JP2019218355A - Ion-bonding salt, ion-bonding salt composition and resin composition containing the same - Google Patents

Abstract

To provide a novel technique that can improve antistatic properties of a resin composition containing a silicone compound or a fluorine compound without using an expensive conductive polymer or a metal that impairs the lightness or color tone of a resin.SOLUTION: The present invention provides an ion-bonding salt represented by the following formula (1). In the formula (1), Qis a cation derived from a silane compound containing an amino group or an imino group; in the formula (1), Tis a sulfate ester anion, phosphate anion, or sulfonic acid anion having an oxyalkylene chain.SELECTED DRAWING: None

Description

The present invention relates to an ion-binding salt, an ion-binding salt composition, and a resin composition containing the same.

Conventionally, coatings, adhesives, adhesives, fiber auxiliaries, building materials films, protective films such as hard coats, housing for home appliances, papermaking applications (surface coating agents, etc.), civil engineering applications (concrete admixtures, etc.) In order to impart water repellency and oil repellency to a resin surface, a technique of adding a silicone compound or a fluorine compound to the resin is known. In this technique, a resin having excellent antifouling properties can be obtained by arranging a silicone compound or a fluorine-based compound on the resin surface and utilizing the water repellency or oil repellency of these compounds themselves.

On the other hand, from a practical point of view, in the resin composition in which the above-mentioned silicone compound or fluorine compound is disposed on the resin surface, not only water repellency or oil repellency but also antistatic properties are important factors. One.

Here, in order to impart antistatic properties to the resin, a method of applying a surfactant to the resin surface or a method of dispersing the surfactant inside the resin during polymerization of the resin is generally used.
At this time, a part of the surfactant stays on (or is exposed to) the resin surface to form a conductive path, thereby exhibiting antistatic properties. Such surfactants are generally classified according to ionicity into cationic, anionic, amphoteric and nonionic, and it is said that the antistatic effect has the highest cationicity.

However, in a resin composition containing a silicone compound or a fluorine-based compound, these compounds are arranged on the surface of the resin composition. However, since the affinity between these compounds and the surfactant is extremely low, an interface is formed on the surface of the resin composition. The activator can hardly be arranged (dispersed). That is, it is known that even when a surfactant is added to a resin composition containing a silicone compound or a fluorine-based compound, the surfactant is not arranged on the surface of the resin composition and sufficient antistatic properties cannot be obtained. I have. Therefore, a technique of further adding a conductive polymer or a metal material to impart antistatic properties to a resin composition containing such a silicone compound or a fluorine-based compound has been studied. However, adding conductive polymers and metallic materials is costly,
In particular, when a metal material is added, there is a problem that the lightness and color tone of the resin are impaired.

In view of this, a technique has been proposed in which an agglomerate obtained by adhering conductive material particles around polymer solid electrolyte base particles is mixed with a resin (for example, Patent Document 1).

JP-A-2004-107555

According to the technique of Patent Document 1, antistatic properties can be imparted to a resin composition containing a silicone compound or a fluorine-based compound. However, the technique disclosed in Patent Document 1 does not substantially solve the above-described problem because a polymer solid electrolyte and a metal oxide as a conductive material are used. That is, in the technique of Patent Document 1, since the metal oxide is used, the problem that the lightness and color tone of the resin are impaired is not completely solved.
In addition, since solid polymer electrolytes are generally expensive, there is still a need for a cheaper method.

Therefore, the present invention can improve the antistatic property of a resin composition containing a silicone compound or a fluorine-based compound without using an expensive conductive polymer or a metal that impairs the lightness and color tone of the resin. It aims to provide technology.

In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, surprisingly, an ion-binding salt composed of a cation derived from a silane compound containing an amino group or an imino group, and a sulfate ester anion, a phosphate ester anion or a sulfonate anion having an oxyalkylene chain is formed. It has been found that the addition thereof improves the antistatic properties of a resin composition containing a silicone compound or a fluorine-based compound, thereby completing the present invention.

  That is, the present invention is an ion-binding salt represented by the following formula (1):

In the above equation (1),
Q ⁺ is a cation derived from a silane compound containing an amino group or an imino group;
In the above formula (1), T ⁻ is the following formula (t-1):

In the above formula (t-1),
R ¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbon group; An aryl group having 6 to 30 atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms,
A ¹ is a linear or branched alkylene group having 2 to 4 carbon atoms,
s is an integer of 0 to 50;
A sulfate ester anion represented by
The following formula (t-2):

In the above formula (t-2),
R ² and R ³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon group having 3 to 2 carbon atoms.
A cycloalkyl group of 0, 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, wherein R ² and R ³ are not simultaneously hydrogen atoms,
A ² and A ³ are each independently a linear or branched alkylene group having 2 to 4 carbon atoms;
t and u are each independently an integer of 0 to 50;
Represented by a phosphate ester anion, or
The following formula (t-3):

In the above formula (t-3),
R ⁴ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbon group; An aryl group having 6 to 30 atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms,
A ⁴ is a linear or branched alkylene group having 2 to 4 carbon atoms,
v is an integer of 0 to 50;
Is a sulfonate anion represented by

According to the present invention, by adding a cation derived from a silane compound containing an amino group or an imino group, and an ion-binding salt composed of a specific anion having an oxyalkylene chain, a silicone compound or a fluorine-based compound is included. The antistatic property of the resin composition can be improved. Therefore, a novel technology is provided that can improve the antistatic property of a resin composition containing a silicone compound or a fluorine-based compound without using an expensive conductive polymer or a metal that impairs the lightness and color tone of the resin. sell.

According to a first aspect of the present invention, there is provided an ion-bonding salt represented by the above formula (1) (hereinafter, sometimes simply referred to as “ion-binding salt (1)”). As described above, the ion-bonding salt (1) of the present invention comprises a cation derived from a silane compound containing an amino group or an imino group, and a specific anion having an oxyalkylene chain.

As described above, in a resin composition containing a silicone compound or a fluorine-based compound, since a silicone compound or a fluorine-based compound is arranged on the surface of the resin composition, a surfactant having a low affinity for these compounds is a resin. The surface of the composition cannot be coated (or exposed), and it is difficult to improve the antistatic property. Therefore, with respect to such a resin composition, conventionally, an antistatic property has been improved by using a conductive polymer, a metal material, or the like.

On the other hand, by adding the ion-binding salt (1) having the above structure of the present invention,
The antistatic properties of the resin compositions containing these silicone compounds and fluorine compounds can be improved. The mechanism is not clear, but speculates as follows.

The ion-binding salt (1) according to the present invention has a cation and an anion
The resin composition containing a silicone compound or a fluorine-based compound has a characteristic structure for improving the antistatic property.

First, the cation constituting the ion-binding salt (1) according to the present invention is a cation derived from a silane compound having an amino group or an imino group. Here, the silane compound containing an amino group or an imino group can become a cation when the amino group or the imino group is positively charged. And by further containing a silicon atom (Si), the affinity between this silicon part and a silicone compound or a fluorine compound contained in the resin composition is improved. As a result, the affinity between the resin composition and the ion-bonding salt (1) is improved, and the cation moiety (and a paired anion moiety) derived from the amino group or imino group is arranged on the surface of the resin composition. (Exposed on the surface).

Here, the ion-bonding salt (1) is not only arranged (dispersed) only on the surface of the resin composition, but is further contained in the interior, thereby further improving the antistatic property. It is presumed that it will be in a state where it can be made to work. When the ion-bonding salt (1) is taken into the inside of the resin composition, a conductive path is formed not only on the surface of the resin composition but also inside the resin composition, so that the antistatic property is further improved. In other words, the cation portion of the ion-bonding salt (1) (and the anion portion that forms a pair) is arranged on the surface of the resin composition (the cation portion of the ion-binding salt (1) and the like on the surface of the resin composition). Exposure), the conductive path formed by the ion-bonding salt (1) contained in the resin composition can be used more effectively, and as a result, the antistatic property is improved. You can do it.

Next, since the anion constituting the ion-bonding salt (1) provides a counter anion having a structure containing no halogen as a counter anion of the cation, it has an advantage that it can be used even in applications that dislike halogen. Have.

  Hereinafter, the ion-binding salt (1) according to the present invention will be specifically described.

[Ion-binding salt (1)]
The ion-bonding salt (1) is represented by the cation (Q ⁺ ) derived from a silane compound containing an amino group or an imino group, as represented by the above formula (1), and by the above formula (t-1). Sulfate anion, phosphate anion represented by formula (t-2) or formula (t-3)
And a sulfonate anion (T ⁻ ) represented by

(Cation Q ⁺ )
In the above formula (1), the “cation derived from a silane compound containing an amino group or an imino group” refers to a cation obtained by adding a proton or carbocation to a silane compound containing an amino group or an imino group. What is necessary is just to be charged. Therefore, Q ⁺ does not need to be positively charged by the addition of a proton or the like to an amino group or an imino group in a silane compound containing an amino group or an imino group. May be positively charged, but from the viewpoint of availability, it is preferable that a proton or the like is added to the amino group or imino group to be positively charged.

Here, the “silane compound containing an amino group or an imino group” refers to any compound having at least one or more silicon atoms (Si) and at least one or more amino or imino groups. However, it can be used. In the above, the amino group is represented by "
—N (R ′) ₂ ”, wherein the substituent represented by R ′ is not particularly limited. For example, each independently represents a hydrogen atom, an alkyl group, an aryl group, or the like. No. The imino group is a substituent represented by “—N ＝ C (R ′) ₂ ”, wherein R ′ is the same as described above. Further, the “silane compound containing an amino group or imino group” may contain both an amino group and an imino group.

Examples of such a compound include a silicone compound having an amino group-containing substituent (amino-modified silicone compound), a silane compound having an amino group-containing substituent (a silane compound other than the amino-modified silicone compound), and an imino group. And a silane compound having a substituent containing

Here, the amino-modified silicone compound is a compound in which an organic group containing an amino group is introduced into a side chain of polysiloxane (side chain type), or a compound in which an organic group containing an amino group is introduced into both ends of polysiloxane (both sides). (Terminal type), those having an organic group containing an amino group introduced at one end of polysiloxane (one end type), those having an amino group-containing organic group introduced at the side chain and both ends of the polysiloxane (
Side-chain type) and those obtained by introducing an organic group containing an amino group into the side chain and one end of polysiloxane (one-side chain type).

