixture. Details of the polymerizable compound are the same as those described above as the polymerizable compound in Composition 1. The surfactant is the same as the surfactant described above in Composition 1. The content of the polymerizable compound, PEDOT:PSS, and surfactant may be the same as those described above as the content of each compound in Composition 1.

[0043] The amount of polymerizable compound mixed in step B1 may be 40% by mass or more, 50% by mass or more, or 60% by mass or more, and may be 95% by mass or less, 90% by mass or less, or 85% by mass or less, based on the total amount of polymerizable compound and surfactant.

[0044] In step A1, a polymerization initiator capable of initiating the polymerization of the polymerizable compound may be further contained. Step B1 may be a step of obtaining a polymer by polymerizing a hydrophobic polymerizable compound in the presence of a polymerization initiator capable of initiating the polymerization of the polymerizable compound in addition to a surfactant. The polymerization initiator capable of initiating the polymerization of the polymerizable compound is the same as that described as the polymerization initiator in the above composition 1. The type and content of the solvent are the same as those described as the solvent in the above composition 1.

[0045] Step A1 may further include a step of dispersing PEDOT:PSS in a solvent using ultrasonic waves after mixing a hydrophobic polymerizable compound, PEDOT:PSS, a surfactant, and a solvent. In step B2, before mixing the polymer and the solution of PEDOT:PSS, a step of dispersing PEDOT:PSS in the solution of PEDOT:PSS using ultrasonic waves may be further included. The dispersion by ultrasonic waves may be performed using an ultrasonic bath from the viewpoint of further enhancing the dispersibility of PEDOT:PSS, and may be performed using an ultrasonic homogenizer from the viewpoint of further enhancing the conductivity of the composition.

[0046] The polymerization reaction in step B1 may be carried out while cooling. The cooling temperature may be 0 °C or higher, 5 °C or higher, 10 °C or higher, 15 °C or higher, 20 °C or higher, or 25 °C or higher, and from the viewpoint of further enhancing the conductivity of the composition, it may be 30 °C or lower, 25 °C or lower, 20 °C or lower, 15 °C or lower, or 10 °C or lower. The cooling method may be a known method, and examples include air cooling, water cooling, etc.

[0047] From the viewpoint of further enhancing the conductivity of composition 2, production method A may further include a step of adding alkylene glycol to the solution between step A1 and step A2. In step B2 of production method B, the solution of PEDOT:PSS may further contain alkylene glycol from the viewpoint of further enhancing the conductivity of composition 2.

[0048] The number of carbon atoms in the alkylene group of an alkylene glycol may be two or more, or six or less. Examples of alkylene glycols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, and 1,6-hexanediol.

[0049] Manufacturing method A may further include step C, in which the composition (also called a masterbatch) obtained in step A2 is melt-kneaded with a polymer. Manufacturing method B may further include step C, in which the composition (also called a masterbatch) obtained in step B3 is melt-kneaded with a polymer.

[0050] The polymer in step C may be a polymer of a polymerizable compound similar to the polymerizable compound described above in composition 1. The amount of polymer mixed in step C may be 60% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, 87% by mass or more, or 90% by mass or more, based on the total amount of composition obtained in step C, and may be 99% by mass or less, 97% by mass or less, 95% by mass or less, 93% by mass or less, 91% by mass or less, or 90% by mass or less. The amount of polymer mixed in step C may be, for example, 60 to 99% by mass based on the total amount of composition obtained in step C.

[0051] The composition 2 described above may be molded. That is, one embodiment of the present invention is a molded body comprising composition 2. The molded body may be composed of composition 2.

[0052] The thickness of the molded body may be 0.1 mm or more, 0.5 mm or more, 1 mm or more, 2 mm or more, 3 mm or more, 4 mm or more, or 5 mm or more, and may be 100 mm or less, 50 mm or less, 30 mm or less, 20 mm or less, 10 mm or less, 8 mm or less, 6 mm or less, or 5 mm or less. The thickness of the molded body may be, for example, 0.1 to 100 mm. Because composition 2 according to one embodiment has high transparency, transparency of the molded body can be ensured even when the thickness of the molded body is large.

[0053] The shape of the molded body is not particularly limited and includes, for example, plate-shaped, rod-shaped, sheet-shaped, tape-shaped, cylindrical, cup-shaped, conical, annular, circular, elliptical, disc-shaped, gear-shaped, polygonal, hollow, frame-shaped, box-shaped, etc.

[0054] The molded body according to this embodiment is conductive and therefore suitable for applications requiring antistatic properties. While not particularly limited, it may be used in, for example, carrier tapes, electronic component packaging materials such as IC trays, home appliances, office automation equipment, antistatic coatings, and antistatic paints.

