Conductive additive

Abstract

To provide an auxiliary conductive agent with which an amount of a conductive filler which is used can be reduced in a conductive film formed by a polymer binder method.SOLUTION: An auxiliary conductive agent contains an ionic bonding salt represented by a formula (1) and is used for improving conductivity of a conductive resin composition containing a conductive filler and a resin. In the formula (1), n represents a valence of Q and is 1 or 2, Qn+ represents a univalent metal ion, a divalent metal ion, or a nitrogen compound ion, and T- represents a sulfate ester ion represented by a formula (t-1). (R1 is a substituted or unsubstituted 1-20C linear or branched alkyl group, a substituted or unsubstituted 3-20C cycloalkyl group, a substituted or unsubstituted 6-30C aryl group, or a substituted or unsubstituted 7-31C arylalkyl group.)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a conductive aid.

Background Art

[0002] Conductive films used in liquid crystal panels, touch panels, etc. have been manufactured by forming a film of a conductive material such as a conductive filler by a sputtering method or a vacuum evaporation method. However, there are problems in terms of manufacturing cost and environmental impact, and the polymer binder method has been applied as a simpler method.

[0003] For example, as an example to which the polymer binder method is applied, Patent Document 1 discloses a transparent conductive film-forming composition containing a conductive filler, a dispersion stabilizer, an ionic liquid, and a binder.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in order to obtain sufficient performance by the polymer binder method, it is necessary to use a large amount of conductive filler with respect to the binder (resin). Therefore, there is still a problem in terms of cost in that a large amount of expensive conductive filler is blended, and in the case of a transparent conductive film, there is a problem that the transparency is impaired by using a large amount of conductive filler.

[0006] Therefore, in the case of being manufactured by the polymer binder method, means for reducing the amount of the conductive filler used have been demanded.

[0007] Therefore, the object of the present invention is to provide a novel technology that can reduce the amount of conductive filler used in conductive films formed by the polymer binder method. [Means for solving the problem]

[0008] To solve the above problems, the inventors diligently conducted extensive research. As a result, they surprisingly discovered that the conductivity of a conductive resin composition containing a conductive filler and a resin is significantly improved by including a predetermined ionic salt in the composition. In other words, it was found that a predetermined ionic salt can function as a conductive additive that improves the conductivity of the conductive filler contained in the conductive resin composition. Based on this finding, the inventors completed the present invention.

[0009] In other words, according to one embodiment of the present invention, a conductive additive is provided which comprises an ionic salt represented by the following formula (1) and is used to improve the conductivity of a conductive resin composition comprising a conductive filler and a resin:

[0010] [ka]

[0011] In the above equation (1), n represents the valence of Q, which is either 1 or 2. n+ This represents a monovalent metal ion, a divalent metal ion, or a nitrogen-containing compound ion (wherein the nitrogen-containing compound ion, it may have an ethylenically unsaturated bond and may contain Si), T - The following equation (t-1):

[0012] [ka]

[0013] In the above formula (t-1), R 1These are substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, or substituted or unsubstituted arylalkyl groups having 7 to 31 carbon atoms. A 1 This is a linear or branched alkylene group having 2 to 4 carbon atoms, and if s is 2 or more, A 1 The types may be different. s is an integer between 0 and 50. A sulfate ester ion represented by, The following equation (t-2):

[0014] [ka]

[0015] In the above formula (t-2), R 4 These are substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, or substituted or unsubstituted arylalkyl groups having 7 to 31 carbon atoms. A 4 This is a linear or branched alkylene group having 2 to 4 carbon atoms. v is an integer between 0 and 50. This is a sulfonate ion represented by [formula]. [Effects of the Invention]

[0016] According to the present invention, a novel technology is provided that can reduce the amount of conductive filler used in a conductive film formed by the polymer binder method. [Modes for carrying out the invention]

[0017] [Conductive additive] One embodiment of the present invention is a conductive auxiliary agent that contains an ionic bond salt represented by the following formula (1) and is used to improve the conductivity of a conductive resin composition containing a conductive filler and a resin.

[0018]

Chemical formula

[0019] In the above formula (1), n represents the valence of Q and is 1 or 2.

[0020] In the above formula (1), Q n+ represents a monovalent metal ion, a divalent metal ion or a nitrogen-containing compound ion (where the nitrogen-containing compound ion may have an ethylenic unsaturated bond and may contain Si).

[0021] In the above formula (1), T - is a sulfate ion represented by the following formula (t-1): n+ 79>

[0022]

Chemical formula

[0023] or a sulfonic acid ion represented by the following formula (t-2): The following formula (t-2):

[0024]

Chemical formula

[0025] is a sulfonic acid ion represented by the formula.

[0026] In the above formula (t-1), R 1A is a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. 1 This is a linear or branched alkylene group having 2 to 4 carbon atoms, and if s is 2 or more, A 1 The types of elements may be different, and s is an integer between 0 and 50.

[0027] In the above equation (t-2), R 4 A is a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. 4 is a linear or branched alkylene group having 2 to 4 carbon atoms, and v is an integer from 0 to 50.

[0028] In the present invention, the "resin" contained in the "conductive resin composition" may be in an uncured state, or it may be in a cured state, obtained by undergoing a curing (polymerization) process from resin raw materials that can function as monomers. In either of these forms, the predetermined ionic bonded salt can function as a conductive additive to improve the conductivity of the conductive filler contained in the conductive resin composition.

[0029] As described above, the conductive additive of the present invention can improve the conductivity of a conductive resin composition containing a conductive filler and a resin. Although the details of this mechanism are not clear, it is presumed to be as follows: In the present invention, the conductive filler is well dispersed in the conductive resin composition containing an ionic salt and a resin. This is thought to allow for the efficient formation of conductive paths in the coating film (uncured or cured) made of the conductive resin composition.

[0030] According to the conductive additive of the present invention, the amount of conductive filler used in a conductive resin composition can be reduced. For example, even if the conductive filler is 200 parts by mass or less (e.g., 150 parts by mass or less) per 100 parts by mass of resin, good conductivity can be achieved. For example, by incorporating the conductive additive according to the present invention into a conductive resin composition that exhibits surface resistivity in the antistatic region, the conductivity of the conductive resin composition is improved, resulting in a conductive resin composition that exhibits surface resistivity in the antistatic region. As an example, 1 × 10 8 By adding the conductive additive according to the present invention to a conductive resin composition that forms a coating film having a surface resistivity exceeding Ω / sq, the surface resistivity of the coating film made of the conductive resin composition becomes 1 × 10⁻⁶ 6 ~9.5×10 7 The surface resistivity can be reduced to Ω / sq. The method for measuring the surface resistivity is as described in the examples below.

[0031] Furthermore, the conductive additive according to the present invention can improve the transparency of a coating film made of a conductive resin composition by improving the dispersibility of conductive fillers.

[0032] The embodiments of the present invention will be described in detail below.

[0033] (Cation Q n+ ) Q n+ Q is a monovalent metal ion, a divalent metal ion, or a nitrogen-containing compound ion. The nitrogen-containing compound ion may have an ethylenically unsaturated bond or may contain Si. In the following, Q n+This is also called a "cation."

[0034] Examples of monovalent metal ions include sodium ions, potassium ions, and lithium ions.

[0035] Examples of divalent metal ions include calcium ions and magnesium ions.

[0036] The nitrogen-containing compound ion is at least one selected from the group consisting of ammonium ions, imidazolium ions, pyridinium ions, pyrrolidinium ions, pyrrolinium ions, piperidinium ions, pyrazinium ions, pyrimidinium ions, triazolium ions, triazinium ions, quinolinium ions, isoquinolinium ions, indolinium ions, quinoxalinium ions, piperadinium ions, oxazolinium ions, thiazolinium ions, and morpholinium ions. The ammonium ion also includes organic ammonium ions.

[0037] The above nitrogen-containing compound ions may have ethylenically unsaturated bonds such as vinyl groups. The nitrogen-containing compound ions having ethylenically unsaturated bonds are at least one selected from the group consisting of ammonium ions having ethylenically unsaturated bonds, imidazolium ions having ethylenically unsaturated bonds, pyridinium ions having ethylenically unsaturated bonds, pyrrolidinium ions having ethylenically unsaturated bonds, pyrrolinium ions having ethylenically unsaturated bonds, piperidinium ions having ethylenically unsaturated bonds, pyrazinium ions having ethylenically unsaturated bonds, pyramidinium ions having ethylenically unsaturated bonds, triazolium ions having ethylenically unsaturated bonds, triazinium ions having ethylenically unsaturated bonds, quinolinium ions having ethylenically unsaturated bonds, isoquinolinium ions having ethylenically unsaturated bonds, indolinium ions having ethylenically unsaturated bonds, quinoxalinium ions having ethylenically unsaturated bonds, piperadinium ions having ethylenically unsaturated bonds, oxazolinium ions having ethylenically unsaturated bonds, thiazolinium ions having ethylenically unsaturated bonds, and morpholinium ions having ethylenically unsaturated bonds.

[0038] The nitrogen-containing compound ion may contain Si. The Si-containing nitrogen-containing compound ion is at least one selected from the group consisting of Si-containing ammonium ion, Si-containing imidazolium ion, Si-containing pyridinium ion, Si-containing pyrrolidinium ion, Si-containing pyrrolium ion, Si-containing piperidinium ion, Si-containing pyrazinium ion, Si-containing pyramidinium ion, Si-containing triazolium ion, Si-containing triazinium ion, Si-containing quinolinium ion, Si-containing isoquinolinium ion, Si-containing indolinium ion, Si-containing quinoxalinium ion, Si-containing piperadinium ion, Si-containing oxazolinium ion, Si-containing thiazolinium ion, and Si-containing morpholinium ion.

[0039] Specific examples of the above nitrogen-containing compound ions are similar to those described in paragraphs

[0033] to

[0056] of Japanese Patent Publication No. 2020-081905, but from the viewpoint of availability and other factors, organic ammonium ions are particularly preferred among the above compounds.