The amino-modified silicone compound is not particularly limited, but may have an amine equivalent (amino group 1).
It is preferable to use a compound having a mass (g) of 15000 g / mol or less, more preferably 300 to 13000 g / mol. Moreover, kinematic viscosity (25 ° C.) are preferably the use of what is 1~20000mm ² / s, more preferably used those which are 10~5000mm ² / s.

Commercially available silicone compounds that can satisfy these conditions include, for example, X-22-16
1A, X-22-161B, KF-8010, KF-8012 (all manufactured by Shin-Etsu Chemical Co., Ltd.), Dynasylan (registered trademark) 1122, 1124, 1146, 1161,
1189, 1411, 1505, 1506, 2627, 2909; Dynasylan (
(Registered trademark) SIVO210, SIVO214, DAMO-M, AMEO-T, AMMO;
HYDROSIL (registered trademark) 1151, 2627, 2776, 2909 (EVO)
NIK INDUSTRIAL), BY16-871, 16-853U, 16-84
9, 16-872, 16-878, 16-890, 16-891, 16-893, 16-
And amino-modified silicone compounds such as FZ-3705, 3785, 3789; SF8147 (manufactured by Dow Corning Toray Co., Ltd.).

The silane compound having a substituent having an amino group (a silane compound other than the amino-modified silicone compound) may be any one having at least one silicon atom and an amino group as described above. For example, aminosilane, diaminosilane, triaminosilane, alkylaminosilane (N- (trimethylsilyl) diethylamine, N
-(Trimethylsilyl) dimethylamine, N- (triethylsilyl) diethylamine, N
-(Triethylsilyl) dimethylamine, etc.), alkyl (alkylamino) silane, (
Alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, cycloalkyl (alkylamino) alkoxysilane, tetrakis (alkylamino) silane, alkyltris (alkylamino) silane, dialkylbis (alkylamino) silane, trialkyl (alkyl) Amino) silane, tris (alkylamino) alkoxysilane, bis (alkylamino) dialkoxysilane, and (alkylamino) trialkoxysilane.

As the silane compound having a substituent containing an imino group, any silane compound having one or more silicon atoms and an imino group as described above may be used.
Examples thereof include alkyl (trialkylsilyl) alkanimine, N-alkyl (alkoxydialkylsilyl) alkanimine, N-alkyl (dialkoxyalkylsilyl) alkanimine, and N-alkyl (trialkoxysilyl) alkanimine.

Further, the amino-modified silicone compound and the silane compound having a substituent containing an amino group (a silane compound other than the silicone compound) are preferably those in which the amino group contained in the compound is primary, secondary or tertiary. Primary or secondary is more preferred, and primary is particularly preferred. Primary to tertiary amines are preferred from the viewpoint of simplification of the reaction process. And from such a viewpoint, it is particularly preferable that the silane compound containing an amino group or an imino group contains a primary amine.

As described above, examples of the silane compound containing an amino group or an imino group include an amino-modified silicone compound, a silane compound having a substituent containing an amino group (a silane compound other than the amino-modified silicone compound), and a substituted silane compound containing an imino group. A silane compound having a group can be used. These compounds can be appropriately selected depending on the silicone compound used from the viewpoint of compatibility with the silicone compound contained in the resin composition.

In the silane compound having a substituent having an amino group (a silane compound other than the amino-modified silicone compound) or the silane compound having a substituent having an imino group, the position of an amino group or an imino group and a silicon atom (in the molecule) The position) is not particularly limited, but preferably has a silicon atom at one end of the molecular main chain and an amino group or imino group at the other end. If the distance between the amino group or the imino group and the silicon atom is too short, the affinity between the resin composition and the silicon may be inhibited by a cation derived from the amino group or the imino group. Thus, a certain distance can be maintained between the silicon atom and the amino group or imino group. As a result, the silicon terminal can be arranged on the surface side of the resin composition and the amino group (amino cation) or imino group (imino cation) can be arranged at a predetermined distance from the surface of the resin composition. The ion-binding salt according to (1)
) Can stably coat the surface of the resin composition. Here, the term “coating” includes a form in which the ion-bonding salt (1) is adsorbed on the surface and a form in which the salt is protruded from the surface.

Therefore, the silane compound preferably has a certain size, and the molecular weight is preferably 100 or more, and more preferably 150 or more. On the other hand, the upper limit is not particularly limited, but considering the substantially available silane compound, 20
It is preferably at most 00 (excluding the amino-modified silicone compound).

More specifically, the silane compound having a substituent having an amino group (a silane compound other than the amino-modified silicone compound) preferably has the following structure.

That is, the ion-binding salt (1) is represented by the following formula (1):
Q ⁺ is represented by the following formula (q-1):

In the above formula (q-1),
X is, -CH ₂ - is or oxygen atom (-O-),
Y is -NH-,
Z is, -N ^(R _{6) 2} or -N = ^{C (R} _{6) 2,}
R ⁵ is each independently a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom having 1 carbon atom.
~ 20 alkoxy groups, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, substituted or An unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms (—OR ⁷ , wherein R ⁷ is a substituted or unsubstituted group; Represents a substituted aryl group having 6 to 30 carbon atoms)
R ⁶ is each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms,
A substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted 6 carbon atom 30 aryloxy group (-OR ^8, this time, ^{R 8} represents whether or unsubstituted aryl group having 6 to 30 carbon atoms which is substituted), and
m is an integer of 0 to 5,
n is an integer of 0 to 5,
q is 0 or 1,
r is 0 or 1,
And an ion-binding salt which is a cation derived from the compound represented by the formula (1).

In this specification, “substituted or unsubstituted” means that a hydrogen atom of a certain group may or may not be substituted with another group. Here, the substituent that can be substituted is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms (for example, cyclopentyl group, cyclohexyl group), a hydroxyalkyl group having 1 to 20 carbon atoms (for example, , A hydroxymethyl group, a hydroxyethyl group), an alkoxyalkyl group having 2 to 20 carbon atoms (for example, methoxyethyl group and the like), an alkoxy group having 1 to 20 carbon atoms (for example, methoxy group,
Ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, dodecyloxy group, etc.),
A cycloalkoxy group having 3 to 20 carbon atoms (for example, cyclopentyloxy group, cyclohexyloxy group), an alkenyl group, an alkynyl group, an amino group, an aryl group, and a carbon atom having 6 to 20 carbon atoms;
30 aryloxy groups (e.g., phenoxy group, naphthyloxy group), having 1 to 1 carbon atoms
20 alkylthio groups (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group), and cycloalkylthio groups having 3 to 20 carbon atoms (eg, cyclopentylthio group, cyclohexylthio group) An arylthio group having 6 to 30 carbon atoms (eg, phenylthio group, naphthylthio group), an alkoxycarbonyl group having 1 to 20 carbon atoms (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxy Carbonyl group, dodecyloxycarbonyl group), aryloxycarbonyl group having 7 to 20 carbon atoms (for example, phenyloxycarbonyl group, naphthyloxycarbonyl group), hydroxyl group (-OH), carboxyl group (-COOH), Lumpur group (-SH), and the like cyano group (-CN) is.
Further, the number of substituents further substituted with one substituent is not particularly limited, and can be appropriately selected in consideration of a desired effect (improvement of antistatic property). Note that, in the above, there is no substitution with the same substituent. For example, a substituted alkyl group is not substituted with an alkyl group.

In the above formula (q-1), X is a divalent group directly substituting on a silicon atom, and represents —CH ₂ —
Or an oxygen atom (-O-). Here, q represents the number of X and is 0 or 1. Therefore, the substituent represented by X may not necessarily be included. From the viewpoint of improving the antistatic properties, and preferably q = 1, this time, X is -CH 2 _- when is preferred.

In the above formula (q-1), Y is a divalent substituent and represents -NH-. Where r is Y
Is 0 or 1. Therefore, the substituent (—NH—) represented by Y does not necessarily have to be included. From the viewpoints of improvement in antistatic properties, stability of the ion-bonding salt (1), ease of arrangement of the ion-binding salt (1) on the surface of the resin composition, and the like, r = 0, that is, Y does not exist. Is more preferred. On the other hand, when Y is present, the substituent can be a secondary amino cation. Therefore, it is preferable that Y be present from the viewpoint of the stability of the amino cation itself.

In the above formula (q-1), Z is a monovalent substituent, and -N (R ⁶ ) ₂ or -N = C (R
⁶ ) ₂ . Incidentally, R ^6, since detailed below, a detailed description thereof will be omitted here. As described above, since the compound represented by the formula (q-1) contains an amino group or an imino group as Z, a proton or the like is added to the nitrogen atom in the amino group or the imino group, and the compound represented by the formula (q-1) The compounds shown tend to be cations. As a result, the ion binding salt (1) can improve the antistatic property of the resin composition.

Here, from the viewpoint of improving the antistatic performance and the stability of the ion-bonding salt (1), Z is -N
(R ⁶ ) ₂ is preferred. At this time, Z easily forms a stable ammonium ion ([-N (R ⁶ ) ₃ ] ⁺ ) by adding a proton or the like.

In the ammonium ion ([—N (R ⁶ ) ₃ ] ⁺ ), R ⁶ is each independently a hydrogen atom or another substituent (such as an alkyl group) containing a carbon atom described in detail below. From the viewpoint of improving antistatic properties, it is preferable that at least one of R ⁶ is a hydrogen atom (that is, Z is a primary to tertiary amino cation), and two or more of R ⁶ are hydrogen atoms (that is, Z is a primary amino cation). And a secondary amino cation, and all three are hydrogen atoms (ie,
Z is particularly preferably a primary amino cation).