[0055] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0056] <Production of Composition (Masterbatch)> (Example 1) (1) PEDOT:PSS (manufactured by Agfa Materials Japan Ltd., product name "Organon DRY", pellet form, the same applies hereinafter) and ethanol (EtOH) were placed in a 50cc sample bottle in a mass ratio of 1:99 (0.1g:9.9g) and mixed in an ultrasonic bath for 1 hour and 30 minutes to obtain a mixture. (2) Styrene (St) monomer and dodecylbenzenesulfonic acid (DBSA) were mixed in a mass ratio of 69:30 (3.45g:1.5g) and polymerization was carried out. The polymerization conditions at this time were air cooling (room temperature 25°C) and polymerization time of 3 minutes. (3) The mixture prepared in (1) was mixed into a 20cc sample bottle containing the polymer prepared in (2) so that the amount of PEDOT:PSS was 1% by mass (0.05 g) based on the total amount of styrene (St) monomer, dodecylbenzenesulfonic acid (DBSA), and PEDOT:PSS. (5.00 g of PEDOT:PSS / EtOH solution was added dropwise.) (4) The sample bottle from (3) was heated and stirred on a hot plate (conditions: 150°C, 300 rpm, 1 hour) to volatilize the EtOH. (5) The EtOH was further completely removed using a vacuum dryer (40°C, 2 hours).

[0057] (Example 2) The procedure was the same as in Example 1, except for the following changes. (1) PEDOT:PSS and ethanol (EtOH) were placed in a 50cc sample bottle in a mass ratio of 1:99 (0.3g:29.7g), and mixed in an ultrasonic homogenizer for 5 minutes to obtain the mixture.

[0058] (Example 3) The procedure was the same as in Example 1, except for the following changes. (2) Styrene (St) monomer and dodecylbenzenesulfonic acid (DBSA) were mixed in a mass ratio of 69.5:30 (3.475 g: 1.5 g) and polymerization was carried out. The polymerization conditions at this time were air cooling (room temperature 25°C) and polymerization time of 3 minutes. (3) The mixture prepared in (1) was mixed into a 20 cc sample bottle containing the polymer prepared in (2) so that the amount of PEDOT:PSS was 0.5% by mass (0.025 g) based on the total amount of styrene (St) monomer, dodecylbenzenesulfonic acid (DBSA), and PEDOT:PSS. (2.5 g of PEDOT:PSS / EtOH solution was added dropwise.)

[0059] (Example 4) The procedure was the same as in Example 1, except for the following changes. (1) PEDOT:PSS and ethanol (EtOH) were placed in a 50cc sample bottle in a mass ratio of 1:99 (0.3g:29.7g) and mixed in an ultrasonic homogenizer for 5 minutes to obtain a mixture. (2) Styrene (St) monomer and dodecylbenzenesulfonic acid (DBSA) were mixed in a mass ratio of 69.9:30 (3.495g:1.5g) and polymerization was carried out. The polymerization conditions at this time were air cooling (room temperature 25°C) and polymerization time 3 minutes. (3) The mixture prepared in (1) was mixed into a 20cc sample bottle containing the polymer prepared in (2) so that the amount of PEDOT:PSS was 0.1% by mass (0.005g) based on the total amount of styrene (St) monomer, dodecylbenzenesulfonic acid (DBSA), and PEDOT:PSS. (0.5 g of PEDOT:PSS / EtOH solution was added dropwise.)

[0060] (Example 5) The procedure was the same as in Example 1, except for the following changes. (1) PEDOT:PSS and ethanol (EtOH) were placed in a 50cc sample bottle in a mass ratio of 1:99 (0.3g:29.7g) and mixed in an ultrasonic homogenizer for 5 minutes to obtain a mixture. (2) Styrene (St) monomer and dodecylbenzenesulfonic acid (DBSA) were mixed in a mass ratio of 60:30 (3.0g:1.5g) and polymerization was carried out. The polymerization conditions at this time were air cooling (room temperature 25°C) and polymerization time 3 minutes. (3) The mixture prepared in (1) was mixed into a 20cc sample bottle containing the polymer prepared in (2) so that the amount of PEDOT:PSS was 10% by mass (0.5g) based on the total amount of styrene (St) monomer, dodecylbenzenesulfonic acid (DBSA), and PEDOT:PSS. (50 g of PEDOT:PSS / EtOH solution was added dropwise.)

[0061] (Example 6) The procedure was the same as in Example 1, except for the following changes. (2) Styrene (St) monomer and dodecylbenzenesulfonic acid (DBSA) were mixed in a mass ratio of 79:20 (3.95 g:1 g) and polymerization was carried out. The polymerization conditions at this time were air cooling (room temperature 25°C) and polymerization time of 3 minutes.