[0040] In the present invention, Q n+ It is preferable that Q is a monovalent ion, a nitrogen-containing compound ion (where the nitrogen-containing compound ion may have an ethylenically unsaturated bond and may contain Si). That is, Q n+ It is preferable that the ion is a monovalent ion (preferably sodium), a nitrogen-containing compound ion (other than nitrogen-containing compound ions having ethylenically unsaturated bonds and nitrogen-containing compound ions containing Si), a nitrogen-containing compound ion having ethylenically unsaturated bonds, or a nitrogen-containing compound ion containing Si. Also, Q n+ It is more preferably a monovalent ion (preferably sodium), an ammonium ion (wherein the ammonium ion may have an ethylenically unsaturated bond and may contain Si), and particularly preferably an organic ammonium ion (wherein the organic ammonium ion may have an ethylenically unsaturated bond and may contain Si).

[0041] Q n+ If it is an organic ammonium compound, Q n+ (Ammonium ion) is "N +It is represented as "(R')4". Here, R' is independently a hydrogen atom, a C1-C10 alkyl group, a C1-C10 hydroxyalkylene group, a C1-C10 silylalkylene group, a C1-C5 trialkylsilyl group, a C1-C5 trialkoxysilyl group, a trialkylsilylalkylene group (where the alkyl group has C1-C5 and the alkylene group has C1-C10), a trialkoxysilylalkylene group (where the alkoxy group has C1-C5 and the alkylene group has C1-C10), a C1-C10 (meth)acryloyloxyalkylene group, or a C5-C20 aryl group. In this case, it is preferable that one of R' is a hydroxyalkylene group having 1 to 10 carbon atoms, a silylalkylene group having 1 to 10 carbon atoms, a trialkylsilylalkylene group (where the alkyl group has 1 to 5 carbon atoms and the alkylene group has 1 to 10 carbon atoms), a trialkoxysilylalkylene group (where the alkoxy group has 1 to 5 carbon atoms and the alkylene group has 1 to 10 carbon atoms), or a (meth)acryloyloxyalkylene group having 1 to 10 carbon atoms; one of R' is a hydroxyalkylene group having 1 to 10 carbon atoms It is more preferable that the remaining R' is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0042] Note that "N + If R' in (R')4 is a silylalkylene group having 1 to 10 carbon atoms, a trialkylsilyl group having 1 to 5 carbon atoms, a trialkoxysilyl group having 1 to 5 carbon atoms, a trialkylsilylalkylene group (where the alkyl group has 1 to 5 carbon atoms and the alkylene group has 1 to 10 carbon atoms), then Q n+ This corresponds to the case where "an organic ammonium ion containing Si" is "N+ If R' in (R')4 is a (meth)acryloyloxyalkylene group having 1 to 10 carbon atoms, then Q n+ This corresponds to the case where it is an "organic ammonium ion having an ethylenically unsaturated bond."

[0043] Here, "N + The alkyl group that R' in (R')4 may be a linear, branched, or cyclic alkyl group. The alkylene group may be a linear, branched, or cyclic alkylene group.

[0044] In this specification, (meth)acryloyl refers to an acryloyl group and / or methacryloyl, (meth)acrylic acid refers to acrylic acid and / or methacrylic acid, and (meth)acrylate refers to acrylate and / or methacrylate.

[0045] Among organic ammonium ions, alkylammonium ions such as dimethylammonium ion, diethylammonium ion, monopropylammonium ion, dipropylammonium ion, monobutylammonium ion, dibutylammonium ion, methyl(ethyl)ammonium ion, methyl(propyl)ammonium ion, methyl(butyl)ammonium ion, methyl(pentyl)ammonium ion, methyl(hexyl)ammonium ion, ethyl(propyl)ammonium ion, ethyl(butyl)ammonium ion, ethyl(pentyl)ammonium ion, and ethyl(hexyl)ammonium ion; aromatic substituted alkylammonium ions such as monobenzylammonium ion, (1-phenethyl)ammonium ion, (2-phenethyl)ammonium ion (also known as monophenethylammonium ion), dibenzylammonium ion, bis(1-phenethyl)ammonium ion, and bis(2-phenethyl)ammonium ion (also known as diphenethylammonium ion); and monocyclopentylammonium ion, dicyclopentylammonium Cycloalkylammonium ions such as monocyclohexylammonium ion, dicyclohexylammonium ion, monocycloheptylammonium ion, dicycloheptylammonium ion; monomethanolammonium ion, dimethanolammonium ion, monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion, mono(n-propanol)ammonium ion, di(n-propanol)ammonium ion, monoisopropanolammonium ion, diisopropanolammonium ion, monobutanolammonium ion, dibutanolammonium ion, monopentanolammonium ion, dipentanolammonium ion, tripentanolammonium ion, monohexanolammonium ion, dihexanolammonium ion, monomethylmonoethanolammonium ion, dimethylmonoethanolammonium ion, monoethylmonoethanolammonium ion (also known as N-ethylethanolammonium ion), diethylmonoethanolammonium ion,Alkanolammonium ions such as monoethyl monopropanolammonium ion, diethyl monopropanolammonium ion, monoethyl monobutanolammonium ion, diethyl monobutanolammonium ion, monoethyl monopentanolammonium ion, diethyl monopentanolammonium ion, monopropyl monoethanolammonium ion, dipropyl monoethanolammonium ion, monopropyl monopropanolammonium ion, dipropyl monopropanolammonium ion, monopropyl monobutanolammonium ion, dipropyl monobutanolammonium ion, monopropyl monopentanolammonium ion, monopropyl monopentanolammonium ion, monobutyl monoethanolammonium ion, dibutyl monoethanolammonium ion, monobutyl monopropanolammonium ion, dibutyl monopropanolammonium ion, monobutyl monobutanolammonium ion, dibutyl monobutanolammonium ion, monobutyl monopentanolammonium ion, monobutyl monopentanolammonium ion, and dibutyl monopentanolammonium ion are preferred. These organic ammonium ions are preferred from the viewpoint of availability. In particular, the use of alkanolammonium ions is preferred from the viewpoint of forming good conductive paths in the conductive resin composition (coating film).

[0046] Furthermore, preferred organic ammonium ions having an ethylenically unsaturated bond include monomethylmonoacrylate ethylammonium ion, monomethylmonomethacrylate ethylammonium ion, monoethylmonoacrylate ethylammonium ion, monoethylmonomethacrylate ethylammonium ion, N,N-dimethylmonoacrylate ethylammonium ion, N,N-dimethylmonomethacrylate ethylammonium ion, N,N-diethylmonoacrylate ethylammonium ion, N,N-diethylmonomethacrylate ethylammonium ion, N,N-diethylmonomethacrylate ethylammonium ion, N,N-diethylmono(2-isocyanoethyl)ammonium ion, N,N-diethylmono(2-cyanopropyl)ammonium ion, and N,N-diethylmono(1,2-epoxypropane)ammonium ion. More preferably, the organic ammonium ions having an ethylammonium ethyl monoacrylate ion, N,N-ethylammonium ethyl monomethacrylate ion, N,N-ethylammonium diethyl monoacrylate ion, and N,N-ethyl monomethacrylate ion are used as organic ammonium ions having an ethylammonium ethyl bond. Particularly preferred are N,N-ethylammonium monoacrylate ion and N,N-ethyl monomethacrylate ion.

[0047] Furthermore, from the viewpoint of simplifying the reaction steps for preparing the ionic salt, it is preferable that the organic ammonium ion contains primary, secondary, or tertiary amino groups. Furthermore, from the viewpoint of easily obtaining the effects of the present invention, it is more preferable that the amino groups are secondary or tertiary (i.e., secondary ammonium ions or tertiary ammonium ions), and it is particularly preferable that the amino groups are secondary ammonium ions (i.e., secondary ammonium ions). Furthermore, from the viewpoint of easily obtaining the effects of the present invention, Q n+It is preferable that the organic ammonium ion has a structure in which a hydroxyethyl group, (meth)acryloyloxyethyl group, trimethoxysilylpropyl group, triethoxysilylpropyl group, or triisopropoxysilylpropyl group is bonded to the nitrogen atom, and therefore it is more preferable that the organic ammonium ion has a structure in which a hydroxyethyl group, (meth)acryloyloxyethyl group, trimethoxysilylpropyl group, triethoxysilylpropyl group, or triisopropoxysilylpropyl group is bonded to the nitrogen atom.

[0048] In one embodiment, the nitrogen-containing compound ion is an ammonium ion or iminium ion containing Si. Preferably, the nitrogen-containing compound ion is an ammonium ion (organic ammonium ion) containing Si. n+ When the ion is a nitrogen-containing compound ion containing Si (preferably an ammonium ion or iminium ion containing Si), it has the effect of improving conductivity and providing excellent water-resistant adhesion.

[0049] Q n+ If the Si-containing ammonium ion or iminium ion is, then the Si-containing ammonium ion is "N + (R')4" is represented as "N +(R')2 = C(R')2. Here, R' is independently a hydrogen atom, a C1-C10 alkyl group, a C1-C10 hydroxyalkylene group, a C1-C10 silylalkylene group, a C1-C5 trialkylsilyl group, a C1-C5 trialkoxysilyl group, a trialkylsilylalkylene group (where the alkyl group has C1-C5 and the alkylene group has C1-C10), and a trialkoxysilylalkylene group (where the alkoxy group has C1-C5 and the alkylene group has C1-C10). The R' group is either a C1-C10 or C5-C20 aryl group, where one of the R' groups is a C1-C10 silylalkylene group, a C1-C5 trialkylsilyl group, a C1-C5 trialkoxysilyl group, a trialkylsilylalkylene group (where the alkyl group has C1-C5 and the alkylene group has C1-C10), or a trialkoxysilylalkylene group (where the alkoxy group has C1-C5 and the alkylene group has C1-C10). In the case of an ammonium ion containing Si, R' other than a trialkylsilyl group having 1 to 5 carbon atoms, a trialkoxysilyl group having 1 to 5 carbon atoms, a silylalkylene group having 1 to 10 carbon atoms, a trialkylsilylalkylene group (where the alkyl group has 1 to 5 carbon atoms and the alkylene group has 1 to 10 carbon atoms), and a trialkoxysilylalkylene group (where the alkoxy group has 1 to 5 carbon atoms and the alkylene group has 1 to 10 carbon atoms) is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Also, Q n+ It may contain both ammonium ions and iminium ions. Q n+ In the case of an ammonium ion containing Si, it is preferable that it has a structure in which a trimethoxysilylpropyl group, a triethoxysilylpropyl group, or a triisopropoxysilylpropyl group is bonded to the nitrogen atom.