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms represented by R ⁵ and R ⁶ in the above formula (q-1) include, for example, methyl group, ethyl group, n -Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isoamyl, tert-pentyl, neopentyl, n-hexyl, 3-methyl Pentan-2-yl group, 3-methylpentane-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-dimethylhexane-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-methylheptane-2-yl group, 3-methylheptane-3-yl group, 4-methylheptane-3 -Yl group, 4-methylheptane-4-yl group, 1-ethylhexyl group, 2-ethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, 1,1-dimethylhexyl group, 1,4-dimethyl Hexyl group, 1,5-dimethyl hexyl 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, n-nonyl, 1-methyloctyl, 6-methyloctyl, 1-ethylheptyl, 1- (n-butyl) pentyl, 4-
Methyl-1- (n-propyl) pentyl group, 1,5,5-trimethylhexyl group, 1,1
, 5-Trimethylhexyl group, 2-methyloctane-3-yl group, n-decyl group, 1-methylnonyl group, 1-ethyloctyl group, 1- (n-butyl) hexyl group, 1,1-dimethyloctyl group A 3,7-dimethyloctyl group, an n-undecyl group, a 1-methyldecyl group,
1-ethylnonyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, 1-methyltridecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n
Linear and branched alkyl groups such as -octadecyl group and n-nonadecyl group. From the viewpoint of availability and antistatic performance, substituted or unsubstituted carbon atoms having 1 to 1 carbon atoms
10 alkyl groups are preferred, and a methyl group, an ethyl group, a 2-ethylhexyl group, a tridecyl group, and a 1,2-bis (2-ethylhexyloxycarbonyl) ethyl group are more preferred, and a methyl group, an ethyl group, and a 2-ethylhexyl group are preferred. Particularly preferred.

Examples of the substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms represented by R ⁵ and R ⁶ in the above formula (q-1) include, for example, a methoxy group, an ethoxy group, and a propoxy group Linear and branched alkoxy groups such as isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, and octyloxy group. In terms of availability and antistatic performance, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms is more preferable, and a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, An ethylhexyloxy group is more preferred.

Examples of the substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms represented by R ⁵ and R ⁶ in the formula (q-1) include, for example, cyclopropyl group, cyclopentyl group, Examples include a cyclohexyl group, a norbornyl group, and an adamantyl group. From the viewpoint of availability and antistatic performance, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms is more preferable, and a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group are more preferable.

Examples of the substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms represented by R ⁵ and R ⁶ in the formula (q-1) include, for example, a cyclopropyloxy group and a cyclopentyloxy group And a cyclohexyloxy group. In terms of availability and antistatic performance, a substituted or unsubstituted cycloalkoxy group having 1 to 10 carbon atoms is more preferable, and a cyclopropyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group are more preferable.

Examples of the substituted or unsubstituted aryl group having 6 to 30 carbon atoms represented by R ⁵ and R ⁶ in the above formula (q-1) include, for example, phenyl group, biphenyl group, -Naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl Group, mesityl group, pentalenyl group,
Binaphthalenyl group, ternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl Group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthenyl group, preyadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, Examples thereof include a rubicenyl group, a colonenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptaenyl group, a pyrantrenyl group, and an ovalenyl group. In terms of availability and antistatic performance, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms is preferable, and a phenyl group, a dimethylphenyl group (2,3-dimethylphenyl group,
2,4-dimethylphenyl group, 3,4-dimethylphenyl group, etc., isopropylphenyl group (2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group), dodecylphenyl group (2-dodecylphenyl group) , 3-dodecylphenyl group, 4
-Dodecylphenyl group) is particularly preferred.

The substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms represented by R ⁵ and R ⁶ in the above formula (q-1) has the chemical formula “—OR ⁷ ” or “−
OR ⁸ ”, wherein R ⁷ represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Here, the description of R ^{7 is} the same as that of the above-described aryl group, and thus the detailed description is omitted here. In light of availability and antistatic performance, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms is preferable, and a phenoxy group and a naphthyloxy group are particularly preferable.

M and n in the above formula (q-1) each independently represent the number of methylene groups (—CH ₂ —), m is an integer of 0 to 5, and n is an integer of 0 to 5 is there. Here, m + n is 0-1.
It is an integer of 0. In the case where Y does not exist (r = 0), the numbers of the methylene groups are synonymous when the value of m + n is the same. For example, m = 1 and n = 2 (m +
When n = 3), it is substantially the same as m = 3 and n = 0, m = 0 and n = 3, m = 2 and n = 1.

Here, when Y does not exist (r = 0), it is preferable that m + n = 1 to 8, more preferably 1 to 5.

When Y is present (r = 1), it is preferable that m + n = 1 to 8, more preferably 2 to 6. Here, it is particularly preferable that m = 1 to 3 and n = 1 to 3.

In the above formula (q-1), when X is present (q = 1) and X is —CH ₂ —, the number is further defined by an adjacent methylene group (—CH ₂ —: m). Are also present (m = 1 to 5), these are synonymous when the value of q + m is the same. Furthermore, X is present (q = 1) and X is -CH ₂ - in the case which is absent Y is (r
= 0), they have the same meaning when the values of q + m + n are the same.

In the above formula (q-1), at least one of R ⁵ substituted on the silicon atom is a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group. Alternatively, it is preferably an unsubstituted cycloalkoxy group having 3 to 20 carbon atoms or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. When the substituent R ⁵ on silicon is a hydroxy group, an alkoxy group, a cycloalkoxy group, or an aryloxy group, the effect of improving the antistatic property of the resin composition can be maintained for a long time. This is because the above substituents (hydroxy group, alkoxy group, cycloalkoxy group,
Aryloxy group) is condensed with a nearby silicon atom by hydrolysis to form-(Si-O-Si)
It is considered that this is for forming the network of-.

Among the compounds represented by the formula (q-1), from the viewpoint that the antistatic property is improved and the antistatic property is particularly long-lasting (that is, the durability is improved), the following effect is obtained. Compounds are preferred. That is, the ionic bonding salt (1) is represented by the formula (q)
In -1), X is —CH ₂ —, Z is —N (R ⁶ ) ₂ , and R ⁵ is each independently a hydrogen atom, a hydroxy group, substituted or unsubstituted. 1 to 2 carbon atoms
A zero alkoxy group, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, at least one hydroxy group, a substituted or whether the unsubstituted 1 to 20 carbon atoms alkoxy groups, or is substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms for R ^5, or substituted, A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, R ⁶ is a hydrogen atom, m is an integer of 0 to 3, n is 0, and q is 1 And r is 0; and preferably includes a cation Q ⁺ derived from the compound represented by the following formula:

Furthermore, among the compounds represented by the above formula (q-1), it is preferable that all R ⁵ be a hydroxy group or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms. More preferably, it is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. The ion-bonding salt (1) containing the cation Q ⁺ derived from such a compound can maintain the effect of particularly improving the antistatic performance for a long time.

Specific compounds preferably used as the silane compound containing an amino group or an imino group in the present invention include the following compounds.

For example, N- (trimethylsilyl) diethylamine, N- (trimethylsilyl) dimethylamine, N- (triethylsilyl) diethylamine, N- (triethylsilyl) dimethylamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-2 (-
Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl)-
3-aminopropyldimethoxymethylsilane, 3-triethoxysilyl-N- (1,3-
Dimethyl-butylidene) propylamine, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and the like.

(Anion T ⁻ )
In the above formula (1), the anion (T ⁻ ) is represented by the sulfate anion represented by the formula (t-1), the phosphate anion represented by the formula (t-2) or the formula (t-3). Is a sulfonic acid anion. As described above, since these anions are specific anions having an oxyalkylene chain, they have excellent conductivity, and as a result, can greatly contribute to improvement of the antistatic property of the resin composition. In addition, these anions, as a counter anion of the cation, to provide a counter anion of a structure containing no halogen,
Suitable for use in applications that dislike halogens. Hereinafter, the structures of these anions will be specifically described.

A linear or branched group represented by A ¹ in the above formula (t-1), A ² and A ³ in the formula (t-2), and A ⁴ in the formula (t-3), respectively. Examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, and a butylene group. From the viewpoint of availability, an ethylene group and a propylene group are particularly preferred.

A substituted or unsubstituted group represented by R ¹ in the above formula (t-1), R ² and R ³ in the formula (t-2), and R ⁴ in the formula (t-3), respectively. 1-20 carbon atoms
An alkyl group, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,
Since the same substituents as those in the compound represented by the formula (q-1) described above are exemplified, the detailed description is omitted here.

In addition, examples of the substituted or unsubstituted arylalkyl group 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-
Examples thereof include a naphthyl) ethyl group, a 3- (1-naphthyl) propyl group, and a 3- (2-naphthyl) propyl group.

From the viewpoints of availability and antistatic properties, R ^{1 to} R ⁴ represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted carbon group having 6 carbon atoms. It is more preferably an aryl group having from 30 to 30, furthermore, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Is particularly preferred. Further, in consideration of easy availability and handling such as viscosity, etc., preferred are an n-butyl group, an n-hexyl group, a 2-ethylhexyl group, a dimethylphenyl group, an isopropylphenyl group, and a dodecylphenyl group.

S in the above formula (t-1), t and u in the formula (t-2), and v in the formula (t-3) represent the number of divalent substituents-(OA ^1-4 )- And an integer of 0 to 50. From the viewpoint of ease of handling due to a decrease in viscosity or the like, or interface characteristics, s, t, u and v are each independently preferably an integer of 1 to 40, more preferably an integer of 2 to 30. Where s
, T, u and v are 1 or more, the ion-bonding salt (1) has an oxyalkylene chain. And since the said oxyalkylene chain is excellent in electroconductivity, the ion binding salt (1) containing such an anion further enhances the effect of improving the antistatic property of the resin composition. Therefore, s, t, u and v are more preferably 1 or more, and particularly preferably 2 or more. On the other hand, if the oxyalkylene chain is too long, the viscosity will be high, and in consideration of handling properties, the upper limits of s, t, u and v are preferably 50, and 40
Is more preferable, and 30 is particularly preferable.

In the ion-binding salt (1), a sulfate ester anion represented by the formula (t-1):
The phosphate anion represented by t-2) or the sulfonate anion represented by the formula (t-3) is appropriately selected depending on its use. For example, when heating is required in the use step, a sulfonate anion is preferred, and when heating is not required, other anions are preferred.

(Specific Example of Ion-Binding Salt (1))
More preferable compounds of the ion-bonding salt (1) represented by the formula (1) include ion-binding salts represented by the following chemical formulas (101) to (116).

(Method for producing ionic bonding salt (1))
The method for producing the ion-binding salt (1) is not particularly limited as long as it can produce the ion-binding property having the structure of the formula (1), and any method can be employed. it can. For example, an anion exchange method, a neutralization method, an acid ester method and the like can be mentioned. Further, the following deammonification method and the like are also preferably used.