[0062] (Example 7) The procedure was the same as in Example 1, except for the following changes. (1) PEDOT:PSS and ethanol (EtOH) were placed in a 50cc sample bottle in a mass ratio of 1:99 (0.3g:29.7g) and mixed in an ultrasonic homogenizer for 5 minutes to obtain a mixture. (2) Styrene (St) monomer and dodecylbenzenesulfonic acid (DBSA) were mixed in a mass ratio of 79:20 (3.95g:1g) and polymerization was carried out. The polymerization conditions at this time were air cooling (room temperature 25°C) and polymerization time of 3 minutes.

[0063] (Comparative Example 1) The procedure was the same as in Example 1, except for the following changes. (2) 4.95 g of styrene (St) monomer was weighed and polymerized in a 20 cc sample bottle. (3) (1) was mixed into the 20 cc sample bottle containing the polymer prepared in (2) so that the amount of PEDOT:PSS was 1% by mass (0.05 g) based on the total amount of styrene (St) monomer and PEDOT:PSS. (5.00 g of PEDOT:PSS / EtOH solution was added dropwise.)

[0064] <PEDOT: PSS particle size> Each composition (masterbatch) from Examples 1 to 7 and Comparative Example 1, removed from the vacuum dryer, was heated at 130°C for 5 minutes to soften and placed on a glass slide. Using a bar coater or doctor blade with a clearance of 0.1 mm, the composition (masterbatch) on the glass slide was spread to a thickness of approximately 0.1 mm at a speed of about 1 cm per second, and the dispersion state on the surface of the thin film composition (masterbatch) was checked using an optical microscope (Hirox Co., Ltd., product name "DIGITAL MICROSCOPE RH-2000", magnification: 100x, field of view: 0.9 mm × 0.6 mm). The evaluation was performed according to the following criteria. The results are shown in Table 1. A: The maximum length of the particles is 0.1 μm or more and 1 μm or less (particles are dispersed). B: The maximum length of the particles is greater than 1 μm and 10 μm or less (particles are dispersed). C: The maximum length of the particles is greater than 10 μm but less than or equal to 100 μm (particles are dispersed). D: The maximum length of the particles is greater than 100 μm (particles are phase-separated).

[0065] <Transparency> Each composition (masterbatch) of Examples 1 to 7 and Comparative Example 1, prepared in the same manner as described above and having a thickness of 0.1 mm, was visually inspected. The evaluation was performed according to the following criteria. The results are shown in Table 1. A: No particles are visible, and it is transparent, although slightly bluish. B: It is transparent, but upon closer inspection, small blue particles are scattered. C: Large, bluish-black particles are visible scattered. D: It is black and opaque.

[0066] <Measurement of Resistance> The surface resistance of each composition (masterbatch) of Examples 1 to 7, which was prepared in the same manner as above and had a thickness of 0.1 mm, was measured using a Loresta (manufactured by Nitto Seikou Analytech Co., Ltd., product name "Loresta-GP MCP-T600") and a probe (manufactured by Nitto Seikou Analytech Co., Ltd., PSP probe). In addition, the surface resistance of the composition (masterbatch) of Comparative Example 1, which was prepared in the same manner as above and had a thickness of 0.1 mm, was measured using a Hiresta (manufactured by Nitto Seikou Analytech Co., Ltd., product name "Hiresta-UP MCP-HT450") and a probe (manufactured by Nitto Seikou Analytech Co., Ltd., URS probe). The measurements were performed using the four-probe method (in accordance with JIS K 7194) (the thickness was corrected to 1 mm at this time). The ambient temperature during measurement was 25°C. The results are shown in Table 1.

[0067]

[0068] (Example 8) (1) The composition prepared in Example 1 and commercially available polystyrene (PS, manufactured by Toyo Styrene Co., Ltd., product name "Toyo Styrofoam HRM10N", the same applies hereinafter) were mixed in a mass ratio of 10:90 (0.3 g:2.7 g) using a melting and mixing machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name "Labo Plastomill μ") and a high shear blade (manufactured by Toyo Seiki Seisakusho Co., Ltd., model "KF6HB", tip clearance 0.3 mm, maximum shear speed 1.2 × 10⁻⁶) ３ Using a 3 / s mixture, a kneaded material was prepared under the conditions of a temperature of 200°C, a rotation speed of 90 rpm, and a time of 10 minutes. (2) The kneaded material obtained in (1) was pulverized in a rotary mill (2 mm mesh, 10,000 rpm) to obtain a mixture. (3) The mixture pulverized in (2) was subjected to heat processing using a hot press (150°C, 5 minutes preheating, 5 minutes heating and 3 MPa pressurization, 2 minutes rapid cooling and 3 MPa pressurization) to produce a 1 mm thick disc.