[0050] Here, "ammonium ions or iminium ions containing Si" can also be referred to as "cations derived from silane compounds containing amino or imino groups." Details of the above-mentioned silane compounds containing amino or imino groups (cations derived from silane compounds containing amino or imino groups) can be found in paragraphs

[0030] to

[0066] of Japanese Patent Publication No. 2016-29041, the disclosures of which are in Q. n+ This invention can also be applied to cases where the ammonium ion or iminium ion contains Si. In this invention, "cation derived from a silane compound containing an amino group or imino group" means a form in which a proton or the like is added to the amino group or imino group, resulting in a positive charge.

[0051] Examples of ammonium ions containing Si include N-(trimethylsilyl)diethylammonium ion, N-(trimethylsilyl)dimethylammonium ion, N-(triethylsilyl)diethylammonium ion, N-(triethylsilyl)dimethylammonium ion, 3-(trimethoxysilyl)-propylammonium ion, 3-(triethoxysilyl)-propylammonium ion, 3-(triisopropoxysilyl)-propylammonium ion, 3-(dimethoxymethylsilyl)-propylammonium ion, and 3-(diethoxymethylsilyl)-propylammonium ion. Examples include N-phenyl-N-(3-(trimethoxysilyl)-propyl)ammonium ion, N-methyl-N-(3-(trimethoxysilyl)-propyl)ammonium ion, N-(2-aminoethyl)-N-(3-(trimethoxysilyl)-propyl)ammonium ion, N-(2-aminoethyl)-N-(3-(dimethoxymethylsilyl)-propyl)ammonium ion, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylammonium ion, and 3-trimethoxysilyl-N-(1,3-dimethyl-butylidene)propylammonium ion.

[0052] Q n+In the case of an ammonium ion containing Si, it is preferable that the amino group contained in the ammonium ion is primary, secondary, or tertiary (i.e., primary ammonium ion, secondary ammonium ion, or tertiary ammonium ion) due to its availability.

[0053] (Anion T - ) In the above equation (1), T - is the sulfate ester ion represented by formula (t-1) above, or the sulfonate ion represented by formula (t-2). In the following, T - These are also called "anions." These anions, by possessing a surfactant structure, improve the dispersibility of conductive fillers, and as a result, can significantly contribute to the improvement of conductivity by ionic salts. Furthermore, these anions, as counter-anions for the above-mentioned cations, provide halogen-free counter-anions, making them suitable for use in applications where halogens are undesirable. The structures of these anions will be described in detail below.

[0054] A in the above equation (t-1) 1 , and A in equation (t-2) 4 Examples of linear or branched alkylene groups having 2 to 4 carbon atoms, as shown below, include ethylene, propylene, and butylene groups. From the viewpoint of availability, ethylene and propylene groups are particularly preferred.

[0055] In the above equation (t-1), R 1 , and R in equation (t-2) 4Examples of substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms, shown as follows: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isoamyl group, tert-pentyl group, neopentyl group, n-hexyl group, 3-methylpentan-2-yl group, 3-methylpentan-3-yl group, 4-methylpentyl group, 4-methylpentan-2-yl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group 3,3-dimethylbutan-2-yl group, n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 1-(n-propyl)butyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group, 1,1-diethylpropyl group, 1,3,3-trimethylbutyl group, 1-ethyl-2,2-dimethylpropyl group, n-octyl group, 2-methylhexane-2-yl group, 2,4-dimethylpentan-3-yl group, 1,1-dimethylpentan-1-yl group, 2,2-dimethylhexyl San-3-yl group, 2,3-dimethylhexane-2-yl group, 2,5-dimethylhexane-2-yl group, 2,5-dimethylhexane-3-yl group, 3,4-dimethylhexane-3-yl group, 3,5-dimethylhexane-3-yl group, 1-methylheptyl group, 2-methylheptyl group, 5-methylheptyl group, 2-methylheptan-2-yl group, 3-methylheptan-3-yl group, 4-methylheptan-3-yl group, 4-methylheptan-4-yl group, 1-ethylhexyl group, 2-ethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, 1 ,1-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 1-ethyl-1-methylpentyl group, 1-ethyl-4-methylpentyl group, 1,1,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 1-isopropyl-1,2-dimethylpropyl group, 1,1,3,3-tetramethylbutyl group, n-nonyl group, 1-methyloctyl group, 6-methyloctyl group, 1-ethylheptyl group, 1-(n-butyl)pentyl group, 4-methyl-1-(n-propyl)pentyl group, 1,5,5-trimethylhexyl group, 1,1,Examples of linear and branched alkyl groups include 5-trimethylhexyl group, 2-methyloctan-3-yl group, n-decyl group, 1-methylnonyl group, 1-ethyloctyl group, 1-(n-butyl)hexyl group, 1,1-dimethyloctyl group, 3,7-dimethyloctyl group, n-undecyl group, 1-methyldecyl group, 1-ethylnonyl group, n-dodecyl group, n-tridecyl group, isotridecyl group, n-tetradecyl group, 1-methyltridecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, and n-nonadecyl group. From the viewpoint of availability and dispersibility of conductive fillers in conductive resin compositions, substituted or unsubstituted linear or branched alkyl groups having 1 to 14 carbon atoms are preferred, with 2-ethylhexyl, tridecyl, isotridecyl, and 1,2-bis(2-ethylhexyloxycarbonyl)ethyl groups being more preferred, and tridecyl, 1,2-bis(2-ethylhexyloxycarbonyl)ethyl, and 2-ethylhexyl groups being particularly preferred.

[0056] Examples of substituted or unsubstituted cycloalkyl groups having 3 to 20 carbon atoms include, for example, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl groups. From the viewpoint of availability and dispersibility of conductive fillers in conductive resin compositions, substituted or unsubstituted cycloalkyl groups having 3 to 10 carbon atoms are more preferred, with cyclopropyl, cyclopentyl, and cyclohexyl groups being even more preferred.

[0057] Examples of substituted or unsubstituted aryl groups with 6 to 30 carbon atoms include, for example, phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 9-anthuryl, 9-phenanthryl, 1-pyrenyl, 5-naphthacenyl, 1-indenyl, 2-azlenyl, 9-fluorenyl, terphenyl, quarterphenyl, mesityl, pentarenyl, binaphthalenyl, ternaphthalenyl, heptarenyl, biphenylenyl, indacenyl, fluoranthenyl, acenaphthyleneyl, and aceanthrenyl. Examples include the flu group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, pleiadenyl group, picenyl group, perilenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group, heptacenyl group, pyrantrenyl group, and ovalenyl group. From the viewpoint of availability and dispersibility of conductive fillers in conductive resin compositions, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms are preferred, and phenyl groups, dimethylphenyl groups (2,3-dimethylphenyl, 2,4-dimethylphenyl, 3,4-dimethylphenyl, etc.), isopropylphenyl groups (2-isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl), and dodecylphenyl groups (2-dodecylphenyl, 3-dodecylphenyl, 4-dodecylphenyl) are particularly preferred.

[0058] Examples of substituted or unsubstituted arylalkyl groups having 7 to 31 carbon atoms include, for example, benzyl group, phenylethyl group, 3-phenylpropyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 2-(1-naphthyl)ethyl group, 2-(2-naphthyl)ethyl group, 3-(1-naphthyl)propyl group, or 3-(2-naphthyl)propyl group.

[0059] From the perspective of availability, R 1and R 4 It is more preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and more preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Furthermore, considering ease of handling such as availability and viscosity, it is preferably an n-butyl group, n-hexyl group, 2-ethylhexyl group, dimethylphenyl group, isopropylphenyl group, or dodecylphenyl group.

[0060] In formula (t-1) above, s, and in formula (t-2), v are divalent substituents -(OA) 1 )-and-(OA) 4 ) represents the number of ) and is an integer from 0 to 50. From the viewpoint of ease of handling due to a decrease in viscosity, etc., s and v are each independently preferably integers from 0 to 40, and more preferably integers from 0 to 30. Here, when s and v are 1 or more, the ionic bonded salt has an oxyalkylene chain.

[0061] In the sulfate ester ion represented by formula (t-1), the above values ​​of s are preferably integers from 1 to 40, and more preferably integers from 2 to 30. In the sulfate ester ion, in order to further improve the effects of the present invention, it is preferable that s be 1 or more. Thus, if the ionic bonded salt contains an oxyalkylene chain, the effect of improving conductivity can be further enhanced. Therefore, in the sulfate ester ion, it is even more preferable that s be 1 or more, and particularly preferable that s be 2 or more. On the other hand, if the oxyalkylene chain is too long, the viscosity becomes high, so considering handling properties, the upper limit of s is preferably 50, more preferably 40, and particularly preferably 30.

[0062] In the sulfonate ion represented by formula (t-2), the above values ​​of v are preferably integers from 0 to 20, and more preferably integers from 0 to 10. When v is within the above range in the sulfonate ion, the effect of improving conductivity can be further enhanced.

[0063] R 1 and R 4 Substituents that can be present in linear or branched alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, and arylalkyl groups having 7 to 31 carbon atoms include, for example, alkyl groups such as methyl, ethyl, tert-butyl, and dodecyl groups; aryl groups such as phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthuryl, and phenanthryl groups; alkoxy groups such as methoxy, ethoxy, and tert-butoxy groups; aryloxy groups such as phenoxy and p-tolyloxy groups; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, and phenoxycarbonyl groups; and acyl groups such as acetoxy, propionyloxy, and benzoyloxy groups. Examples of substituents include oxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acyl groups such as acryloyl groups, methacryloyl groups, and methoxalyl groups, alkylsulfanyl groups such as methylsulfanyl groups and tert-butylsulfanyl groups, arylsulfanyl groups such as phenylsulfanyl groups and p-tolylsulfanyl groups, alkylamino groups such as methylamino groups and cyclohexylamino groups, dialkylamino groups such as dimethylamino groups, diethylamino groups, morpholino groups, and piperidino groups, and arylamino groups such as phenylamino groups and p-tolylamino groups. Other examples include hydroxyl groups, carboxyl groups, formyl groups, mercapto groups, sulfo groups, mesyl groups, p-toluenesulfonyl groups, amino groups, nitro groups, cyano groups, trifluoromethyl groups, trichloromethyl groups, trimethylsilyl groups, phosphinico groups, and phosphono groups. However, the substituents present in some cases will not be the same as the group being substituted. For example, an alkyl group will not be substituted with another alkyl group.