That is, the ammonium salt of the sulfate anion represented by the formula (t-1) ([t
_{^{-1] - [NH 4] +}} ), Formula (t-2) phosphoric acid ester anion of the ammonium salt represented by ^([t-2] - represented by _[NH ^{4] +)} or formula (t-3) By reacting an ammonium salt of a sulfonate anion ([t-3] ⁻ [NH ₄ ] ⁺ ) with the silane compound containing an amino group or an imino group, the ion-bonding salt (1) can be obtained. it can.
Here, as the ammonium salt of the sulfate, the ammonium salt of the phosphoric acid ester, or the ammonium salt of the sulfonic acid, a commercially available product or one synthesized in advance may be used. The synthesis method is not particularly limited. For example, the ammonium salt of a sulfate may be produced by a conventionally known method such as a method of reacting an alcohol, a phenol or a (poly) oxyalkylene alkyl ether with a sulfamic acid. Can be.

In addition, the reaction conditions at the time of producing the ion-bonding salt (1) are not particularly limited, but are preferably the following conditions.

The molar ratio (charge ratio) of the ammonium salt of the sulfate, the ammonium salt of the phosphoric acid ester, or the ammonium salt of the sulfonic acid to the silane compound having an amino group or an imino group is 1: 1 to 1: 2. The ratio is preferably 1: 1.2 to 1: 1.6. Within such a range, the reaction proceeds efficiently.

The reaction solvent that can be used at the time of use is not particularly limited, and examples thereof include toluene, xylene, and ethanol.

The reaction atmosphere is not particularly limited, and may be, for example, air or an inert gas atmosphere such as nitrogen or argon. However, from the viewpoint of preventing coloring, an inert gas atmosphere such as nitrogen or argon is used. It is preferably below. Under such conditions, the by-product ammonia is distilled off simultaneously with the reaction.

The reaction proceeds simultaneously with the generation of ammonia as a by-product, and the reaction temperature is preferably 20 to 150 ° C, more preferably 50 to 130 ° C. The reaction time is 1 to
The time is preferably 6 hours, more preferably 2 to 5 hours.

After completion of the reaction, a solution containing the ion-binding salt (1), an unreacted raw material containing an amino group or an imino group, and a reaction solvent are obtained, and the silane compound containing an amino group or an imino group and the reaction are obtained. By evaporating the solvent under reduced pressure, the desired ion-bonding salt (1) is obtained. The temperature range during the distillation under reduced pressure is preferably 40 to 170 ° C,
More preferably, it is 50 to 160 ° C. The time for distillation under reduced pressure is preferably 0.5 to 5 minutes.
It is in the range of time, more preferably in the range of 1-2 hours. Further, the degree of reduced pressure during the distillation under reduced pressure is preferably in the range of 0.66 to 6.67 kPa (5 to 50 mmHg), and more preferably in the range of 1.07 to 2.00 kPa (8 to 15 mmHg). .

[Ion-binding salt (2)]
In order to further improve the effect of improving the antistatic property of the ion-bonding salt (1) with respect to the resin composition, another ion-bonding salt may be further added. The cation of the other ion-binding salt is preferably a cation derived from a nitrogen-containing compound and having a structure different from that of the cation of the ion-binding salt (1). On the other hand, the anion of the other ion-binding salt is not particularly limited, and examples thereof include a halide ion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ) and an oxo acid anion (borate anion, carbonate anion, and acetate anion). , A sulfate anion, a sulfate anion, a phosphate anion, a phosphate anion, a sulfonate anion, etc.), a boron-based anion (BF ₄ ⁻ ; tetraalkyl borate such as tetramethyl borate, tetraethyl borate, etc.), tetraphenyl borate, tetrakis (penta tetraarylborate such fluorophenyl) borate), phosphorus-based anion (PF ₆ ^-, etc.), imide anion (bis (trifluoromethanesulfonyl) imide anion of bis (perfluoroalkanesulfonyl) imide anion) and the like.

Among the above, from the viewpoints of improving the antistatic property of the resin composition and easiness in handling, C
l ⁻ , Br ⁻ , sulfate ester anion, phosphate ester anion, sulfonate anion,
Tetraphenyl borate, PF ₆ ⁻ , bis (trifluoromethanesulfonyl) imide anion and the like are preferable. Further, from the viewpoint of improving the antistatic property, the anion of the other ion-bonding salt is a sulfate anion represented by the formula (t-1) of the ion-bonding salt (1) or a formula (t-2) ) Or a sulfonate anion represented by the formula (t-3).

Therefore, according to the second aspect of the present invention, the ion-bonding salt (1) is combined with the following formula (2)
) (Hereinafter sometimes simply referred to as “ion-binding salt (2)”).

In the above equation (2),
(Q ′) ⁺ represents an ammonium ion, an imidazolium ion, a pyridinium ion, a pyrrolidinium ion, a pyrrolium ion, a pyrazinium ion, a pyrimidinium ion,
Consists of triazolium, triazinium, quinolinium, isoquinolinium, indolinium, quinoxalinium, piperazinium, oxazolinium, thiazolinium, and morpholinium ions At least one selected from the group and a structure different from Q ⁺ in the above formula (1);
(T ') ^- is sulfate anion represented by the formula (t-1), the formula (t-2)
Or a sulfonate anion represented by the above formula (t-3).

As described above, the ion-bonding salt composition according to the present invention is an ion-binding salt composition that is a sulfate, phosphate, or sulfonate of a cation derived from a silane compound containing the amino group or imino group. The salt (1) is a sulfate, phosphate, or sulfonate of a cation having a structure different from that of the cation of the ion-binding salt (1);
An ion-binding salt (2). Since the ion-binding salt composition will be described in detail below, first, the cations and anions constituting the ion-binding salt (2) will be described.

(Cation (Q ') ⁺ )
The above (Q ′) ⁺ represents an amine compound (including NH ₃ ), an imidazole compound, a pyridine compound, a pyrrolidine compound, a pyrrole compound, a pyrazine compound, a pyrimidine compound, a triazole compound, a triazine compound, a quinoline compound, an isoquinoline compound, an indole compound, It is a cation derived from at least one compound (nitrogen-containing compound) selected from the group consisting of a quinoxaline compound, a piperazine compound, an oxazoline compound, a thiazoline compound, and a morpholine compound.

Specific examples of the respective nitrogen-containing compounds are described in paragraph [00] of JP-A-2012-72130.
71] to [0091], and among these compounds, amine compounds are particularly preferable from the viewpoint of improvement of antistatic property and availability.

Among the amine compounds, ammonia (NH ₃ ); dimethylamine, diethylamine, monopropylamine, dipropylamine, monobutylamine, dibutylamine,
Methyl (ethyl) amine, methyl (propyl) amine, methyl (butyl) amine, methyl (pentyl) amine, methyl (hexyl) amine, ethyl (propyl) amine, ethyl (
Alkylamines such as butyl) amine, ethyl (pentyl) amine and ethyl (hexyl) amine; monobenzylamine, (1-phenethyl) amine, (2-phenethyl) amine (
Synonyms: monophenethylamine), dibenzylamine, bis (1-phenethyl) amine, bis (2-phenethyl) amine (alias: diphenethylamine) and other aromatic substituted alkylamines; monocyclopentylamine, dicyclopentylamine, monocyclohexylamine , Cycloalkylamines such as dicyclohexylamine, monocycloheptylamine and dicycloheptylamine; monomethanolamine, dimethanolamine, monoethanolamine, diethanolamine, triethanolamine, mono (n-propanol) amine;
Di (n-propanol) amine, monoisopropanolamine, diisopropanolamine, monobutanolamine, dibutanolamine, monopentanolamine, dipentanolamine, tripentanolamine, monohexanolamine, dihexanolamine, monomethylmonoethanol Amine, monoethylmonoethanolamine (alias: N-ethylethanolamine), monoethylmonopropanolamine, monoethylmonobutanolamine, monoethylmonopentanolamine, monopropylmonoethanolamine, monopropylmonopropanolamine, monopropyl Monobutanolamine, monopropylmonopentanolamine, monobutylmonoethanolamine, monobutylmonopropanolamine, monobutylmonobuta Ruamin, alkanolamines such monobutyl mono pentanol amines are preferred. These amine compounds are excellent in the availability and the effect of improving the antistatic property of the resin composition.

Among them, it is preferable to use alkanolamine, particularly because it is easy to improve the antistatic property of the resin composition.

(Anion (T ′) ⁻ )
In the above formula (2), the anion ((T ′) ⁻ ) is a sulfate ester anion represented by the formula (t-1) related to the ionic bonding salt (1), and a phosphorus represented by the formula (t-2). Since it is the same as the acid ester anion or the sulfonic acid anion represented by the formula (t-3), detailed description is omitted here.

When the ion-bonding salt (2) constitutes the ion-binding salt composition together with the ion-binding salt (1), from the viewpoint of improving the antistatic property of the resin composition, the ion-bonding salt ( The anion (T ⁻ ) of 1) and the anion ((T ′) ⁻ ) of the ion-binding salt (2) are preferably the same. When these anions are the same, the compatibility of the mutual ionic bonding salt is improved, so that the conductivity in the resin composition is easily uniform, and the antistatic property is easily improved.

(Method for producing ionic bonding salt (2))
The method for producing the ion-bonding salt (2) is not particularly limited as long as it can produce ion-bonding having the structure of the formula (2), and any method can be adopted. it can. For example, the method for producing the ion-binding salt (1) can be appropriately modified and modified for use. More specifically, the silane compound containing an amino group or an imino group used in the production of the ion-binding salt (1) may be changed to a nitrogen-containing compound constituting the cation (Q ′) ⁺ . In addition, the reaction conditions at the time of manufacturing the ion-bonding salt (2) are not particularly limited, and are substantially the same as those of the ion-bonding salt (1).

(Specific examples of the ion-binding salt (2))
More preferable compounds of the ion-bonding salt (2) represented by the chemical formula (2) include ion-bonding salts represented by the following chemical formulas (201) to (211).

[Ion-binding salt composition]
The composition ratio of the above-mentioned ionic bonding salt (1) and the ionic bonding salt (2) contained in the ionic bonding salt composition according to the present invention is not particularly limited, but the ionic bonding salt (1) And the ion-binding salt (2) are preferably contained in a mass ratio of 1: 0.1 to 1:80. Further, the ratio of the ion-binding salt (1) and the ion-binding salt (2) is more preferably 1: 1 to 1:75, more preferably 1: 2 to 1:70, and 1: 1. It is particularly preferred that the ratio is 2 to 1:30.

