JP2016029041A - Ion-bonding salt, ion-bonding salt composition and resin composition comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel technique which can improve the antistatic properties of a resin composition comprising a silicone compound or a fluorine compound without using an expensive conductive polymer or a metal that impairs the lightness in weight and the color tone of resin.SOLUTION: The present invention provides an ion-bonding salt represented by the following formula (1), where Qis a cation derived from a silane compound comprising an amino group or imino group; and Tis a sulfate ester anion, a phosphoester anion, or a 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.

  Conventional fields such as paints, adhesives, adhesives, fiber auxiliaries, protective films for building materials films, hard coats, housings for home appliances, papermaking (surface coatings, etc.), civil engineering (concrete admixtures, etc.) Then, in order to impart water repellency and oil repellency to the resin surface, a technique of adding a silicone compound or a fluorine compound to the resin is known. In this technique, a resin excellent in antifouling property can be obtained by arranging a silicone compound or a fluorine compound on the resin surface and utilizing the water repellency and oil repellency of these compounds themselves.

  On the other hand, from a practical point of view, not only water repellency or oil repellency but also antistatic properties are important factors in the resin composition in which the silicone compound or fluorine compound as described above is arranged on the resin surface. 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 (or is exposed) on the resin surface, thereby forming a conductive path and exhibiting antistatic properties. Such surfactants are generally classified into cationic, anionic, amphoteric, and nonionic according to ionicity, and are said to have the highest antistatic effect.

  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, but since the affinity between these compounds and the surfactant is extremely low, an interface is formed on the surface of the resin composition. Almost no active agent can 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. Yes. Therefore, in order to impart an antistatic property to such a resin composition containing a silicone compound or a fluorine-based compound, a technique for further adding a conductive polymer or a metal material has been studied. However, the addition of a conductive polymer or a metal material is expensive, and particularly when a metal material is added, there is a problem that the lightness and color tone of the resin are impaired.

  Therefore, a technique has been proposed in which an aggregate in which conductive material particles are attached around polymer solid electrolyte mother particles is blended with a resin (for example, Patent Document 1).

JP 2004-107555 A

  According to the technique of Patent Document 1, antistatic properties can be imparted to a resin composition containing a silicone compound or a fluorine compound. However, in the technique of Patent Document 1, since the polymer solid electrolyte and the metal oxide as the conductive material are used, the above problems are not substantially solved. 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 eliminated, and the polymer solid electrolyte is generally expensive. There is still a need for cheaper methods.

  Therefore, the present invention is a novel 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. The purpose is 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 comprising a cation derived from a silane compound containing an amino group or an imino group and a sulfate ester anion, phosphate ester anion or sulfonate anion having an oxyalkylene chain is obtained. By adding, it discovered that the antistatic property of the resin composition containing a silicone compound and a fluorine-type compound improved, and came to complete this invention.

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

In the above formula (1),
Q ⁺ is a cation derived from a silane compound containing an amino group or an imino group;
In the above formula (1), T ⁻ represents 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 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 from 0 to 50,
Sulfate anion represented by
Following formula (t-2):

In the above formula (t-2),
R ² and R ³ are each independently a hydrogen atom, 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 group, 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 Is not a hydrogen atom at the same time,
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;
A phosphate ester anion represented by
The following formula (t-3):

In the above formula (t-3),
R ⁴ represents 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 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 from 0 to 50,
It is a sulfonate anion shown by.

  According to the present invention, a silicone compound or a fluorine compound is included by adding an ionic bond salt composed of a cation derived from a silane compound containing an amino group or an imino group and a specific anion having an oxyalkylene chain. The antistatic property of the resin composition can be improved. Therefore, a novel technique capable of improving 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 is provided. sell.

  According to the first aspect of the present invention, there is provided an ion-binding salt represented by the above formula (1) (hereinafter sometimes simply referred to as “ion-binding salt (1)”). Thus, the ion binding 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, since the silicone compound and the fluorine compound are arranged on the surface of the resin composition of the resin composition containing the silicone compound and the fluorine compound, the surfactant having a low affinity with these compounds is a resin. The surface of the composition cannot be coated (or exposed to the surface), and it is difficult to improve antistatic properties. Therefore, for such a resin composition, the antistatic property has been conventionally improved by using a conductive polymer, a metal material, or the like.