[0064] In ionic salts, the sulfate ester ion represented by formula (t-1) or the sulfonate ion represented by formula (t-2) is appropriately selected depending on the application.

[0065] (Specific examples of ionic salts) More preferred compounds of the ionic bonded salt represented by formula (1) above include the ionic bonded salts represented by the following chemical formulas (101) to (154). In particular, from the viewpoint of more easily obtaining the effects of the present invention, the ionic bonded salts represented by chemical formulas (101) to (116), (121) to (138), (139) to (151) are preferred, the ionic bonded salts represented by chemical formulas (101) to (116), (121) to (136), (139) to (150) are more preferred, and the ionic bonded salts represented by chemical formulas (102), (106), (110), (114), (121), (123), (125), (127), (129), and (139) are especially preferred. Note that in the following chemical formulas (101) to (154), -C8H 13 , -C 13 H 27 The alkyl groups indicated as such represent linear or branched alkyl groups.

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] [Uses of conductive additives] The conductive additive according to the present invention comprises an ionic salt represented by formula (1) above, and is used to improve the conductivity of a conductive resin composition containing a conductive filler and a resin.

[0074] One embodiment of improving the conductivity of a conductive resin composition containing a conductive filler and a resin is, for example, a conductive film-forming composition containing a conductive filler and a resin capable of functioning as a monomer, in which an ionically bonded salt is present, and then the conductivity of the cured conductive resin composition obtained through a curing (polymerization) process is improved. In this specification, the composition in the state before the cured conductive resin composition is cured is also referred to as the "conductive film-forming composition". Here, in the ionically bonded salt represented by formula (1), Q n+ When the ion is a nitrogen-containing compound ion having an ethylenically unsaturated bond, the ionic salt can copolymerize with the resin as a monomer during the curing (polymerization) process of the conductive film-forming composition. In this case, since the ionic salt is immobilized on the polymer that forms the conductive film, the ionic salt is less likely to bleed out, i.e., durability is improved. Note that the "resin as a monomer" may be a monomer (simple monomer) that constitutes the resin, or a resin having a reactive group (macromonomer).

[0075] In other words, in the conductive resin composition according to the present invention, the resin may contain constituent units derived from monomers for constituting the resin, or it may contain constituent units derived from monomers for constituting the resin and constituent units derived from ionic salts.

[0076] The content of conductive additives (ionically bonded salts) in a conductive resin composition is not particularly limited as it varies depending on the application. However, the amount of conductive additive is preferably 0.05 parts by mass or more and 100 parts by mass or less, more preferably 0.1 parts by mass or more and 70 parts by mass or less, even more preferably 0.3 parts by mass or more and 50 parts by mass or less, particularly preferably 0.5 parts by mass or more and 30 parts by mass or less, and most preferably 0.8 parts by mass or more and 20 parts by mass or less, per 100 parts by mass of conductive filler. Within the above range, sufficient conductivity is imparted to the conductive resin composition containing the conductive filler and resin, and the amount of conductive filler used can be reduced, which is also economically advantageous.

[0077] Generally, the higher the content of a conductive additive in a conductive resin composition, the more the conductivity of the conductive resin composition tends to improve. However, the conductive additive according to the present invention has been found to exhibit sufficient conductivity even at low concentrations in the conductive resin composition, and furthermore, to further improve the conductivity of the conductive resin composition when the content of the conductive additive in the conductive resin composition is within a predetermined range. That is, in one embodiment of the conductive resin composition according to the present invention, in order to further improve conductivity, the content of the conductive additive is preferably 0.1 parts by mass or more and 6 parts by mass or less, and more preferably 0.2 parts by mass or more and 2 parts by mass or less, per 100 parts by mass of conductive filler. By being within this range, the effect of improving conductivity by the conductive additive can be further exhibited.

[0078] Furthermore, a transparent conductive resin composition can be obtained using the conductive additive according to the present invention. When transparency is important, even higher transparency can be achieved by setting the content of the conductive additive in the conductive resin composition to a predetermined range. That is, in one embodiment of the conductive resin composition according to the present invention, in order to have high transparency, the content of the conductive additive is preferably 1.5 parts by mass or more and 10 parts by mass or less, and more preferably 2 parts by mass or more and 8 parts by mass or less, per 100 parts by mass of conductive filler.

[0079] When a conductive resin composition contains additives such as conductive additives, these additives may reduce the performance of the substrate to which the conductive resin composition is applied. Generally, resins have excellent adhesion to other resins, but additives contained in a conductive resin composition may reduce the adhesion between, for example, the substrate (resin) and the conductive resin composition. The conductive additive according to the present invention, even when included in a conductive resin composition, does not reduce the adhesion to the substrate (resin) and can maintain suitable adhesion. When resins such as polyethylene terephthalate (PET), acrylic resins, acrylonitrile butadiene styrene resin (ABS resin), polyolefin resins such as polypropylene, polycarbonate resins, and talc-containing chlorinated polypropylene are used as the substrate, the conductive additive according to the present invention can particularly reduce the influence on the substrate (resin) and maintain the adhesion between the conductive resin composition containing the conductive additive according to the present invention and the substrate (resin). Such adhesion between the conductive resin composition and the substrate can be evaluated, for example, by the water-resistant adhesion evaluated in the examples.

[0080] As described above, the conductive resin composition to which the conductive additive according to the present invention is added contains a conductive filler and a resin. The composition of the conductive resin composition (composition for forming a conductive film) will be described below.

[0081] [Conductive filler] Examples of conductive fillers according to the present invention include silver, copper, gold, silver-coated copper, bimetallic powder, graphite particles, carbon nanotubes, conductive carbon black or other carbon allotropes, titanium oxide, barium titanate, iron oxide, barium sulfate, zinc sulfide, zinc oxide, zirconium oxide, silicon oxide, aluminum oxide, cerium oxide, indium oxide, phosphorus-doped tin oxide (PTO), tin oxide (TO), antimond-doped tin oxide (ATO), tin-doped indium oxide (ITO), antimony pentoxide, and the like.

[0082] Among these, from the viewpoint of the conductivity-improving effect of ionic salts, tin-doped indium oxide, phosphorus-doped tin oxide, tin oxide, antimond-doped tin oxide, graphite particles, carbon nanotubes, conductive carbon black, and titanium oxide are preferred, phosphorus-doped tin oxide, tin oxide, antimond-doped tin oxide, and titanium oxide are more preferred, and phosphorus-doped tin oxide and antimond-doped tin oxide are even more preferred.

[0083] The average particle diameter (volume-average primary particle diameter) of the conductive filler according to the present invention is preferably 5.0 μm or less, more preferably 1.0 μm or less, and even more preferably 0.2 μm or less. In the case of a transparent conductive material, the effect of improved transparency is achieved when the average particle diameter of the conductive filler is within the above range. There is no particular lower limit to the average particle diameter of the conductive filler, but for practical purposes, it is preferably 0.1 nm or more. The average particle diameter of the conductive filler is a value measured, for example, by dynamic light scattering.

[0084] The content of conductive filler in a conductive resin composition is not particularly limited as it varies depending on the application, but for example, it is preferably 5 to 500 parts by mass per 100 parts by mass of resin, more preferably 10 to 400 parts by mass, even more preferably 20 to 350 parts by mass, particularly preferably 50 to 300 parts by mass, and most preferably 100 to 250 parts by mass. When the conductive filler is contained within the above range, the conductive additive can further improve the conductivity of the conductive resin composition.

[0085] [resin] A conductive resin composition contains a resin. Specifically, the conductive resin composition according to the present invention is obtained by dispersing a conductive filler in a resin and a conductive additive, and examples include conductive pastes, conductive paints, conductive adhesives, conductive inks, conductive films, conductive fibers, conductive rubber (such as rollers for photocopiers), industrial packaging materials (such as IC tapes and carrier tapes), and electrostatic coating primers (especially those used for automotive parts, etc.). Such a conductive resin composition can be manufactured, for example, by dispersing a conductive filler in monomers that constitute a conductive additive and resin, and then undergoing a curing process.

[0086] Examples of resins include (meth)acrylic resins, melamine resins, phenolic resins, urea resins, epoxy resins, polyester resins, silicone resins, polyamide resins, polycarbonate resins, polyurethane resins, polystyrene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl acetate resins, polyvinylidene fluoride resins, acrylonitrile butadiene styrene resins (ABS resins), acrylonitrile styrene resins (AS resins), polyolefin resins such as polyethylene and polypropylene, hydroxyethylcellulose resins, polyvinyl alcohol resins, polyethylene glycol (PEG) resins, polyethylene oxide resins, polypropylene oxide resins, polysaccharide resins, other photopolymerizable resins, and combinations thereof.

[0087] Among these, it is preferable that the resin be one or more selected from the group consisting of (meth)acrylic resin, polystyrene resin, polyolefin resin, polyurethane resin, polyester resin, epoxy resin, melamine resin, and silicone resin.

[0088] In one embodiment of the present invention, the resin included in the conductive resin composition is a (meth)acrylic resin obtained by homopolymerizing or copolymerizing various (meth)acrylic acid ester monomers.

[0089] Examples of monomers used in the production of the above-mentioned resin (i.e., monomers that constitute the resin) include (meth)acrylic monomers, other monomers, unsaturated ethylenic monomers having an amide group, unsaturated ethylenic monomers having a urea group, unsaturated ethylenic monomers having an isocyanate group, and unsaturated ethylenic monomers having a urethane group.

[0090] Specific examples of monofunctional (meth)acrylic monomers include alkyl esters of (meth)acrylates having 1 to 18 carbon atoms, such as (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate; glycidyl (meth)acrylate; and (meth)acrylonitrile.