[0069] (Comparative Example 2) (1) Using the above-mentioned melting mixer and high-shear blade, a mixture of PEDOT:PSS and commercially available PS was prepared in a mass ratio of 10:90 (0.3g:2.7g) at a temperature of 200°C, a rotation speed of 90 rpm, and a time of 10 minutes. (2) The mixture obtained in (1) was pulverized in a rotary mill (2 mm mesh, 10,000 rpm) to obtain a mixture. (3) The mixture pulverized in (2) was subjected to heat processing by hot pressing (150°C, 5 minutes preheating, 5 minutes heating and 2 MPa pressurization, 2 minutes rapid cooling and 2 MPa pressurization) to produce a 1 mm thick disc.

[0070] (Comparative Example 3) (1) A polymer was prepared by mixing styrene (St) monomer and dodecylbenzenesulfonic acid (DBSA) in a mass ratio of 70:30 and polymerizing it in advance. This polymer was then mixed with commercially available PS in a mass ratio of 10:90 (0.3 g:2.7 g) using the above-described melt kneader and high-shear blade, under the conditions of a temperature of 200°C, a rotation speed of 90 rpm, and a time of 10 minutes. (2) The mixture obtained in (1) was pulverized in a rotary mill (2 mm mesh, 10,000 rpm) to obtain a mixture. (3) The mixture pulverized in (2) was subjected to heat processing using a hot press (150°C, 5 minutes preheating, 5 minutes heating and 3 MPa pressurization, 2 minutes rapid cooling and 3 MPa pressurization) to produce a 1 mm thick disc.

[0071] <Size of PEDOT:PSS Particles> The size of PEDOT:PSS particles in the prepared disks of Example 8 and Comparative Examples 2 and 3 was observed using the high-scope image of the optical microscope (magnification: 100x, field of view: 0.9 mm × 0.6 mm) described above. The evaluation criteria were the same as those for the size of PEDOT:PSS particles in the compositions described above. The results are shown in Table 2. Comparative Example 3 did not contain PEDOT:PSS, so the size of PEDOT:PSS particles was not evaluated.

[0072] <Transparency> A 1 mm thick disc was visually inspected. The evaluation criteria were the same as those for transparency in the compositions described above. The results are shown in Table 2.

[0073] <Measurement of Resistance> The surface resistance of the disk in Example 8 was measured using the above-described Rolester and probe, and the surface resistance of each disk in Comparative Examples 2 and 3 was measured using the above-described Hi-Lester and probe, using the four-probe method (in accordance with JIS K 7194). The ambient temperature during measurement was 25°C. The results are shown in Table 2.

[0074]

Claims

1. A composition containing a polymer of a hydrophobic polymerizable compound, PEDOT:PSS, and a surfactant.

2. The composition according to claim 1, wherein the surfactant has a functional group capable of initiating the polymerization of the polymerizable compound.

3. The composition according to claim 1 or 2, wherein the surfactant has a strongly acidic functional group.

4. The composition according to claim 1 or 2, wherein the surfactant has a sulfo group.

5. The composition according to claim 1 or 2, wherein the surfactant comprises dodecylbenzenesulfonic acid.

6. The composition according to claim 1 or 2, wherein the polymerizable compound comprises a styrene-based compound.

7. The composition according to claim 1 or 2, wherein the content of the polymer of the polymerizable compound is 30% by mass or more and 99% by mass or less, based on the total amount of the composition.

8. The composition according to claim 1 or 2, wherein the content of PEDOT:PSS is 0.01% by mass or more and 30% by mass or less based on the total amount of the composition.

9. The composition according to claim 1 or 2, wherein the content of the surfactant is 0.01% by mass or more and 50% by mass or less, based on the total amount of the composition.

10. A method for producing a composition, comprising: step B1 of polymerizing a hydrophobic polymerizable compound in the presence of a surfactant to obtain a polymer; step B2 of mixing the polymer with a PEDOT:PSS solution containing PEDOT:PSS and a solvent to obtain a mixture; and step B3 of removing the solvent from the mixture.

11. A method for producing the composition according to claim 10, wherein the PEDOT:PSS solution further comprises alkylene glycol.

12. A method for producing the composition according to claim 10 or 11, further comprising step C of melt-kneading the composition obtained in step B3 with a polymer.

13. A molded article comprising the composition described in claim 1 or 2, having a thickness of 0.1 mm or more.

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