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

  The ion-binding salt (1) according to the present invention has a characteristic structure for improving the antistatic properties of a resin composition containing a silicone compound or a fluorine-based compound in the cation and anion constituting the salt, respectively. ing.

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

  Here, the ion-binding salt (1) is not only arranged (dispersed) only on the surface of the resin composition, but is further improved in antistatic properties by being included inside. It is presumed that it will be in a state that can be made. When the ion-binding salt (1) is taken into the resin composition, a conductive path is formed not only on the surface of the resin composition but also on the inside thereof, so that the antistatic property is further improved. In other words, the cation part (and anion anion part) of the ion binding salt (1) is arranged on the surface of the resin composition (the cation part of the ion binding salt (1) and the like are on the surface of the resin composition). As a result, the conductive path formed by the ion-binding salt (1) contained in the resin composition can be used more effectively, thereby improving the antistatic property. Can do it.

  Next, since the anion constituting the ion-binding salt (1) provides a counter anion having a halogen-free structure as the counter anion of the cation, it can be used in applications where halogens are hated. Have.

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

[Ion-binding salt (1)]
The ion-binding 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 the above formula (t-1). Sulfate anion, a phosphate anion represented by formula (t-2) or a sulfonate anion (T ⁻ ) represented by formula (t-3).

(Cation Q ⁺ )
In the above formula (1), “a cation derived from a silane compound containing an amino group or an imino group” means that a cation or a carbocation is added to the silane compound containing an amino group or an imino group. Any charged one is acceptable. Therefore, Q ⁺ does not need to be positively charged by adding a proton or the like to the amino group or imino group in the silane compound containing an amino group or imino group, and the proton or the like is added to another cationic group. However, 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, “a silane compound containing an amino group or imino group” means any one having at least one silicon atom (Si) and at least one amino group or imino group. But it can also be used. In the above, the amino group is a substituent represented by “—N (R ′) ₂ ”, and the substituent represented by R ′ is not particularly limited, but for example, each independently, Examples include a hydrogen atom, an alkyl group, and an aryl group. The imino group is a substituent represented by “—N═C (R ′) ₂ ”, wherein R ′ is the same as described above. The “silane compound containing an amino group or an imino group” may contain both an amino group and an imino group.

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

  Here, the amino-modified silicone compound is one in which an organic group containing an amino group is introduced into the side chain of the polysiloxane (side chain type), or one in which an organic group containing an amino group is introduced into both ends of the polysiloxane (both Terminal type), polysiloxane introduced with an organic group containing an amino group at one end (single end type), polysiloxane introduced with an organic group containing an amino group at both ends and side chains (both ends of the side chain) Type), and those having an organic group containing an amino group introduced into the side chain and one end of the polysiloxane (side chain one end type).

Although it does not restrict | limit especially as an amino modified silicone compound, It is preferable to use a thing below 15000 g / mol as an amine equivalent (mass (g) of the silicone compound containing 1 mol of amino groups), In the range of 300-13000 g / mol. It is more preferable to use a certain one. 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.

  Examples of commercially available silicone compounds that can satisfy these conditions include X-22-161A, X-22-161B, KF-8010, KF-8012 (above, 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 (above, EVONIK INDUSTRIAL), BY16-871, 16-853U, 16-849, 16-872, 16-878, 16-890, 16-891, 16-893, 16-208, FZ-3705 3 85,3789; SF8147, (Toray-Dow Corning Co., Ltd.) Amino-modified silicone compounds and the like.

  The silane compound having a substituent containing an amino group (a silane compound other than an amino-modified silicone compound) may be any one as long as it has one or more silicon atoms 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 (alkyl) Amino) silane, (alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, cycloalkyl (alkylamino) alkoxysilane, tetrakis (alkylamino) silane, alkyltris (alkyl) Mino) silane, dialkyl bis (alkylamino) silane, tri (alkyl) silane, tris (alkylamino) alkoxysilane, bis (alkylamino) dialkoxysilane, and (alkylamino) trialkoxysilanes.