[0091] Specific examples of polyfunctional (meth)acrylic monomers include polyethylene glycol diacrylate, decanediol diacrylate, nonanediol diacrylate, hexanediol diacrylate, tricyclodecanedimethanol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0092] Other specific examples of monomers include glycidyl (meth)acrylate, monoesters of (meth)acrylic acid and polyethylene glycol, 2-aminoethyl (meth)acrylate and its salts, caprolactone-modified (meth)acrylic acid, 2,2,6,6-tetramethylpiperidine (meth)acrylate, 1,2,2,6,6-pentamethylpiperidine (meth)acrylate, and other (meth)acrylic acid esters; sodium (meth)acrylate, potassium (meth)acrylate, ammonium (meth)acrylate, and other (meth)acrylate salts; acrylonitrile, methacrylo Examples include unsaturated nitriles such as nitriles; unsaturated amides such as (meth)acrylamide, N-methylol(meth)acrylamide, and N-(2-hydroxyethyl)(meth)acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α,β-unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene chloride, and vinyl fluoride; and α,β-unsaturated aromatic hydrocarbons such as styrene, divinylbenzene, α-methylstyrene, and sodium styrenesulfonate. These may be used individually or in combination of two or more, but the use of two or more in combination is preferable.

[0093] Specific examples of unsaturated ethylenically occurring monomers having an amide group include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, Nn-butyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-methylol(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methyl-N-ethyl(meth)acrylamide, N-hydroxyethyl-N-methyl(meth)acrylamide, (meth)acryloylmorpholine, vinylacetamide, and the like.

[0094] Examples of unsaturated ethylene monomers having a urea group include (meth)acryloyloxyethyl ethyleneurea and (meth)acryloyloxypropyl ethyleneurea. Examples of unsaturated ethylene monomers having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate. Examples of unsaturated ethylene monomers having a urethane group include (meth)acryloyloxyethyl methyl carbamate and urethane acrylate. These monomers can be used in appropriate combinations depending on the required conductive properties.

[0095] The conductive additive according to the present invention can improve the conductivity of a conductive resin composition (conductive filler) by being incorporated into a conductive resin composition containing a conductive filler and a resin. For example, when the conductive additive according to the present invention is compound (102), (106), (110), (114), (123), (129), or (139), it is preferable to use the conductive additive in combination with a conductive resin composition containing one or more conductive fillers selected from antimond-doped tin oxide, titanium oxide, and conductive carbon black, and a resin composed of one or more monomers selected from dipentaerythritol hexaacrylate, methyl (meth)acrylate, butyl (meth)acrylate, styrene, hydroxyethyl (meth)acrylate, and urethane acrylate.

[0096] [solvent] The conductive film-forming composition to which the conductive additive according to the present invention is added preferably contains a solvent. The solvent adjusts the viscosity of the conductive film-forming composition and improves the coatability when the conductive film-forming composition is applied to the substrate. The conductive resin composition after the conductive film-forming composition has been applied and cured may also contain a solvent.

[0097] The type of solvent is not particularly limited, but it is preferable to include a protic polar solvent, an aprotic polar solvent, or a nonpolar solvent. Examples of protic polar solvents include water; alcohol-based solvents such as ethyl alcohol, methyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol (1-butanol), 2-butyl alcohol (2-butanol), isobutyl alcohol, ethylene glycol, and propylene glycol; and acetic acid. Examples of aprotic polar solvents include ketone solvents such as dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone; monoalkylene glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether; and dialkylene glycol ether solvents such as diethylene glycol diethyl ether and triethylene glycol diethyl ether. Examples of nonpolar solvents include hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, decalin, tetralin, methylene chloride, chloroform, and dichloroethane and their derivatives. The water used is not particularly limited and may be industrial water, purified water, deionized water, or ultrapure water. The solvent may be used alone or as a mixture of two or more solvents, or as a mixed solvent with water.

[0098] Of these, ethyl alcohol, methyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol, toluene, and xylene are preferred from the viewpoint of dispersibility of conductive fillers, and 2-butyl alcohol, propylene glycol monomethyl ether, toluene, and xylene are more preferred.

[0099] The solvent can be appropriately selected depending on the components of the conductive resin composition. For example, when antimond-doped tin oxide is used as the conductive filler and the resin is composed of dipentaerythritol hexaacrylate, the solvent is preferably 2-butanol. Also, for example, when titanium dioxide is used as the conductive filler and the resin is composed of dipentaerythritol hexaacrylate, the solvent is preferably 2-butanol or toluene, and more preferably toluene. For example, when antimond-doped tin oxide is used as the conductive filler and the resin is composed of two or more selected from dipentaerythritol hexaacrylate, methyl (meth)acrylate, butyl (meth)acrylate, styrene, and urethane acrylate, the solvent is preferably propylene glycol monomethyl ether. For example, when antimond-doped tin oxide or conductive carbon black is used as the conductive filler and the resin is an acrylic resin, the solvent is preferably 2-butanol or toluene, and more preferably toluene.

[0100] [Polymerization initiator] In conductive resin compositions, it is preferable to use polymerization initiators such as thermal polymerization initiators and photopolymerization initiators, which may be used alone or in combination of two or more. The amount of polymerization initiator added is preferably 0.1 to 5 parts by mass per 100 parts by mass of the total amount of monomers.

[0101] Examples of thermal polymerization initiators include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetacetate peroxide, acetylacetate peroxide, 1,1-bis(t-hexyl peroxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexyl peroxy)-cyclohexane, 1,1-bis(t-butyl peroxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butyl peroxy)-2-methylcyclohexane, and 1,1-bis(t -butylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-bis(t-butylperoxy)butane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α,α'-bis(t-butylperoxy)diisopropyl Pyrbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyn-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinate peroxide, m-toluylbenzoyl peroxide, benzoyl peroxide, di-n-p Peroxy peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3-Tetramethylbutyl peroxyneodecanoate, 1-Cyclohexyl-1-methylethyl peroxyneodecanoate, t-Hexyl peroxyneodecanoate, t-Butyl peroxyneodecanoate, t-Hexyl peroxypivalate, t-Butyl peroxypivalate, 1,1,3,3-Tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-Dimethyl-2,5-Bis(2-ethylhexanoyl peroxy)hexanoate, 1-Cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate t-hexyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisobutyrate, t-butyl peroxymalate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxyacetate, t-butyl peroxy-m-butylyl benzoate Organic peroxide initiators such as benzoates, t-butyl peroxybenzoate, bis(t-butyl peroxy) isophthalate, 2,5-dimethyl-2,5-bis(m-toluyl peroxy)hexane, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoyl peroxy)hexane, t-butyl peroxyallyl monocarbonate, t-butyl trimethylsilyl peroxide, 3,3',4,4'-tetra(t-butyl peroxycarbonyl) benzophenone, and 2,3-dimethyl-2,3-diphenylbutane; 2-Phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1'-azobis(cyclohexane-1-carbonitride), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionamidine)dihydrochloride, 2,2'-azobis(2-methyl-N-phenylpropionamidine)dihydrochloride, 2,2'-Azobis[N-(4-chlorophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-Azobis[N-(4-hydrophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-Azobis[2-methyl-N-(phenylmethyl)propionamidine]dihydrochloride, 2,2'-Azobis[2-methyl-N-(2-propenyl)propionamidine]dihydrochloride, 2,2'-Azobis[N-(2-hydroxyethyl)-2-methylpropionamidine 2,2'-Azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-Azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepine-2-yl)propane]dihydrochloride, 2,2'-Azobis[2-(3,4,5,6-tetrahydropyrimidine-2-yl)propane]dihydrochloride, 2,2'-Azobis[2-(5- [Hydroxy-3,4,5,6-tetrahydropyrimidine-2-yl)propane]dihydrochloride, 2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl Examples of azo-based initiators include ethyl propionamide, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis(4-cyanopentanoic acid), and 2,2'-azobis[2-(hydroxymethyl)propionitrile]. These thermal polymerization initiators may be used individually or in combination of two or more.

[0102] Examples of photopolymerization initiators include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-be Acetophenones such as benzoin-2-dimethylamino-1-(4-morpholinophenyl)butanone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, and 3,3',4,4'-tetrapropyl benzoate. Benzophenones such as la(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminonium bromide, (4-benzoylbenzyl)trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylthioxanthone) Examples include thioxanthones such as tylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride; acyl phosphonate oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; oxime esters; cationic photopolymerization initiators; intramolecular hydrogen abstraction type photopolymerization initiators; and the like. These photopolymerization initiators may be used alone or in combination of two or more.

[0103] [Other ingredients] The conductive resin composition according to the present invention may, in addition to the conductive filler and resin described above, optionally contain conventionally known additives (hereinafter referred to as "other additives"). Examples of other additives include glass frit, metal alkoxides, dispersants, viscosity modifiers, surface modifiers, plasticizers, pH adjusters, UV stabilizers, color inhibitors, matting agents, deodorizers, flame retardants, weathering agents, thread friction reducers, slip agents, mold release agents, antioxidants, ion exchange agents, and coloring pigments. These other additives may be appropriately blended depending on the intended use of the conductive resin composition.

[0104] Here, the conductive film-forming composition (conductive resin composition) to which the conductive additive according to the present invention is added may contain a dispersant, but even without the addition of a dispersant, the conductive filler can be well dispersed in the conductive resin composition. This is because the structure of the anionic portion of the ionic bonded salt has the structure of a surfactant, and therefore it is thought to act not only as a conductive additive but also as a dispersant. In other words, in a conductive resin composition containing the conductive additive according to the present invention, the conductive filler can be well dispersed in the conductive resin composition even without containing a dispersant, and it is presumed that this allows for the efficient formation of conductive paths in the conductive resin composition (coating film).

[0105] As described above, by adding the conductive additive according to the present invention to a conductive film-forming composition, conductive fillers can be dispersed well, and the conductivity of the resulting conductive resin composition can be improved. In other words, by including the conductive additive in the conductive resin composition, the conductivity of the conductive fillers can be expressed more effectively. Therefore, the amount of conductive filler used in the conductive resin composition can be reduced. Thus, the conductive additive according to the present invention has the advantage of reducing the amount of expensive conductive fillers used, thereby lowering the product price.

[0106] The form in which the conductive additive according to the present invention is used is not particularly limited. For example, a conductive film-forming composition may be made by mixing a conductive filler with monomers for constituting a resin (and a solvent if necessary), and then adding the conductive additive to obtain a dispersion; or a conductive film-forming composition may be made by dispersing the conductive filler in the conductive additive (and a solvent if necessary), and then adding monomers for constituting a resin to the dispersion; or a conductive film-forming composition may be made by mixing the conductive additive with monomers for constituting a resin (and a solvent if necessary), and then dispersing the conductive filler in the mixture; or any combination of these forms may be used as appropriate.