Furthermore, in the ion-bonding salt composition of the present invention, the content ratio of the ion-binding salt (2) to the ion-bonding salt (1) containing a cation derived from a silane compound having an amino group or an imino group is included. Is preferably increased. According to such an embodiment, the ion-bonding salt (2) is easily incorporated into the resin composition, and the ion-bonding salt (1) is easily dispersed on the surface of the resin composition. As a result, the conductivity of the ion-bonding salt (1) dispersed on the surface of the resin composition can be further improved by using the conductive path formed inside the resin composition by the ion-binding salt (2). it can. In other words, simply adding only the ion-bonding salt (2) does not contribute to the improvement of the antistatic property because the ion-bonding salt (2) is only taken into the resin composition. By adding the ion-bonding salt (1) and dispersing it on the surface of the resin composition, the ion-bonding salt (2) is greatly improved in the antistatic property starting from the ion-bonding salt (1). It is possible to contribute.

In addition, the ion binding salt (1) and the ion binding salt (2) may be used alone or as a mixture of two or more.

[Antistatic agent]
The ion-binding salt (1) according to the present invention or the above-mentioned ion-binding salt composition containing the same exhibits an extremely excellent effect as an antistatic agent for a resin composition or the like. That is, according to the third aspect of the present invention, the composition comprises the above-mentioned ion-binding salt (1) or the above-mentioned ion-binding salt composition.
An antistatic agent is provided.

In particular, the ion-bonding salt (1) according to the present invention or the ion-binding salt composition containing the same has a high effect of improving the antistatic property of the resin composition, and is excellent as an antistatic agent for the resin composition. It is effective.

Further, the ion-bonding salt (1) and the ion-bonding salt composition containing the same according to the present invention can be used as a resin composition to which a silicone compound or a fluorine-based compound is added (particularly, when the silicone compound or the fluorine-based compound has a resin surface). (A resin composition arranged in the same manner). Therefore, since it can be arranged on the surface of such a resin composition, the ion-bonding salt (1) according to the present invention and the ion-binding salt composition containing the same have an antistatic property of the resin composition. It has the effect of improving.

As described above, the antistatic agent according to the present invention has a high effect of improving the antistatic property of a resin composition containing a silicone compound or a fluorine-based compound among the resin compositions. Therefore, according to the fourth aspect of the present invention, there is also provided an antistatic agent for a resin composition containing a silicone compound or a fluorine-based compound.

Since the ion-bonding composition (1) contains a silicon atom, it has a high affinity for a silicon compound containing a silicon atom. Therefore, when dispersed on the surface of the silicone compound-containing resin composition, it is not easily detached. Therefore, the antistatic property of the silicone compound-containing resin composition can be improved.

Further, the use form of the antistatic agent according to the present invention is not particularly limited. For example, it may be used in a form in which an antistatic agent is dispersed in the resin composition, may be used in a form in which the antistatic agent is kneaded in the resin composition, or may be charged on the surface of the resin composition. It may be used in a form in which an inhibitor is applied, or in a form in which these are appropriately combined. Any form can be used as long as at least a part of the antistatic agent can be exposed on the surface of the resin composition, but preferably, a form in which the antistatic agent is dispersed in the resin composition Is adopted. With such a form, the manufacturing process of the resin composition is simplified,
preferable.

[Resin composition]
As described above, the antistatic agent containing the ion-bonding salt (1) of the present invention can improve the antistatic property of the resin composition containing a silicone compound or a fluorine-based compound. Therefore, according to the fifth aspect of the present invention, there is also provided a resin composition containing the above antistatic agent, a resin, and a silicone compound or a fluorine-based compound. In the above embodiment, "the resin composition contains an antistatic agent" includes the case where the antistatic agent reacts with the resin or the like and does not remain in the form at the time of addition. That is, “the resin composition contains an antistatic agent” means that the resin composition has a molecular structure derived from a compound constituting the antistatic agent.

(resin)
The resin composition according to the present invention contains a resin as a main component. Antistatic agent according to the present invention,
It does not matter what kind of resin can improve the antistatic performance. Therefore, any of a thermosetting resin and a thermoplastic resin can be used as the resin used in the resin composition according to the present invention.

Thermosetting resin used in the present invention is not particularly limited, for example, phenolic resin,
Epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, urethane resins, thermosetting polyimide resins, and the like. The thermosetting resins can be used alone or in combination of two or more.

The thermoplastic resin used in the present invention is not particularly limited, but includes, for example, (meth) acrylic resin, styrene resin, polyester resin, polycarbonate resin, olefin resin (such as polyethylene and polypropylene; and also includes cyclic olefin resin), Polyamide resin, halogen-containing resin (polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, etc.), polyvinyl ester resin such as polyvinyl acetate, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), polyacetal resin and the like. The above thermoplastic resins can be used alone or in combination of two or more.

When the thermosetting resin or the thermoplastic resin is a copolymer, the form of the copolymer may be any of a block copolymer, a random copolymer, a graft copolymer, and an alternating copolymer.

As the thermoplastic resin, a synthetic product or a commercially available product may be used. The polymerization method for synthesizing these thermoplastic resins is not particularly limited, and a known method can be used. For example, high pressure radical polymerization, medium / low pressure polymerization, UV polymerization, solution polymerization, slurry polymerization, bulk polymerization, emulsion polymerization, gas phase polymerization, and the like can be given. The catalyst used for the polymerization is not particularly limited, and examples thereof include a peroxide catalyst, a Ziegler-Natta catalyst, a metallocene catalyst, and a tin catalyst.

The resin preferably contains at least one selected from the group consisting of a urethane resin, a (meth) acrylic resin, a styrene resin, and a polyester resin.
The antistatic agent according to the present invention exhibits particularly excellent antistatic properties when added together with these resins.

Further, the ion-binding salt (1) contained in the resin composition contains a cation derived from the compound represented by the above formula (q-1), and at least one of R ⁵ is a hydroxy group;
A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted carbon atom When the number of the aryloxy groups is from 6 to 30, it is preferable that the monomer compound as a raw material of the resin has a hydroxy group. The above equation (q
In the case where at least one of the substituents (R ⁵ ) on the silicon atom in -1) has a hydroxy group, an alkoxy group, a cycloalkoxy group or an aryloxy group, these substituents and a monomer compound constituting the resin Reacts and crosslinks, whereby the ionic bonding salt (1) is more firmly incorporated into the resin composition, and the effect of improving the antistatic property is more easily maintained.

The content of the antistatic agent in the resin composition is not particularly limited, but is 0.01 to 100 parts by mass of the resin (excluding the silicone compound and the fluorine-based compound) in order to obtain sufficient antistatic properties. The amount is preferably 100 parts by mass, more preferably 0.05 to 70 parts by mass, even more preferably 0.1 to 50 parts by mass, and particularly preferably 0.1 to 30 parts by mass. When the content is 0.01 parts by mass or more, the effect of improving the antistatic property by the ion-bonding salt (1) can be sufficiently obtained. On the other hand, when the amount is 100 parts by mass or less, the antistatic agent is not added in a large amount, so that the resin composition can be sufficiently exhibited without impairing its original properties. The antistatic agent can be used alone or in combination of two or more.

Further, the content of the ion-bonding salt (1) in the resin composition is not particularly limited,
0.01 parts by mass per 100 parts by mass of resin (excluding silicone compound and fluorine compound)
To 100 parts by mass, more preferably 0.05 to 70 parts by mass, and 0.1
The amount is even more preferably from 50 to 50 parts by mass, and particularly preferably from 0.1 to 10 parts by mass.
Within the above range, the antistatic properties of the resin composition can be sufficiently improved, and the original properties of the resin composition can be sufficiently exhibited.

(Silicone compound)
The resin composition according to the present invention contains a silicone compound or a fluorine compound for the purpose of improving the water repellency or the like of the resin. Hereinafter, the silicone compound will be described first.

The silicone compound used in the present invention is not particularly limited as long as it can achieve the above object, and known compounds can be used.

The silicone compound is not particularly limited, but preferably has a kinematic viscosity (25 ° C.) of 10 to 1000 mm ² / s from the viewpoint of ease of handling and the like, and 50 to ⁵ mm ² / s.
It is more preferable to use one having a thickness of 00 mm ² / s.

As the silicone compound used in the present invention, for example, dimethyl silicone,
Methyl hydrogen silicone, methyl phenyl silicone, cyclic dimethyl silicone, amino-modified silicone, organopolysiloxane in which a part of the methyl group on the side chain or terminal of dimethyl silicone is a hydroxy group (in the present specification, “hydroxy silicone” And the like. Further, a so-called “silicone-acrylic resin” in the form of a graft polymer synthesized by copolymerization of a silicone macromonomer and an acrylic monomer may be used as the silicone compound. These silicone compounds may be synthesized or commercially available products may be used.

Among the above silicone compounds, it is preferable to use dimethyl silicone, hydroxysilicone, and silicone-acrylic resin from the viewpoint of availability, price, and the like, and from the viewpoint of easily improving the water repellency and oil repellency of the resin composition. Here, the hydroxy silicone is
The hydroxyl value is preferably in the range of 1 to 500 mg KOH / g, and 10 to 300 mg KO
More preferably, it is in the range of H / g. Here, the hydroxyl value means JIS-K-007.
0: Refers to a value measured according to 1992.

Commercial products of dimethyl silicone include, for example, KM-780, KM-782, KM-
785, KM-797, KM-9705, KM-860A, KM-862T, KS-70
2, KS-725 and KS-707 (all manufactured by Shin-Etsu Chemical Co., Ltd.) can be used. Also, SR2462, SR2306, SR2316, dry seal S, 804
RESIN, 840 RESIN, SR2400, 220 FLAKE, 233 FLAKE,
249FLAKE, 52ADDITIVE (all manufactured by Dow Corning Toray Co., Ltd.) and the like can be used.

Commercially available products of hydroxysilicone include, for example, X-21-5841, KF-970
1, X-22-160AS, KF-6001, KF-6002, and KF-6003 (
As described above, PRX413 (both manufactured by Dow Corning Toray Co., Ltd.) and the like can be used.

As a commercially available product of silicone-acrylic resin, for example, Cymac (registered trademark) series (manufactured by Toagosei Co., Ltd.) can be used.

In addition, the said silicone compound can be used individually or in combination of 2 or more types.