  The silane compound having a substituent containing an imino group may be any silane compound having at least one silicon atom and imino group as described above. For example, N-alkyl (trialkylsilyl) alkane Examples include imine, N-alkyl (alkoxydialkylsilyl) alkaneimine, N-alkyl (dialkoxyalkylsilyl) alkaneimine, and N-alkyl (trialkoxysilyl) alkaneimine.

  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. Those that are primary or secondary are more preferred, and those that are primary are particularly preferred. A primary to tertiary amine is preferable from the viewpoint of simplifying the reaction process. And from such a viewpoint, it is especially preferable that the silane compound containing an amino group or an imino group contains a primary amine.

  As described above, the silane compound containing an amino group or imino group includes an amino-modified silicone compound, a silane compound having a substituent containing an amino group (a silane compound other than an amino-modified silicone compound), and a substitution containing an imino group. A silane compound having a group or the like can be used. These compounds may 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 containing an amino group (a silane compound other than an amino-modified silicone compound) or a silane compound having a substituent containing an imino group, the position of the amino group or imino group and the 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 imino group and the silicon atom is too close, the affinity between the resin composition and silicon may be inhibited by a cation derived from the amino group or 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 ends are arranged on the surface side of the resin composition, and an amino group (amino cation) or imino group (imino cation) can be arranged at a certain distance from the surface of the resin composition. The ion-binding salt (1) according to the above can stably coat the surface of the resin composition. Here, the “coating” includes a form in which the ion-binding salt (1) is adsorbed on the surface and a form protruding from the surface.

  Accordingly, 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 it is preferably 2000 or less in consideration of substantially available silane compounds (however, excluding amino-modified silicone compounds).

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

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

In the above formula (q-1),
X is —CH ₂ — or an oxygen atom (—O—);
Y is -NH-,
Z is —N (R ⁶ ) ₂ or —N═C (R ⁶ ) ₂ ;
R ⁵ each independently represents a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms. Groups, substituted or unsubstituted cycloalkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkoxy groups having 3 to 20 carbon atoms, substituted or unsubstituted carbon atoms An 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 carbon atom; Represents 6 to 30 aryl groups),
R ⁶ each independently represents 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, substituted Substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, substituted or unsubstituted 6 to 6 carbon atoms 30 aryl groups, or substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms (-OR ⁸ , wherein R ⁸ is substituted or unsubstituted carbon atoms having 6 to 30 carbon atoms. Represents an aryl group of
m is an integer from 0 to 5,
n is an integer of 0 to 5,
q is 0 or 1;
r is 0 or 1;
It is preferable that it is an ion binding salt which is a cation derived from the compound shown by these.

  In the present specification, “substituted or unsubstituted” means that a hydrogen atom of a certain group may be substituted with another group or may not be substituted. 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, a methoxyethyl group), an alkoxy group having 1 to 20 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group, An isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, a dodecyloxy group, etc., and a cycloalkoxy group having 3 to 20 carbon atoms (for example, a cyclopentyloxy group, cyclohexyloxy group) Group) Alkenyl group, alkynyl group, amino group, aryl group C6-C30 aryloxy group (for example, phenoxy group, naphthyloxy group), C1-C20 alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group) , Dodecylthio group), cycloalkylthio group having 3 to 20 carbon atoms (for example, cyclopentylthio group, cyclohexylthio group), arylthio group having 6 to 30 carbon atoms (for example, phenylthio group, naphthylthio group), 1 carbon atom To 20 alkoxycarbonyl groups (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group), aryloxycarbonyl groups having 7 to 20 carbon atoms (for example, phenyloxycarbonyl group) Carbonyl group, naphthyloxy group), a hydroxyl group (-OH), carboxyl group (-COOH), a thiol group (-SH), and the like cyano group (-CN) is. Further, the number of substituents to be further substituted for one substituent is not particularly limited, and can be appropriately selected in consideration of a desired effect (improvement of antistatic properties). In the above, they are not substituted with the same substituent. For example, a substituted alkyl group is not substituted with an alkyl group.