[0107] Furthermore, the method for dispersing the conductive filler is not particularly limited, but for example, the conductive filler can be dispersed using a roller mill, jet mill, bead mill, ball mill, homogenizer, homomixer, disperser mixer, or rotation / revolution mixer. In the conductive film-forming composition of the present invention, grinders such as roller mills, jet mills, bead mills, and ball mills can be preferably used for dispersing the conductive filler because they can grind the secondary particles of the conductive filler down to primary particles.

[0108] [Conductive coating] According to the present invention, a conductive coating film (hereinafter referred to as "coating film") made of a conductive resin composition is also provided. As described above, the conductive resin composition according to the present invention exhibits the effect of the conductive additive according to the present invention, and therefore the coating film according to the present invention also exhibits the effect of the conductive additive and has high conductivity.

[0109] The coating film according to the present invention is obtained by applying the conductive film-forming composition according to the present invention onto a substrate, drying, and polymerization. The drying conditions and polymerization conditions are not particularly limited. For example, in the case of solution polymerization, the polymerization temperature can be appropriately set depending on the type of polymerization initiator used, but is preferably 50 to 120°C. The polymerization time is also not particularly limited, but is preferably 1 to 10 hours.

[0110] When polymerization is performed by irradiation with ultraviolet light, mercury lamps (e.g., high-pressure mercury lamps, low-pressure mercury lamps), metal halide lamps, etc., can be used as the irradiation light source. There are no particular restrictions on the irradiation conditions of ultraviolet light, but the integrated light intensity should be 100 mJ / cm². 2 The above is preferable, and 200 mJ / cm² is preferred. 2 The above is more preferable. Furthermore, while there are no particular restrictions on the irradiation time, it is preferably between 0.01 and 300 seconds.

[0111] [Conductive coatings] According to the present invention, a coated article is also provided, having a substrate and a conductive coating film formed on the substrate according to the present invention. As described above, the conductive coating film according to the present invention exhibits the effect of the conductive additive according to the present invention, and therefore, a coated article having such a conductive coating film on a substrate can also exhibit the effect of the conductive additive according to the present invention.

[0112] Examples of conductive coatings include electrodes, wiring, circuits, conductive bonding structures, and conductive adhesive tapes. The shape and thickness of the coating film are not particularly limited, and a desired thickness can be adopted depending on the application.

[0113] The substrate on which the conductive coating film is formed is not particularly limited in material, and can include metals, organic materials such as plastics (resins), inorganic materials such as ceramics and glass, paper, and wood. When a resin such as polyethylene terephthalate (PET), acrylic resin, polyolefin resin such as polypropylene, or talc-containing chlorinated polypropylene is used as the substrate, the conductive additive according to the present invention can particularly reduce its influence on the substrate (resin) and maintain adhesion between the conductive resin composition containing the conductive additive according to the present invention and the substrate (resin).

[0114] Furthermore, the method for forming a conductive coating film by applying the conductive film-forming composition of the present invention onto a substrate can be any conventionally known coating method without any particular limitations.

[0115] [Molded body] According to the present invention, a molded article made of the conductive resin composition according to the present invention is also provided. As described above, the conductive resin composition according to the present invention exhibits the effects of the conductive additive according to the present invention, and therefore, a molded article made of the conductive resin composition can also exhibit the effects of the conductive additive according to the present invention. Examples of molded articles made of the conductive resin composition include displays, touch panels, antistatic flooring, IC trays, and silicon wafer cases.

[0116] [Method for producing conductive resin composition] The method for producing the conductive resin composition according to the present invention is not particularly limited, but for example, it can be produced by a manufacturing method including the following steps.

[0117] As an example, a method for producing a conductive resin composition according to the present invention includes the steps of: preparing a dispersion in which a conductive filler and a conductive additive comprising an ionic salt according to the present invention are dispersed; mixing the dispersion with monomers for constituting a resin to obtain a conductive film-forming composition; and curing the conductive film-forming composition to obtain a conductive resin composition. [Examples]

[0118] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by the following examples. In the following, the terms "parts" or "%" may be used, but unless otherwise specified, they refer to "parts by mass" or "mass%".

[0119] [Synthesis Example 1: Synthesis of [MEM][EHDG-S]; Synthesis of ionic salts] 150.0 parts by mass of diethylene glycol mono-2-ethylhexyl ether (manufactured by Nippon Emulsifier Co., Ltd., trade name: 2-ethylhexyl diglycol, abbreviation: EHDG) was added to 150.0 parts by mass of toluene and the temperature was raised to 110°C. 80.2 parts by mass of sulfamic acid was added and the mixture was reacted for 3 hours. After the reaction, the excess sulfamic acid was filtered off to obtain diethylene glycol mono-2-ethylhexyl ether sulfate ammonium salt (abbreviation: EHDG-SF; ammonium ion is NH4).+ A toluene solution of ) was obtained.

[0120] To 100.0 parts by mass of a 50% toluene solution of EHDG-SF obtained above, 21.2 parts by mass of N-ethylethanolamine (manufactured by Nippon Emulsifier Co., Ltd., trade name: Amino Alcohol MEM, abbreviation: MEM) was added and the mixture was reacted at 120°C for 3 hours. (The molar ratio of EHDG-SF to MEM was 1:1.5) After the reaction was complete, toluene and unreacted MEM were removed by distillation under reduced pressure (temperature: 150°C, pressure: 1.33 kPa (10 mmHg)) to obtain 61.2 parts by mass of the target ionic salt (abbreviation: [MEM][EHDG-S]; compound represented by chemical formula (102)). The obtained ionic salt was liquid at room temperature (25°C).

[0121] [Synthesis Example 2: Synthesis of [MEM][N-1305-S]; Synthesis of ionic salts] 517.4 parts by mass of polyoxyethylene tridecyl ether sulfate ammonium salt (abbreviation: 1305-SF), synthesized by a conventionally known method, was mixed with 93.6 parts by mass of N-monoethylethanolamine (manufactured by Nippon Emulsifier Co., Ltd., trade name: amino alcohol MEM, abbreviation: MEM) dropwise, and the mixture was reacted for 1 hour. After the reaction, the excess MEM was removed by distillation under reduced pressure to obtain 589.5 parts by mass of the target ionic salt (abbreviation: [MEM][N-1305-S], a compound represented by chemical formula (106)). The obtained ionic salt was liquid at room temperature (25°C).

[0122] [Synthesis Example 3: Synthesis of [MEM][Cum-SO3]; Synthesis of ionic salts] 199.3 parts by mass of cumenesulfonic acid (a mixture of o-,m-,p-cumenesulfonic acid isomers) (manufactured by Teika Co., Ltd., product name: Teika Tox 500, abbreviation: Cum-SO3H) were mixed with 89.1 parts by mass of N-monoethylethanolamine (manufactured by Nippon Emulsifier Co., Ltd., product name: Amino Alcohol MEM, abbreviation: MEM) dropwise, and the mixture was reacted for 1 hour to obtain 288.4 parts by mass of the target ionic salt (abbreviation: [MEM][Cum-SO3], a compound represented by chemical formula (110)). The obtained ionic salt was liquid at room temperature (25°C).

[0123] [Synthesis Example 4: Synthesis of [MEM] and [DOSS]; Synthesis of ionic salts] 200.0 parts by mass of dioctyl fumarate, 116.4 parts by mass of 50% ammonium bisulfite aqueous solution, 37.0 parts by mass of methanol, and 15.6 parts by mass of water were placed in an autoclave and the mixture was heated to 120°C and reacted for 24 hours. The maximum pressure at this time was 0.25 MPa.

[0124] 140.0 parts by mass of ammonium dioctyl sulfosuccinate (abbreviated as DOSS-NH4) obtained above was mixed with 30.4 parts by mass of MEM (the molar ratio of DOSS-NH4 to MEM was 1:1.5).

[0125] After preparation, the mixture was reacted at 80°C for 3 hours. After the reaction was complete, methanol, water, and unreacted MEM were removed by distillation under reduced pressure (temperature: 125°C, pressure: 1.33 kPa (10 mmHg)) to obtain 115.0 parts by mass of the target ionic salt (abbreviation: [MEM][DOSS], compound represented by chemical formula (114)). The obtained ionic salt was liquid at room temperature (25°C).

[0126] [Synthesis Example 5: Synthesis of [Na][DOSS]; Synthesis of ionic salts] 100.0 parts by mass of an aqueous methanol solution of dioctyl sulfosuccinate sodium salt (manufactured by Nippon Emulsifier Co., Ltd., product name: Newcol 291-M, abbreviation: N-291-M) was removed by distillation under reduced pressure (temperature: 150°C, degree of reduced pressure: 1.33 kPa (10 mmHg)) to obtain 65.0 parts by mass of the target ionic bonded salt (abbreviation: [Na][DOSS], compound represented by chemical formula (120)).

[0127] [Synthesis Example 6: Synthesis of [2M-MA] [707-S]; Synthesis of ionic salts] To 185.3 parts by mass of N,N-diethylaminoethyl methacrylate (abbreviation: 2A-MA), 920.1 parts by mass of polyoxyethylene polycyclic phenyl ether sulfate ammonium salt (abbreviation: 707-SF), obtained by removing water under reduced pressure from a 30% aqueous solution of polyoxyethylene polycyclic phenyl ether sulfate ammonium salt (manufactured by Nippon Emulsifier Co., Ltd., trade name: Newcol 707-SF, abbreviation: N-707-SF), was added, and the mixture was reacted for 1 hour. After the reaction, 1088.4 parts by mass of the target ionic salt (abbreviation: [2A-MA][707-S], a compound represented by chemical formula (123)) was obtained.