The content of the silicone compound in the resin composition is not particularly limited as long as the water repellency and oil repellency of the resin composition can be sufficiently obtained, but as a guide, the content of the resin (excluding the silicone compound and the fluorine-based compound) 100 It is preferably 0.1 to 10 parts by mass with respect to parts by mass,
It is more preferably from 0.5 to 8 parts by mass, particularly preferably from 1 to 5 parts by mass. When the amount is 0.1 parts by mass or more, a resin composition having sufficient water repellency and oil repellency can be obtained. On the other hand, when the amount is 10 parts by mass or less, the effect of improving the antistatic property by the antistatic agent of the present invention can be further enhanced.

The content of the silicone-acrylic resin is not particularly limited as long as the water repellency and oil repellency of the resin composition can be sufficiently obtained, but as a guide, the resin (excluding the silicone-acrylic resin and the fluorine-based compound) The amount is preferably 5 to 100 parts by mass, more preferably 5 to 80 parts by mass, and particularly preferably 10 to 60 parts by mass with respect to 100 parts by mass.
When the amount is 5 parts by mass or more, a resin composition having sufficient water repellency and oil repellency can be obtained.
On the other hand, when the amount is 100 parts by mass or less, the effect of improving the antistatic property by the antistatic agent of the present invention can be further enhanced.

Further, the content of the antistatic agent with respect to the silicone compound in the resin composition is not particularly limited, but as a guide, it is preferably 100 to 500 parts by mass, and preferably 250 to 400 parts by mass with respect to 100 parts by mass of the silicone compound. Is more preferable. Within the above range, a resin composition having particularly excellent antistatic properties can be obtained. In addition, when the resin composition contains the fluorine compound described in detail below together with the silicone compound, it is preferable that the total amount of these compounds is 100 parts by mass and the antistatic agent is contained in the same mass ratio as described above.

(Fluorine compound)
The resin composition according to the present invention may contain a fluorine compound for the purpose of improving the water repellency and the like of the resin. The fluorine compound may be used together with the silicone compound.

The fluorine-based compound used in the present invention is not particularly limited as long as it is a silicone compound that can achieve the above object, and known compounds can be used. For example, polytetrafluoroethylene,
Examples thereof include polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, and chlorofluoroethylene / vinylidene fluoride copolymer. These fluorine compounds may be synthesized or commercially available products may be used.

In addition, the said fluorine-type compound can be used individually or in combination of 2 or more types.

The content of the fluorine compound in the resin composition is not particularly limited as long as the water repellency and oil repellency of the resin composition can be sufficiently obtained, but as a guide, the resin (excluding the silicone compound and the fluorine compound) It is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass,
The amount is more preferably 0.1 to 8 parts by mass, and particularly preferably 1 to 5 parts by mass. 0.01
When the amount is at least part by mass, a resin composition having sufficient water repellency and oil repellency can be obtained. On the other hand, when the amount is 10 parts by mass or less, the effect of improving the antistatic property by the antistatic agent of the present invention can be further enhanced.

Further, the content of the antistatic agent with respect to the fluorine-based compound in the resin composition is not particularly limited, but as a guide, it is preferably 100 to 500 parts by mass with respect to 100 parts by mass of the fluorine-based compound, and 250 to 400 parts by mass. It is more preferable that the amount be parts by mass. Within the above range, a resin composition having particularly excellent antistatic properties can be obtained.

(Other additives)
Other additives may be added to the resin composition of the present invention as long as the object of the present invention is not impaired. Other additives that can be added include antioxidants, fillers, lubricants, dyes, organic pigments, inorganic pigments, plasticizers, processing aids, ultraviolet absorbers, light stabilizers, foaming agents, waxes, and crystal nucleating agents. , A release agent, a hydrolysis inhibitor, an anti-blocking agent, a radical scavenger, an anti-fogging agent, an anti-fog agent, an ion trapping agent, a flame retardant, a flame retardant auxiliary, a surfactant and the like.

[Method for producing resin composition]
The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include (I) a dispersion method and (II)
Examples of the method include a kneading method and a (III) coating method.

(I) Dispersion method The ion-bonding salt (1) of the present invention, a monomer compound as a raw material of a resin, a silicone compound, and a catalyst and other additives added as needed are added to the system and dispersed. Then, the monomer compound is polymerized by solution polymerization or ultraviolet polymerization to obtain a resin composition. At this time, the ion-binding salt (2) may also be added as necessary (in this case, this is synonymous with adding the above-mentioned ion-binding salt composition to the system). By employing such a method, a resin composition can be obtained with high productivity. The polymerization conditions (concentration of each monomer, polymerization time, polymerization temperature, etc.) can be appropriately changed depending on the type of the resin.

(II) Kneading Method Another method is a method of melt-kneading the ion-bonding salt (1), the resin, the silicone compound and other additives to be added as required. At this time, the ion-binding salt (2) may also be added as necessary (in this case, this is synonymous with adding the above-mentioned ion-binding salt composition to the system). Here, the method of melt kneading is not particularly limited, and for example, a method using a device such as a single screw extruder, a twin screw extruder, a hot roll, a Banbury mixer, a Henschel mixer, a tumbler mixer, or various kneaders is employed. be able to.

(III) Coating method As still another method, a solution (coating solution) of the above-mentioned ion-bonding salt (1) may be prepared, and the coating solution may be applied to the surface of a kneaded resin and silicone compound. At this time,
The coating liquid may also contain an ion-binding salt (2) if necessary (in this case,
This is synonymous with applying the above-mentioned ion-binding salt composition).

[Other Uses of Ion-Binding Salt (1) and Ion-Binding Salt Composition]
The ion binding salt (1) and the ion binding salt composition according to the present invention act as an antistatic agent as described above. On the other hand, in addition to these, it can also be used as a treating agent that exerts a physical action or a chemical action on plastics, metals, gases such as CO _{2, and the} like. More specifically, the ion-bonding salt (1) and the ion-binding salt composition according to the present invention include, for example, an electrolyte, a lubricant, an antifogging agent, a dispersant, an emulsifier, an acid gas absorbent, and a wastewater treatment agent. , Synthetic catalysts, drug delivery systems (DDS), metalworking, polymerworking, weathering agents. Among the above, typical other uses of the ion-bonding salt (1) and the ion-binding salt composition include, in particular, uses as a dispersant / emulsifier.

[Use of resin composition]
Examples of uses of the resin composition of the present invention include paints, adhesives, pressure-sensitive adhesives, fiber auxiliaries, building materials films, protective films such as hard coats, housings for home appliances, papermaking applications (surface coating agents, etc.), Civil engineering applications (such as concrete admixtures).

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the following, “parts” or “%” may be used, but “parts by mass” or “% by mass” is used unless otherwise specified.

(Synthesis Example 1: Synthesis of [APM-Si] [EHDG-S]; Synthesis of ion-bonding salt (1))
Diethylene glycol mono 2-ethylhexyl ether (manufactured by Nippon Emulsifier Co., Ltd., trade name: 2-ethylhexyl diglycol, abbreviation: EHDG)
50.0 parts by mass was added, and the temperature was raised to 110 ° C. To this, 80.2 parts by mass of sulfamic acid was added and reacted for 3 hours. After the reaction, excess sulfamic acid was filtered off, and diethylene glycol mono 2-ethylhexyl ether sulfate ammonium salt (abbreviation: EHDG-SF;
A toluene solution of ammonium ion (NH ₄ ⁺ ) was obtained.

To 100.0 parts by mass of a 50% toluene solution of EHDG-SF obtained above, 3-aminopropyltrimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd., abbreviation:
APM-Si) was added at 42.7 parts by mass and reacted at 120 ° C. for 3 hours. (EHDG-SF
And the APM-Si molar ratio is 1: 1.5)
After completion of the reaction, toluene and unreacted APM-Si were distilled off under reduced pressure (temperature: 150 ° C., degree of reduced pressure: 1.33 kPa (10 mmHg)), and the desired ion-bonding salt (1) (abbreviation: [
APM-Si] [EHDG-S]; 72.3)
Parts by weight were obtained.

The NMR spectrum data of the obtained [APM-Si] [EHDG-S] is shown below.
_{^{1 H-NMR (CDCl 3,}} 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), 1.71-1.86 (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).

(Synthesis Example 2: Synthesis of [MEM] [EHDG-S]; Synthesis of ion-binding salt (2))
Except for using N-ethylethanolamine (manufactured by Nippon Emulsifier Co., Ltd., trade name: amino alcohol MEM, abbreviation: MEM) in place of APM-Si, the target ionic bond in the same manner as in Synthesis Example 1 above. A salt (2) (abbreviation: [MEM] [EHDG-S]; a compound represented by the chemical formula (201)) was obtained. At this time, the molar ratio of EHDG-SF to MEM was 1: 1.5.