In the formula (q-1), X is a divalent radical substituted directly on the silicon atom, -CH ₂ - shows a or an oxygen atom (-O-). Here, q represents the number of X and is 0 or 1. Therefore, the substituent represented by X is not necessarily contained. From the viewpoint of improving the antistatic property, q = 1 is preferable, and X is preferably —CH ₂ —.

  In said formula (q-1), Y is a bivalent substituent and shows -NH-. Here, r represents the number of Y and is 0 or 1. Therefore, the substituent (—NH—) represented by Y is not necessarily contained. From the viewpoints of improving antistatic properties, stability of the ion-binding salt (1), ease of arrangement of the ion-binding salt (1) on the surface of the resin composition, r = 0, that is, Y does not exist. Is preferred. On the other hand, when Y is present, the substituent can be a secondary amino cation, and therefore Y is preferably present from the viewpoint of the stability of the amino cation itself.

In the above formula (q-1), Z is a monovalent substituent, and is —N (R ⁶ ) ₂ or —N═C (R ⁶ ) ₂ . Since R ⁶ will be described in detail below, detailed description thereof is omitted here. Thus, since the compound represented by the formula (q-1) includes an amino group or imino group as Z, a proton or the like is added to the nitrogen atom in the amino group or 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-binding salt (1), Z is preferably —N (R ⁶ ) ₂ . At this time, Z is likely to form a stable ammonium ion ([—N (R ⁶ ) ₃ ] ⁺ ) by adding a proton or the like.

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

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, which are respectively represented as R ⁵ and R ⁶ in the above formula (q-1), include, for example, a methyl group, an ethyl group, n -Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isoamyl group, tert-pentyl group, neopentyl group, n-hexyl group, 3-methyl Pentan-2-yl group, 3-methylpentan-3-yl group, 4-methylpentyl group, 4-methylpentan-2-yl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 3 , 3-dimethylbutan-2-yl group, n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethyl Nyl 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-methylheptan-2-yl group, 3- Methylheptane 3-yl group, 4-methylheptan-3-yl group, 4-methylheptan-4-yl group, 1-ethylhexyl group, 2-ethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, 1,1 -Dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 1-ethyl-1-methylpentyl group, 1-ethyl-4-methylpentyl group, 1,1,4-trimethylpentyl group 2,4,4-trimethylpentyl group, 1-isopropyl-1,2-dimethylpropyl group, 1,1,3,3-tetramethylbutyl group, n-nonyl group, 1-methyloctyl group, 6-methyl Octyl group, 1-ethylheptyl group, 1- (n-butyl) pentyl group, 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, 3,7-dimethyloctyl group, n-undecyl group, 1-methyldecyl group, 1-ethylnonyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, 1-methyltridecyl group, n-pentadecyl group, Examples thereof include linear and branched alkyl groups such as n-hexadecyl group, n-heptadecyl group, n-octadecyl group and n-nonadecyl group. From the viewpoint of availability and antistatic performance, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group, an ethyl group, a 2-ethylhexyl group, a tridecyl group, or 1,2-bis. (2-Ethylhexyloxycarbonyl) ethyl group is more preferable, and a methyl group, ethyl group, and 2-ethylhexyl group are particularly preferable.

Examples of the substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, which are respectively represented as R ⁵ and R ⁶ in the formula (q-1), include a methoxy group, an ethoxy group, and a propoxy group. Linear, branched alkoxy groups such as isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group and octyloxy group. From the viewpoint 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, 2- An ethylhexyloxy group is more preferable.

Examples of the substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, which are represented as R ⁵ and R ⁶ in the above formula (q-1), include, for example, a cyclopropyl group, a 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, which are respectively represented as R ⁵ and R ⁶ in the above formula (q-1), include a cyclopropyloxy group and a cyclopentyloxy group. And cyclohexyloxy group. From the viewpoints of availability and antistatic performance, a substituted or unsubstituted cycloalkoxy group having 1 to 10 carbon atoms is more preferred, and a cyclopropyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group are more preferred.