[0128] [Synthesis Example 7: Synthesis of [2M-AA] and [130305-S]; Synthesis of ionic salts] 200.4 parts by mass of tridecanol was mixed with 2 parts by mass of potassium hydroxide, and the mixture was heated to 170°C. Then, 216.3 parts by mass of 1,2-butylene oxide was injected under pressure of 1.0 MPa or less, and the mixture was reacted for 10 hours. Subsequently, 220.3 parts by mass of ethylene oxide was injected under pressure of 1.0 MPa or less, and the mixture was reacted for 10 hours to obtain 639 parts by mass of polyoxybutylene / polyoxyethylene tridecyl ether. The obtained polyoxybutylene / polyoxyethylene tridecyl ether was heated to 110°C, and 97.1 parts by mass of sulfamic acid was added and the mixture was reacted for 3 hours. After the reaction, the unreacted sulfamic acid was filtered off, and polyoxybutylene / polyoxyethylene tridecyl ether sulfate ammonium salt ([C 13 H 27 -O-(BO)3-(EO)5-SO3 - ][NH4+ 734.1 parts by mass were obtained.

[0129] 143.2 parts by mass of N,N-dimethylaminoethyl acrylate (abbreviation: 2M-AA) was mixed with 734.1 parts by mass of the polyoxybutylene / polyoxyethylene tridecyl ether sulfate ammonium salt (abbreviation: 130305-SF) synthesized above, and the mixture was reacted at 50°C for 1 hour. After the reaction, 860.1 parts by mass of the target ionic salt (abbreviation: [2M-AA][130305-S], a compound represented by chemical formula (129)) was obtained.

[0130] [Synthesis Example 8: Synthesis of [APM-Si] and [EHDG-S]; Synthesis of ionic salts] 150.0 parts by mass of diethylene glycol mono-2-ethylhexyl ether (manufactured by Nippon Emulsifier Co., Ltd., trade name: 2-ethylhexyl diglycol, abbreviation: EHDG) was added to 150.0 parts by mass of toluene and the temperature was raised to 110°C. 80.2 parts by mass of sulfamic acid was added and the mixture was reacted for 3 hours. After the reaction, the excess sulfamic acid was filtered off to obtain diethylene glycol mono-2-ethylhexyl ether sulfate ammonium salt (abbreviation: EHDG-SF; ammonium ion is NH4). + A toluene solution of ) was obtained.

[0131] To 100.0 parts by mass of a 50% toluene solution of the EHDG-SF obtained above, 42.7 parts by mass of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903, abbreviation: APM-Si) was added, and the mixture was reacted at 120°C for 3 hours. (The molar ratio of EHDG-SF to APM-Si was 1:1.5). After the reaction was complete, toluene and unreacted APM-Si were removed by distillation under reduced pressure (temperature: 150°C, pressure: 1.33 kPa (10 mmHg)) to obtain 72.3 parts by mass of the target ionic salt (abbreviation: [APM-Si][EHDG-S]; compound represented by chemical formula (139)).

[0132] The obtained NMR spectral data for [APM-Si] and [EHDG-S] are shown below. 1H-NMR (CDCl3, 400MHz) δ0.65-0.75(t, 2H), 0.83-0.90(m, 6H), 1.27-1.42(m, 8H), 1.47-1.53(m, 1H), 1.77-1.86(m, 2H), 2.96-3.05(m, 2H), 3.30-3.36(m, 2H), 3.56(s, 11H), 3.62-3.65(t, 2H), 3.73-3.75(t, 2H), 4.25-4.28(t, 2H).

[0133] [Examples 1-14 and Comparative Examples 1-11] 200 parts of antimond-doped tin oxide (ATO) powder (volume-average primary particle size 0.01-0.03 μm; product name "SN-100p"; manufactured by Ishihara Sangyo Co., Ltd.) or phosphorus-doped tin oxide (PTO) (product name "SP-2"; manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.) as conductive fillers were mixed with 2, 5, or 10 parts of the conductive additives listed in Tables 1 to 3, 800 parts of 2-butanol as a solvent, and 5800 parts of zirconia beads. All components were placed in a container and kneaded in a wet grinder for 2 hours. In Comparative Example 11, no conductive additive was added in the above procedure. After kneading, the zirconia beads were removed to obtain a dispersion containing the conductive filler. To this dispersion, 100 parts of DPHA (dipentaerythritol hexaacrylate) as a resin and 3 parts of 1-hydroxycyclohexyl phenyl ketone as a polymerization initiator were added and uniformly dissolved to obtain the conductive film-forming compositions of Examples 1-14 and Comparative Examples 1-11. The obtained conductive film-forming compositions were coated onto a PET plate (100 mm × 200 mm, 1 mm thick) to a wet film thickness of 50 μm, dried in a 70°C oven for 1 minute, and subjected to a pressure test of 500 mJ / cm² using a high-pressure mercury lamp under air. 2 By irradiating with light, test specimens of Examples 1-14 and Comparative Examples 1-11, each having a coating film made of a conductive resin composition, were obtained.

[0134] [Examples 15, 17 and Comparative Examples 12, 14] The conductive film-forming compositions of Examples 15, 17, and Comparative Examples 12, 14 were obtained by following the same procedure as in Examples 1-14 and Comparative Examples 1-11, except that no conductive additive was added to 150 parts of ATO powder or PTO powder, or 1.5 parts of a conductive additive listed in Table 4 were added. The obtained conductive film-forming compositions were applied to PET plates (100 mm × 200 mm, 1 mm thick) by following the same procedure as in Examples 1-14 and Comparative Examples 1-11 to obtain test pieces of Examples 15, 17, and Comparative Examples 12, 14 having a coating made of the conductive resin composition.

[0135] [Examples 16, 18 and Comparative Examples 13, 15] The conductive film-forming compositions of Examples 16, 18, and Comparative Examples 13, 15 were obtained using the same procedure as in Examples 1-14 and Comparative Examples 1-11, except that no conductive additive was added to 133 parts of ATO powder or PTO powder, or 1.3 parts of a conductive additive listed in Table 4 was added. The obtained conductive film-forming compositions were applied to PET plates (100 mm × 200 mm, 1 mm thick) using the same procedure as in Examples 1-14 and Comparative Examples 1-11 to obtain test pieces of Examples 16, 18, and Comparative Examples 13, 15 having a coating made of the conductive resin composition.

[0136] In the comparative example, [Na][EHDG-P] used as a conductive additive is a compound represented by the following formula, and [trimethylpropylammonium][TFSA] is a salt of trimethylpropylammonium and trifluoromethanesulfonic acid.

[0137] [ka]

[0138] [Comparative Examples 16-21] The conductive film-forming compositions of Comparative Examples 16 to 21 were obtained using the same procedure as in Examples 1 to 14 and Comparative Examples 1 to 11, except that the amounts of ATO powder and conductive additive (either acetylacetone or fluorinated ionic liquid (IL-A2, manufactured by Koei Chemical Co., Ltd.)) listed in Table 5 were used. The obtained conductive film-forming compositions were applied to PET plates (100 mm × 200 mm, 1 mm thick) using the same procedure as in Examples 1 to 14 and Comparative Examples 1 to 11 to obtain test pieces of Comparative Examples 16 to 21 having a coating made of the conductive resin composition.

[0139] [Examples 22-33] The conductive film-forming compositions of Examples 22 to 33 were obtained by following the same procedure as in Examples 1 to 14 and Comparative Examples 1 to 11, except that the amount of ATO powder listed in Table 6 or Table 7 and the amount of conductive additive (any of [MEM][EHDG-S], [2M-MA][707-S], [2M-AA][130305-S], or [APM-Si][EHDG-S]) listed in Table 5 were used. The obtained conductive film-forming compositions were applied to PET plates (100 mm × 200 mm, 1 mm thick) by following the same procedure as in Examples 1 to 14 and Comparative Examples 1 to 11 to obtain test pieces of Examples 22 to 33 having a coating made of a conductive resin composition.

[0140] [Examples 34, 35 and Comparative Examples 22, 23] The conductive film-forming compositions of Examples 34, 35 and Comparative Examples 22, 23 were obtained by following the same procedure as in Examples 1-14 and Comparative Examples 1-11, except that the resin was changed from DPHA to a mixture of DPHA and urethane acrylate (UN-350, manufactured by Negami Kogyo Co., Ltd.) (mass ratio: DPHA:urethane acrylate = 33:67) for 200 parts of ATO powder, the solvent was changed from 2-butanol to propylene glycol monomethyl ether (PGM), and the conductive additive was either omitted or used in the amount of conductive additive listed in Table 8 ([MEM][EHDG-S], [MEM][DOSS], or any of the zirconia complexes). The obtained conductive film-forming compositions were applied to PET plates (100 mm × 200 mm, 1 mm thick) using the same procedure as in Examples 1-14 and Comparative Examples 1-11 to obtain test pieces of Examples 34, 35 and Comparative Examples 22, 23 having a coating film made of the conductive resin composition.

[0141] [Examples 36-38 and Comparative Examples 24-27] (Regarding resin) First, the resins to be used in the conductive film-forming compositions of Examples 36-38 and Comparative Examples 24-27 were prepared.

[0142] Preparation of acrylate resin (P1) In a flask equipped with a condenser, nitrogen inlet tube, thermometer, and Teflon crescent-shaped stirring blade, 300.0 parts by mass of toluene, 70.0 parts by mass of n-butyl acrylate (BA), and 130.0 parts by mass of methyl methacrylate (MMA) were charged. 3.0 parts by mass of azobisisobutyronitrile was added as a polymerization catalyst, and polymerization was carried out at 90°C for 3 hours to obtain a resin (P1) with a solid content of 50% toluene solution (mass ratio; BA:MMA = 35:65).

[0143] Preparation of acrylate-styrene resin (P2) Resin (P2) (mass ratio; BA:St = 35:65) was obtained in the same manner as the preparation of resin (P1), except that 130.0 parts by mass of styrene (St) were used instead of methyl methacrylate (MMA).

[0144] (Preparation of resin composition and test specimens) To 200 parts of ATO powder, either no conductive additive was added, or 2 parts of a conductive additive ([MEM][EHDG-S], [MEM][DOSS], or a zirconia complex) were added, along with 800 parts of propylene glycol monomethyl ether (PGM) and 5800 parts of zirconia beads. All components were placed in a container and kneaded in a wet grinder for 2 hours. After kneading, the zirconia beads were removed to obtain a dispersion of zirconium oxide fine particles. To this dispersion, an acrylate-based resin (P1) or acrylate-styrene-based resin (P2) equivalent to 100 parts in solid content was added and uniformly dissolved to obtain a conductive film-forming composition. The obtained conductive film-forming composition was coated onto a glass plate (100 mm × 200 mm, 2 mm thick, chamfered) to a wet film thickness of 50 μm and dried in a dryer at 110°C for 10 minutes to obtain test pieces of Examples 36-38 and Comparative Examples 24-27 having a coating film made of the conductive resin composition.