(Synthesis Example 3: Synthesis of [APE-Si] [EHDG-S]; Synthesis of Ion-Binding Salt (1))
Synthetic Example 1 except that 52.7 parts by mass of 3-aminopropyltriethoxysilane (trade name: KBE-903, abbreviation: APE-Si, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of APM-Si. Similarly, the desired ion-binding salt (abbreviation: [APE-Si] [EHD
GS]; a compound represented by the aforementioned chemical formula (102)).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 0.65-0.75 (t, 2H), 0.83-0.90 (m, 6H), 1.20-1.42 (m, 8H),
1.47-1.56 (m, 1H), 1.71-1.88 (m, 2H), 2.98-3.07 (m, 2H), 3.30-3.36 (m, 2H), 3.55
-3.59 (t, 2H), 3.62-3.65 (t, 2H), 3.72-3.75 (t, 2H), 3.78-3.85 (m, 6H), 4.15-4.
18 (t, 2H)
(Synthesis Example 4: Synthesis of [MSi-N (Et) ₂ ] [EHDG-S]; Ion-binding salt (1
) Synthesis)
Synthesis Example 1 except that 34.6 parts by mass of N- (trimethylsilyl) diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd., MSi-N (Et) ₂ ) was used instead of APM-Si.
In the same manner as described above, the desired ion-bonding salt (abbreviation: [MSi-N (Et) ₂ ] [EHDG-
S]; a compound represented by the above formula (113)).
_{^{1 H-NMR (CDCl 3,}} 400MHz) δ0.08 (s, 9H), 0.83-0.92 (m, 6H), 1.20-1.42 (m, 14H),
1.47-1.56 (m, 1H), 3.03-3.12 (m, 4H), 3.25-3.35 (m, 2H), 3.45-3.52 (t, 2H), 3.55
−3.59 (t, 2H), 3.67−3.70 (t, 2H), 4.09−4.14 (t, 2H)
(Synthesis Example 5: Synthesis of [APM-Si] [Cum-SO ₃ ]; Synthesis of ion-bonding salt (1))
Cumenesulfonic acid (o-, m-, p-cumenesulfonic acid isomer mixture) (manufactured by Teica Co., Ltd., trade name: Takeka Tox 500, abbreviation: Cum-SO ₃ H)
After adding 179.3 parts by mass of PM-Si, the reaction was carried out for 1 hour, and a target ionic liquid (abbreviation: [APM-Si] [Cum-SO ₃ ]; a compound represented by the above chemical formula (107)) 379 0.6 parts by weight were obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 0.52-0.58 (t, 2H), 1.20-1.29 (m, 6H), 1.64-1.71 (m, 2H),
2.73-2.78 (t, 2H), 2.87-2.94 (m, 1H), 3.46 (s, 9H), 7.19-7.22 (d, 2H), 7.78-7.81
(d, 2H)
(Synthesis Example 6: Synthesis of [APM-Si] [1305-S]; Synthesis of Ion-Binding Salt (1))
Instead of the 50% toluene solution of EHDG-SF in Synthesis Example 1, ammonium polyoxyethylene tridecyl ether sulfate (abbreviation: 1305) synthesized by a conventionally known method
-SF; the target ion-binding salt (abbreviation: [APM-) was prepared in the same manner as in Synthesis Example 1 except that 102.7 parts by mass of an 80% methanol solution of NH ₄ ⁺ ) was used as the ammonium ion.
Si] [1305-S]; a compound represented by the aforementioned chemical formula (111)).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 0.68-0.90 (m, 15H), 1.00-1.45 (m, 21H), 1.50-1.65 (m, 2H)
, 1.76-1.88 (m, 2H), 2.99-3.05 (t, 2H), 3.42-3.50 (m, 2H), 3.53-3.75 (t, 33H), 3
.88−3.96 (t, 1H), 4.13−4.21 (t, 2H)
(Synthesis Example 7: Synthesis of [MEM] [DOSS]; Synthesis of Ion-Binding Salt (2))
Dioctyl fumarate 200.0 parts by mass, 50% aqueous ammonium bisulfite solution 116
. 4 parts by mass, 37.0 parts by mass of methanol and 15.6 parts by mass of water were charged into an autoclave,
The temperature was raised to 120 ° C., and the reaction was performed for 24 hours. The maximum pressure at this time was 0.25 MPa.

The ammonium dioctyl sulfosuccinate obtained above (abbreviation: DOSS-NH)
₄ ) 30.4 parts by mass of MEM was added to 140.0 parts by mass (the molar ratio of DOSS-NH ₄ to MEM was 1: 1.5).

After charging, the mixture was reacted at 80 ° C. for 3 hours. After completion of the reaction, methanol, water and unreacted M
EM was distilled off under reduced pressure (temperature: 125 ° C., degree of reduced pressure: 1.33 kPa (10 mmHg)), and the target ionic liquid (abbreviation: [MEM] [DOSS]; compound represented by the above chemical formula (211)) was obtained. 115.0 parts by mass were obtained.

(Reference Example 1)
Put the rotor in a 20 ml glass bottle, add 83.47 parts by mass of Acrydic BU-955 (acrylic polyol, manufactured by DIC, solid content: 59.9%), and dibutyltin dilaurate 0
. 06 parts by mass (0.1% by mass with respect to the resin solids), 30.0 parts by mass of toluene and 3.97 parts by mass of [MEM] [EHDG-S] obtained in Synthesis Example 2 (based on the resin solids) 7% by mass). After mixing for 10 minutes, 6.67 parts by mass of duranate TPA-100 (isocyanate, manufactured by Asahi Kasei Chemicals Corporation) was further added to obtain a mixed solution. The obtained liquid mixture was applied on a glass plate at a film thickness of 75 μm, and dried with a dryer at 110 ° C. for 30 minutes to obtain a test piece.

(Comparative Example 1)
In the above Reference Example 1, 1.13 parts by mass of a dehydrated product of KM-860A (chain dimethyl silicone compound, manufactured by Shin-Etsu Chemical Co., Ltd.) (resin solids) was added to the mixed solution before adding duranate TPA-100 (isocyanate). A test piece was obtained in the same manner as in Reference Example 1 except that 2% by mass (% by mass) was further added.

(Example 1)
In Comparative Example 1 described above, instead of 3.97 parts by mass of [MEM] [EHDG-S], 0.57 parts by mass of [APM-Si] [EHDG-S] obtained in Synthesis Example 1 above (based on resin solid content) Comparative Example 1 except that 1% by mass) and 3.40 parts by mass of [MEM] [EHDG-S] obtained in Synthesis Example 2 (6% by mass with respect to the resin solid content) were added. To obtain a test piece.

(Example 2)
In Example 1 above, [APM-Si] [EHDG-S] and [MEM] [EHD
GS] was changed to 1.14 parts by mass (2% by mass based on resin solids) and 2.83 parts by mass (5% by mass based on resin solids), respectively. In the same manner as in Example 1, a test piece was obtained.

(Example 3)
In Example 1 above, [APM-Si] [EHDG-S] and [MEM] [EHD
GS] was changed to 0.285 parts by mass (0.5% by mass based on resin solids) and 3.68 parts by mass (6.5% by mass based on resin solids), respectively. Except for the changes,
A test piece was obtained in the same manner as in Example 1.

(Example 4)
In Example 1 above, [APM-Si] [EHDG-S] and [MEM] [EHD
GS] was changed to 0.057 parts by mass (0.1% by mass with respect to the resin solids) and 3.90 parts by mass (6.9% by mass with respect to the resin solids), respectively. Except for the changes,
A test piece was obtained in the same manner as in Example 1.

(Comparative Example 2)
In the above Reference Example 1, 1.13 parts by mass of KF-6003 (hydroxysilicone compound, manufactured by Shin-Etsu Chemical Co., Ltd.) (2 parts by mass relative to the resin solid content) was added to the mixed solution before adding duranate TPA-100 (isocyanate). % By mass), and added with duranate TPA.
A test piece was obtained in the same manner as in Reference Example 1, except that the amount of -100 (isocyanate, manufactured by Asahi Kasei Chemicals Corporation) was changed to 6.75 parts by mass. In the above description, KF-6003 as a silicone compound contains hydroxy groups at both ends and exhibits the same action as a polyol. Therefore, the amount of isocyanate added is larger than that of Comparative Example 1 by the number of moles of the silicone compound.

(Example 5)
In Comparative Example 2, instead of 3.97 parts by mass of [MEM] [EHDG-S], 1.14 parts by mass of [APM-Si] [EHDG-S] obtained in Synthesis Example 1 above (based on the resin solid content) The same as Comparative Example 2 except that [MEM] [EHDG-S] obtained in Synthesis Example 2 above and 2.83 parts by weight (5% by weight based on the resin solid content) of Synthesis Example 2 were added. To obtain a test piece.

(Reference Example 2)
Put the rotor in a 20 ml glass bottle, 64.73 parts by mass of Dianal LR-186 (acrylic resin, manufactured by Mitsubishi Rayon Co., Ltd., solid content: 46.3%), Cymac US-350 (silicone-acrylic resin, Toagosei Co., Ltd.) 65.02 parts by mass of a solid content of 32.3%)
25.2 parts by mass of 2-butanone was added and mixed for 10 minutes. The obtained liquid mixture was applied on a glass plate at a film thickness of 75 μm, and dried for 10 minutes with a dryer at 110 ° C. to obtain a test piece.

(Comparative Example 3)
A test piece was prepared in the same manner as in Reference Example 2 except that 2.10 parts by mass of [MEM] [EHDG-S] obtained in Synthesis Example 2 above (4.1% by mass with respect to the resin solid content) was further added. Got.

(Example 6)
[MEM] [EHDG-S] [APM-S obtained in Synthesis Example 1 above in place of 2.10 parts by mass.
Si] [EHDG-S] 0.42 parts by mass (0.8% by mass with respect to resin solids) and [MEM] [EHDG-S] 2.10 parts by mass (resin solids) obtained in Synthesis Example 2 above. For 4.1
% By mass) was obtained in the same manner as in Comparative Example 3 except that a test piece was added.

(Example 7)
[MEM] [EHDG-S] [APM- obtained in Synthesis Example 5 above in place of 2.10 parts by mass.
Si] [Cum-SO ₃ ] 0.42 parts by mass (0.8% by mass with respect to the resin solids) and [MEM] [EHDG-S] 2.10 parts by mass (resin solids) obtained in Synthesis Example 2 above. 3. per minute.
A test piece was obtained in the same manner as in Comparative Example 3 except that 1% by mass) was added.

(Example 8)
[MEM] [EHDG-S] [APM- obtained in Synthesis Example 6 above in place of 2.10 parts by mass.
Si] [1305-S] 0.42 parts by mass (0.8% by mass with respect to the resin solids) and [MEM] [EHDG-S] 2.10 parts by mass (resin solids) obtained in Synthesis Example 2 above. For 4.1
% By mass) was obtained in the same manner as in Comparative Example 3 except that a test piece was added.

(Example 9)
[MEM] [EHDG-S] [APE- obtained in Synthesis Example 3 above in place of 2.10 parts by mass.
Si] [EHDG-S] 0.42 parts by mass (0.8% by mass with respect to resin solids) and [MEM] [EHDG-S] 2.10 parts by mass (resin solids) obtained in Synthesis Example 2 above. For 4.1
% By mass) was obtained in the same manner as in Comparative Example 3 except that a test piece was added.

(Example 10)
[MEM] [EHDG-S] [MSi- obtained in Synthesis Example 4 above in place of 2.10 parts by mass.
N (Et) ₂ ] [EHDG-S] 0.42 parts by mass (0.8% by mass based on the resin solid content) and [MEM] [EHDG-S] 2.10 parts by mass obtained in Synthesis Example 2 above. A test piece was obtained in the same manner as in Comparative Example 3, except that (4.1% by mass based on the resin solid content) was added.

(Example 11)
[MEM] [EHDG-S] [APM-S obtained in Synthesis Example 1 above in place of 2.10 parts by mass.
Si] [EHDG-S] 0.42 parts by mass (0.8% by mass based on resin solids) and [MEM] [DOSS] obtained in Synthesis Example 7 above 2.10 parts by mass (based on resin solids) A test piece was obtained in the same manner as in Comparative Example 3, except that 4.1% by mass was added.