Examples of the substituted or unsubstituted aryl group having 6 to 30 carbon atoms, which are respectively represented as R ⁵ and R ⁶ in the above formula (q-1), include, for example, a phenyl group, a biphenyl group, 1 -Naphtyl, 2-naphthyl, 9-anthryl, 9-phenanthryl, 1-pyrenyl, 5-naphthacenyl, 1-indenyl, 2-azurenyl, 9-fluorenyl, terphenyl, quarterphenyl Group, mesityl group, pentalenyl group, binaphthalenyl group, tannaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthrenyl group Senyl group, quarteranthracenyl group, Nthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group , A coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, an obalenyl group, and the like. From the viewpoint 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-dodecyl group) Phenyl group and 4-dodecylphenyl group) are particularly preferable.

The substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, which is represented as R ⁵ and R ⁶ in the above formula (q-1), has the chemical formula “—OR ⁷ ” or “—OR ⁸ ”. In this case, R ⁷ represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Here, since the description of R ^{7 is} the same as that of the above-described aryl group, detailed description thereof is omitted here. From the viewpoint 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 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 an integer of 0-10. In the case where Y does not exist (r = 0), the number of methylene groups is synonymous when the value of m + n is the same. For example, when m = 1 and n = 2 (m + n = 3), m = 3 and n = 0, m = 0 and n = 3, m = 2 and n = 1. Are synonymous.

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

  Moreover, when Y exists (r = 1), it is preferable that it is m + n = 1-8, and it is more preferable that it is 2-6. Here, it is particularly preferable that m = 1 to 3 and n = 1 to 3.

In the formula (q-1), when X is present (q = 1) and X is —CH ₂ —, the number is further defined by the adjacent methylene group (—CH ₂ —: m). Are also synonymous when the values of q + m are the same. Furthermore, when X is present (q = 1) and X is —CH ₂ — and Y is absent (r = 0), these are synonymous when q + m + n values are the same. .

In the formula (q-1), at least one of R ⁵ substituted on the silicon atom is a hydroxy group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or substituted. 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) are condensed with a nearby silicon atom by hydrolysis to form a network of — (Si—O—Si) —. it is conceivable that.

Among the compounds represented by the above formula (q-1), from the viewpoint that the effect of improving the antistatic property and maintaining the antistatic property for a long period of time (that is, improving the durability) is particularly high as follows. Are preferred. That is, the ion-binding salt (1) is the above formula (q-1), wherein X is —CH ₂ —, Z is —N (R ⁶ ) ₂ , and R ⁵ is independently selected. Hydrogen atom, hydroxy group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, or substituted Or an unsubstituted aryloxy group having 6 to 30 carbon atoms, wherein at least one of R ⁵ is a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted by are one or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms or substituted or or unsubstituted aryloxy group having 6 to 30 carbon atoms,, R ⁶ is hydrogen atoms And a, m is an integer of 0 to 3, n is 0, q is 1, r is 0; preferably includes a cation Q ⁺ derived from a compound represented by .

Furthermore, among the compounds represented by the formula (q-1), all R ⁵ are preferably a hydroxy group or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms. Or an unsubstituted alkoxy group having 1 to 10 carbon atoms. The ion-binding salt (1) containing the cation Q ⁺ derived from such a compound can particularly retain the effect of improving the antistatic performance over a long period of time.

  In the present invention, specific compounds preferably used as the silane compound containing an amino group or imino group 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) propiyl Amine, 3-trimethoxysilylpropyl-N-(1,3-dimethyl - butylidene) propylamine, and the like.

(Anion T ⁻ )
In the 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). Sulfonate anion. As described above, since these anions are specific anions having an oxyalkylene chain, they are excellent in conductivity, and as a result, can greatly contribute to the improvement of the antistatic property of the resin composition. In addition, these anions provide a counter anion having a structure containing no halogen as the counter anion of the cation, and are therefore suitable for use in applications where halogens are hated. Hereinafter, the structure of these anions will be specifically described.

Linear or branched, each represented as 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). 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 preferable.