[0145] [Example 39 and Comparative Example 28] The conductive film-forming compositions of Example 39 and Comparative Example 28 were obtained by following the same procedure as in Examples 1-14 and Comparative Examples 1-11, except that the conductive filler (ATO powder) was replaced with a white conductive material (a mixed system of titanium dioxide and antimond-doped tin oxide, volume-average primary particle size: 0.2-0.3 μm, product name: ET-500W; manufactured by Ishihara Sangyo Co., Ltd.), the solvent was changed from 2-butanol to toluene for 200 parts of this conductive filler, and the conductive additive was either omitted or used in the amount of conductive additive ([MEM][EHDG-S]) listed in Table 10. The obtained conductive film-forming compositions were applied to a PET plate (100 mm × 200 mm, thickness 1 mm) following the same procedure as in Examples 1-14 and Comparative Examples 1-11 to obtain test pieces of Example 39 and Comparative Example 28 having a coating film made of the conductive resin composition.

[0146] [Examples 40, 41 and Comparative Example 29] The conductive film-forming compositions of Examples 40, 41, and Comparative Example 29 were obtained by following the same procedure as in Examples 1-14 and Comparative Examples 1-11, except that 200 parts of ATO powder were used, the resin was changed from DPHA to an acrylic resin (Acrydic A-168; DIC Corporation), the solvent was changed from 2-butanol to toluene, and the conductive additive was either omitted or used in the amount of conductive additive (either [MEM][EHDG-S] or [MEM][DOSS]) listed in Table 11. Two mL of the obtained conductive film-forming composition was applied to a glass plate (100 mm × 200 mm, 2 mm thick, chamfered) to a wet film thickness of 50 μm, and dried in a dryer at 110°C for 10 minutes to obtain test pieces of Examples 40, 41, and Comparative Example 29 having a coating made of the conductive resin composition.

[0147] [Examples 42-44 and Comparative Examples 30, 31] The conductive film-forming compositions of Examples 42-44 and Comparative Examples 30 and 31 were obtained by following the same procedure as in Examples 1-14 and Comparative Examples 1-11, except that the conductive filler (ATO powder) was replaced with carbon (Carbon ECP; manufactured by Lion Specialty Chemicals), the resin was changed from DPHA to acrylic resin (Acrydic A-168; manufactured by DIC Corporation) in the amount of conductive filler listed in Table 12, the solvent was changed from 2-butanol to toluene, and the conductive additive was either omitted or used in the amount of conductive additive listed in Table 12 ([MEM][EHDG-S], [MEM][Cum-S], or any of the zirconia complexes). 2 mL of the obtained conductive film-forming composition was applied to a glass plate (100 mm × 200 mm, 2 mm thick, chamfered) to a wet film thickness of 50 μm, and dried in a 110°C oven for 10 minutes to obtain test pieces of Examples 42-44 and Comparative Examples 30 and 31 having a coating film made of the conductive resin composition.

[0148] "evaluation" [Surface resistivity] In accordance with JIS K 6911 (2006), the surface resistivity (Ω) of the coated surface of the above test specimen (substrate with a coating film formed on it) was measured using a high resistivity meter, Hi-Lester UP (manufactured by Mitsubishi Chemical Analytec Co., Ltd.), at a measurement temperature of 25°C, humidity of 50%RH, and applied voltage of 10V.

[0149] [Surface resistivity after rinsing] The test specimens for which surface resistivity was measured were subjected to running tap water (approximately 1L) for 30 seconds, then rinsed with deionized water, wiped to remove water droplets, and dried at 110°C for 5 minutes. The surface resistivity [Ω / □] after rinsing was measured in the same manner as above, except that the surface resistivity of the test specimens after this process was performed only once.

[0150] [Hayes] In accordance with JIS K 7136 (2000), the haze value of the above test specimen (substrate on which the coating film was formed) was measured using a haze meter (NDH-7000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0151] [Water-resistant adhesion] The test specimens (substrates with a coating film formed on them) were impregnated in 40°C hot water for 24 hours. Subsequently, cross-cuts were performed on the coated surface of the test specimens according to the following procedure, and evaluation was conducted according to the criteria below. (1) On the coated surface of the test specimen (coated surface), make 11 parallel cuts at 1 mm intervals, reaching the substrate, then rotate the specimen by 90° and make 11 more cuts in the same manner; (2) Apply cellophane adhesive tape so that it adheres to the cut surface of the paint film by about 50 mm, and rub it with an eraser to make the tape stick to the paint film; (3) After attaching to the tape, wait 1-2 minutes, then hold the end of the tape, keeping it perpendicular to the painted surface, and peel it off; (4) On the painted surface from which the cellophane adhesive tape has been peeled off, the following evaluation will be performed.

[0152] Evaluation criteria: ○: Out of 100 notched grids, 0 to 4 grids were removed. ×: Out of 100 notched grids, 5 or more grids have been removed.

[0153] Tables 1 to 12 below show the evaluation results for surface resistivity, surface resistivity after washing, haze, and water-resistant adhesion of the test specimens for Examples 1 to 45 and Comparative Examples 1 to 31. In Tables 1 to 12, "-" in the conductive resin composition indicates that the compound is not contained, and "-" in the coating film evaluation indicates that the evaluation was not performed.

[0154] [Water-resistant adhesion to various substrates] The water-resistant adhesion of the conductive resin compositions obtained in Examples 9, 12, 28, and 31, and Comparative Examples 11 and 19, was evaluated on various substrates. Specifically, each conductive resin composition was applied to a PET sheet (100 mm × 200 mm, 1 mm thick), a talc-containing polypropylene sheet (100 mm × 200 mm, 3 mm thick, Daicel PP PT6N1; Daicel Mirise), an ABS resin sheet (5 mm × 150 mm, 1 mm thick, ABS Tough Ace EAR-003; Sumitomo Bakelite Co., Ltd.), a transparent acrylic sheet (75 mm × 150 mm, 2 mm thick, Acrylite L-001; Mitsubishi Chemical Corporation), and a black acrylic sheet (75 mm × 150 mm, 2 mm thick, Acrylite L-502; Mitsubishi Chemical Corporation). After drying in a dryer at 70°C for 1 minute, a pressure test of 500 mJ / cm² was performed using a high-pressure mercury lamp under air. 2 By irradiating the specimen with light, a test piece having a coating made of a conductive resin composition was obtained.

[0155] The water-resistant adhesion of the conductive resin compositions of Examples 9, 12, 28, 31 and Comparative Examples 19 and 11 was evaluated on a 10-point scale when applied to various substrates. Specifically, the number of peeled-off grids out of 100 notched grids was evaluated based on the following evaluation criteria. Table 13 shows the results of the evaluation of the water-resistant adhesion of the conductive resin compositions of Examples 9, 12, 28, 31 and Comparative Examples 19 and 11 to various substrates on a 10-point scale.

[0156] Evaluation criteria: 10: Out of 100 notched grids, 0 grids were removed. 8: Out of 100 notched grids, 1 to 2 grids were removed. 6: Out of 100 notched grids, 3 to 4 grids were removed. 4: Out of 100 notched grids, 5 to 14 grids were removed. 2: Out of 100 notched grids, 15 to 30 grids were removed. 0: Out of 100 notched grids, 31 or more grids have been removed.

[0157] [Table 1]

[0158] [Table 2]

[0159] [Table 3]

[0160] [Table 4]

[0161] [Table 5]

[0162] [Table 6]

[0163] [Table 7]

[0164] [Table 8]

[0165] [Table 9]

[0166] [Table 10]

[0167] [Table 11]

[0168] [Table 12]

[0169] [Table 13]

[0170] The above evaluation demonstrated that a conductive coating film (conductive film) made from a conductive resin composition to which the predetermined ionic bonded salt according to the present invention is added has excellent conductivity. On the other hand, in Comparative Examples 1 to 31, which did not contain the predetermined ionic bonded salt according to the present invention, sufficient conductivity could not be obtained. Thus, it can be seen that the predetermined ionic bonded salt according to the present invention can sufficiently impart conductivity to a conductive resin composition containing a conductive filler and resin even in a relatively small amount (i.e., it is useful as a conductive additive).

[0171] As described above, the conductive additive of the present invention can impart good conductivity to conductive resin compositions. Therefore, the conductive additive of the present invention is suitably used in conductive resin compositions used in conductive pastes, conductive paints, conductive adhesives, conductive inks, conductive films, conductive fibers, conductive rubber (such as rollers for photocopiers), industrial packaging materials (such as IC tapes and carrier tapes), and electrostatic coating primers (especially those used for automotive parts, etc.). It has also been shown that molded articles using such conductive resin compositions are suitably used in displays, touch panels, antistatic flooring, IC trays, silicon wafer cases, etc.

[0172] This application is based on Japanese Patent Application No. 2021-081746, filed on 13 May 2021, the disclosures thereof being incorporated herein by reference in their entirety.

Claims

1. A salt comprising an ionic bond having any of the following structures, Conductive additives used to improve the conductivity of conductive resin compositions containing conductive fillers and resins: 【Chemistry 1-1】 [Chemistry 1-2] [Chemistry 1-3] [Chemistry 1-4] [Chemistry 1-5] [Chemistry 1-6] [Chemistry 1-7]

2. The conductive additive according to Claim 1, wherein the ionic bonded salt has any of the following structures: 【Chemistry 2-1】 【Chemistry 2-2】

3. A conductive resin composition comprising a conductive additive according to claim 1 or 2, a conductive filler, and a resin.

4. The conductive resin composition according to claim 3, wherein the conductive filler is one or more selected from the group consisting of tin-doped indium oxide, phosphorus-doped tin oxide, tin oxide, antimond-doped tin oxide, graphite particles, carbon nanotubes, conductive carbon black, and titanium oxide.

5. The conductive resin composition according to claim 3 or 4, wherein the resin is one or more selected from the group consisting of (meth)acrylic resin, polystyrene resin, polyolefin resin, polyurethane resin, polyester resin, epoxy resin, melamine resin, and silicone resin.

6. A molded article comprising the conductive resin composition described in any one of claims 3 to 5.

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