(Comparative Example 4)
[MEM] [EHDG-S] [MEM] obtained in Synthesis Example 7 above in place of 2.10 parts by mass.
[DOSS] A test piece was obtained in the same manner as in Comparative Example 3, except that 2.10 parts by mass (4.1% by mass with respect to the resin solid content) was added.

(Example 12)
[MEM] [EHDG-S] [APM- obtained in Synthesis Example 5 above in place of 2.10 parts by mass.
Si] [Cum-SO ₃ ] 0.42 parts by mass (0.8% by mass with respect to the resin solids) and 1.68 parts by mass of [MEM] [EHDG-S] obtained in Synthesis Example 2 above (resin solids) 2. For minutes.
A test piece was obtained in the same manner as in Comparative Example 3 except that 3% by mass) was added.

(Comparative Example 5)
[MEM] [EHDG-S] 2. Desolvate of Cotamine 24P (lauryltrimethylammonium chloride, manufactured by Kao Corporation, solid content: 24.0%) instead of 2.10 parts by mass.
A test piece was obtained in the same manner as in Comparative Example 3, except that 10 parts by mass (4.1% by mass with respect to the resin solid content) was added.

(Comparative Example 6)
Place the rotor in a 20 ml glass bottle, 117.98 parts by mass of Byron 20SS (polyester resin, manufactured by Toyobo Co., Ltd., solid content: 35.6%), Cymac US-350 (silicone-acrylic resin, manufactured by Toagosei Co., Ltd., solid 65.02 parts by mass, 25.2 parts by mass of 2-butanone, 1.26 parts by mass of [MEM] [EHDG-S] obtained in the above Synthesis Example 2 (4.32 parts by mass based on the resin solid content). 1% by mass) and mixed for 10 minutes. The obtained liquid mixture was applied on a glass plate at a film thickness of 75 μm, and dried for 10 minutes with a dryer at 110 ° C. to obtain a test piece.

(Example 13)
Same as Comparative Example 6 except that 0.42 parts by mass of [APM-Si] [EHDG-S] obtained in Synthesis Example 1 above (0.8% by mass with respect to the resin solid content) was further added. A test piece was obtained.

Table 1 shows the compositions of the resin compositions (test pieces) produced in the above Reference Examples, Examples and Comparative Examples.
To Table 3 below. In addition, "-" in a table | surface shows that the said component is not contained.

≪Evaluation≫
The antistatic properties, durability and contact angle of the resin compositions obtained in the above Reference Examples, Examples and Comparative Examples were evaluated by the following methods. Tables 1 to 3 show the measurement results. Note that "-" in the table
Indicates that the evaluation item has not been evaluated.

[Measurement of surface resistivity (antistatic test)]
The surface resistivity of the prepared test piece was measured using a high resistivity meter Hiresta UP and URS probe manufactured by Mitsubishi Chemical Analytech Co., Ltd. in an environment of room temperature 23 ° C. and room humidity 50% RH.
The measurement was performed at an applied voltage of 250V.

[Measurement of surface resistivity after washing (durability test)]
Washing water obtained by adding 5 drops of neutral detergent to 1 L of water is moistened with a sponge, and a test piece (only the test piece of Example 1) is rubbed with the sponge 10 times, rinsed with tap water and then with ion-exchanged water in this order. After wiping, it was dried at 110 ° C. for 10 minutes. After repeating this step three times, the surface resistivity of the test piece was measured. The measurement was performed in the same manner as in the above [Measurement of surface resistivity].

[Measurement of contact angle]
The contact angle of a water drop on the test piece after preparation was measured using a contact angle measuring device CA-XP type (manufactured by Kyowa Interface Science Co., Ltd.), and a contact angle with water was measured 30 seconds after dropping a water drop from a micro syringe. Was evaluated. If the measured value of the contact angle is 90 ° or more, it means that the resin has sufficient water repellency.

First, from a comparison between Reference Example 1 and Comparative Example 1 in Table 1 above, it can be seen that the resin composition containing the silicone compound has an extremely low antistatic property. In contrast, Comparative Example 1 and Examples 1-4
As a result, it was found that the addition of the ion-bonding salt (1) significantly improved the antistatic property. In particular, as Example 3, the ion-bonding salt (1) was used in an amount of 6.5% by mass based on the resin (urethane resin formed by a polymerization reaction between a polyol and an isocyanate) (ion-bonding salt based on 100 parts by mass of the resin). When the salt (1) is added by 6.5 parts by mass)
The antistatic property of the resin composition was most improved.

Further, in Example 1 above, the antistatic property of the test piece that was washed three times with water was also evaluated, but it was shown that the antistatic property did not substantially decrease even after washing with water, indicating that the test piece had good durability. Was done. This result indicates that the ion-bonding salt (1) according to the present invention has improved antistatic properties while maintaining good affinity with the resin composition containing the silicone compound. In particular, since the ion-bonding salt (1) used in Example 1 has an alkoxy group on silicon, the group reacts during the polymerization or drying of the urethane resin to form a network. It is presumed that the effect (durability) of maintaining good antistatic properties is high.

Further, Comparative Example 2 and Example 5 are resin compositions containing a silicone compound different from Comparative Example 1 and Examples 1 to 4, and contain a hydroxysilicone compound. And, as a result of Example 5, even when a hydroxysilicone compound is used as the silicone compound contained in the resin composition, the antistatic property can be improved by the ion-bonding salt (1) of the present invention. Was confirmed.

Further, as shown in Tables 2 and 3, as the resin, a resin other than urethane resin (a mixture of an acrylic resin and a silicone-acrylic resin in Table 2 and a mixture of a polyester resin and a silicone-acrylic resin in Table 3) is used. It was confirmed that the effect of improving the antistatic property was exhibited in the same manner as in Table 1 even in the case where the ion-bonding salt (1) had various structures. As shown in Tables 2 and 3, even when the ion-bonding salt according to the present invention was blended, the contact angle was maintained at a sufficiently large value. It was also confirmed that the addition did not adversely affect the water repellency, which is the original purpose when adding the silicone compound or the fluorine compound.

As described above, by using the ion-bonding salt (1) of the present invention (or the ion-binding salt composition further containing the ion-binding salt (2) as necessary), an expensive conductive polymer, It has been shown that the antistatic properties of the resin composition containing the silicone compound can be improved without using a metal that impairs the lightness and color tone of the resin, and that the antistatic properties are also excellent in durability.

Claims (10)

An ion-binding salt represented by the following formula (1):
In the above equation (1),
Q ⁺ is a cation derived from a silane compound containing an amino group or an imino group;
In the above formula (1), T ⁻ is the following formula (t-1):
In the above formula (t-1),
R ¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbon group; An aryl group having 6 to 30 atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms,
A ¹ is a linear or branched alkylene group having 2 to 4 carbon atoms,
s is an integer of 0 to 50;
A sulfate ester anion represented by
The following formula (t-2):
In the above formula (t-2),
R ² and R ³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon group having 3 to 2 carbon atoms.
A cycloalkyl group of 0, 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, wherein R ² and R ³ are not simultaneously hydrogen atoms,
A ² and A ³ are each independently a linear or branched alkylene group having 2 to 4 carbon atoms;
t and u are each independently an integer of 0 to 50;
Represented by a phosphate ester anion, or
The following formula (t-3):
In the above formula (t-3),
R ⁴ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbon group; An aryl group having 6 to 30 atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms,
A ⁴ is a linear or branched alkylene group having 2 to 4 carbon atoms,
v is an integer of 0 to 50;
Is a sulfonate anion represented by In the above equation (1),
Q ⁺ is represented by the following formula (q-1):
In the above formula (q-1),
X is, -CH ₂ - is or oxygen atom (-O-),
Y is -NH-,
Z is, -N ^(R _{6) 2} or -N = ^{C (R} _{6) 2,}
R ⁵ is each independently a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom having 1 carbon atom.
~ 20 alkoxy groups, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, substituted or An unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms (—OR ⁷ , wherein R ⁷ is a substituted or unsubstituted group; Represents a substituted aryl group having 6 to 30 carbon atoms)
R ⁶ is each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms,
A substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted 6 carbon atom 30 aryloxy group (-OR ^8, this time, ^{R 8} represents whether or unsubstituted aryl group having 6 to 30 carbon atoms which is substituted), and
m is an integer of 0 to 5,
n is an integer of 0 to 5,
q is 0 or 1,
r is 0 or 1,
The ion-binding salt according to claim 1, which is a cation derived from the compound represented by the formula: At least one of R ⁵ is a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms. The ion-binding salt according to claim 2, which is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. In the above formula (q-1),
X is, -CH ₂ - is,
Z is -N ^(R _{6) 2,}
R ⁵ is independently a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cyclo group having 3 to 20 carbon atoms. An alkoxy group or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,
R ⁶ is a hydrogen atom,
m is an integer of 0 to 3,
n is 0,
q is 0 or 1,
The ion-binding salt according to claim 2, wherein r is 0. An ionic bonding salt composition comprising the ionic bonding salt according to any one of claims 1 to 4 and an ionic bonding salt represented by the following formula (2):
In the above equation (2),
(Q ′) ⁺ represents an ammonium ion, an imidazolium ion, a pyridinium ion, a pyrrolidinium ion, a pyrrolium ion, a pyrazinium ion, a pyrimidinium ion,
Consists of triazolium, triazinium, quinolinium, isoquinolinium, indolinium, quinoxalinium, piperazinium, oxazolinium, thiazolinium, and morpholinium ions At least one selected from the group and a structure different from Q ⁺ in the above formula (1);
(T ') ^- is sulfate anion represented by the formula (t-1), the formula (t-2)
Or a sulfonate anion represented by the above formula (t-3). An antistatic agent comprising the ion-binding salt according to any one of claims 1 to 4 or the ion-binding salt composition according to claim 5. An antistatic agent for a resin composition containing a silicone compound or a fluorine compound,
The antistatic agent according to claim 6. An antistatic agent according to claim 6,
Resin and
A resin composition comprising: a silicone compound or a fluorine compound. The resin composition according to claim 8, wherein the content of the antistatic agent is 0.1 to 70 parts by mass with respect to 100 parts by mass of the resin. The resin composition according to claim 8, wherein the resin includes at least one selected from the group consisting of a urethane resin, a (meth) acrylic resin, a styrene resin, and a polyester resin.