^{R 1} in the formula (t-1) in the formula (t-2) in ^{R 2} and ^{R 3,} and the formula (t-3) represented respectively as ^{R 4} in the, whether or unsubstituted are substituted An alkyl group having 1 to 20 carbon atoms, 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 thing as each substituent in the compound shown by the formula (q-1) mentioned above is illustrated, detailed description is abbreviate | 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-naphthyl group. Examples thereof include a methyl group, 2- (1-naphthyl) ethyl group, 2- (2-naphthyl) ethyl group, 3- (1-naphthyl) propyl group, and 3- (2-naphthyl) propyl group.

From the viewpoints of availability, antistatic properties and the like, R ^{1 to} R ⁴ are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, or substituted or unsubstituted carbon atoms of 6 It is more preferable that the aryl group is -30, and further is 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. And particularly preferred. Further, in view of easy availability and easy handling such as viscosity, n-butyl group, n-hexyl group, 2-ethylhexyl group, dimethylphenyl group, isopropylphenyl group, and dodecylphenyl group are preferable.

S in the formula (t-1), t and u in the formula (t-2), and v in the formula (t-3) are the number of divalent substituents-(OA ^1-4 )-. Represents an integer of 0 to 50. From the viewpoint of ease of handling due to a decrease in viscosity or the like, or from the viewpoint of interface characteristics, the above s, t, u and v are each independently preferably an integer of 1 to 40, more preferably an integer of 2 to 30. Here, when s, t, u and v are 1 or more, the ion-binding salt (1) has an oxyalkylene chain. And since the said oxyalkylene chain is excellent in electroconductivity, the ion bond salt (1) containing such an anion raises the antistatic improvement effect of the said resin composition further. Therefore, s, t, u and v are more preferably 1 or more, and particularly preferably 2 or more. On the other hand, when the oxyalkylene chain is too long, the viscosity becomes high. Therefore, in consideration of handling properties, the upper limit of s, t, u and v is preferably 50, more preferably 40, and 30. And particularly preferred.

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

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

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

That is, an ammonium salt of a sulfate ester anion represented by the above formula (t-1) ([t-1] ⁻ [NH ₄ ] ⁺ ), an ammonium salt of a phosphate ester anion represented by the formula (t-2) ( [T-2] ^- [NH ₄ ] ⁺ ) or an ammonium salt of a sulfonate anion ([t-3] ^- [NH ₄ ] ⁺ ) represented by the formula (t-3) and the amino group or imino group By reacting the contained silane compound, the ion-binding salt (1) can be obtained. Here, as the ammonium salt of the sulfate ester, the ammonium salt of the phosphate ester, or the ammonium salt of the sulfonic acid, a commercially available product may be used, or one synthesized in advance may be used. The synthesis method is not particularly limited. For example, an ammonium salt of a sulfate ester is produced by a conventionally known method such as a method of reacting alcohols, phenols or (poly) oxyalkylene alkyl ethers with sulfamic acid. Can do.

  The reaction conditions for producing the ion-binding salt (1) are not particularly limited, but are preferably the following conditions.

  The molar ratio (preparation ratio) between the ammonium salt of sulfate ester, the ammonium salt of phosphate ester or the ammonium salt of sulfonic acid and the silane compound containing an amino group or imino group is 1: 1 to 1: 2. It is preferable that the ratio is 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, ethanol and the like.

  The atmosphere of the reaction is not particularly limited, and for example, the atmosphere or an inert gas atmosphere such as nitrogen or argon can be appropriately employed. From the viewpoint of preventing coloring, an inert gas atmosphere such as nitrogen or argon Preferably it is below. Under such conditions, the by-product ammonia is distilled off simultaneously with the reaction.

  The reaction proceeds simultaneously with the production of ammonia as a byproduct, and the reaction temperature is preferably 20 to 150 ° C, more preferably 50 to 130 ° C. Moreover, it is preferable that reaction time is 1 to 6 hours, and it is more preferable that it is 2 to 5 hours.

  After completion of the reaction, a solution containing the ion-binding salt (1), the unreacted raw material amino group or imino group-containing silane compound, and the reaction solvent is obtained, and the amino group or imino group-containing silane compound and reaction are obtained. The target ion-binding salt (1) is obtained by distilling off the solvent under reduced pressure. The temperature range during this vacuum distillation is preferably 40 to 170 ° C, more preferably 50 to 160 ° C. Moreover, the time of vacuum distillation is preferably in the range of 0.5 to 5 hours, more preferably in the range of 1 to 2 hours. Further, the degree of vacuum during the vacuum distillation is preferably in the range of 0.66 to 6.67 kPa (5 to 50 mmHg), 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-binding salt (1) with respect to the resin composition, another ion-binding salt may be added. The cation of the other ion-binding salt is preferably a cation derived from a nitrogen-containing compound 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. For example, a halide ion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), an oxo acid anion (borate anion, carbonate anion, acetate anion) , Sulfate anion, sulfate anion, phosphate anion, phosphate anion, sulfonate anion, etc., boron anions (BF ₄ ⁻ ; tetraalkylborate such as tetramethylborate and tetraethylborate; tetraphenylborate, 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 these, from the viewpoints of improving the antistatic property of the resin composition and ease of handling, Cl ⁻ , Br ⁻ , sulfate ester anion, phosphate ester anion, sulfonate anion, tetraphenylborate, PF ₆ ⁻ Bis (trifluoromethanesulfonyl) imide anion and the like are preferable. Furthermore, from the viewpoint of improving antistatic properties, the anion of the other ion-binding salt is a sulfate anion represented by the formula (t-1) of the ion-binding salt (1), the formula (t-2). And a sulfonate anion represented by formula (t-3).

  Therefore, according to the second embodiment of the present invention, the ion-binding salt (1) and the ion-binding salt represented by the following formula (2) (hereinafter also simply referred to as “ion-binding salt (2)”). Also provided are ion-binding salt compositions comprising:

In the above formula (2),
(Q ′) ⁺ is ammonium ion, imidazolium ion, pyridinium ion, pyrrolidinium ion, pyrrolium ion, pyrazinium ion, pyrimidinium ion, triazolium ion, triazinium ion, quinolinium ion, isoquinolinium And at least one selected from the group consisting of ions, indolinium ions, quinoxalinium ions, piperazinium ions, oxazolinium ions, thiazolinium ions, and morpholinium ions, and the above formula (1) ) In the structure different from Q ⁺
(T ′) ⁻ represents a sulfate ester anion represented by the above formula (t-1), a phosphate ester anion represented by the above formula (t-2), or a sulfonate anion represented by the above formula (t-3). It is.

  Thus, the ion-binding salt composition according to the present invention is an ion-binding property that is a sulfate, phosphate, or sulfonate of a cation derived from the silane compound containing the amino group or imino group. A salt (1) and an ion-binding salt (2) that is a sulfate ester salt, a phosphate ester salt, or a sulfonate salt of a cation having a structure different from the cation of the ion-binding salt (1). Since the ion-binding salt composition will be described in detail below, first, the cation and anion constituting the ion-binding salt (2) will be described.

(Cation (Q ') ⁺ )
(Q ′) ⁺ is 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 quinoxaline compounds, piperazine compounds, oxazoline compounds, thiazoline compounds, and morpholine compounds.

  Specific examples of each of the above nitrogen-containing compounds can include the same compounds as those described in paragraphs [0071] to [0091] of JP 2012-72130 A. From the standpoint of availability, an amine compound is particularly preferable among the above compounds.

Among the amine compounds, ammonia (NH ₃ ); dimethylamine, diethylamine, monopropylamine, dipropylamine, monobutylamine, dibutylamine, methyl (ethyl) amine, methyl (propyl) amine, methyl (butyl) amine Alkylamines such as methyl (pentyl) amine, methyl (hexyl) amine, ethyl (propyl) amine, ethyl (butyl) amine, ethyl (pentyl) amine, ethyl (hexyl) amine; monobenzylamine, (1-phenethyl) Aromatic substituted alkylamines such as amine, (2-phenethyl) amine (also known as monophenethylamine), dibenzylamine, bis (1-phenethyl) amine, bis (2-phenethyl) amine (also known as diphenethylamine); monocyclopentyl A , Cycloalkylamines such as dicyclopentylamine, monocyclohexylamine, dicyclohexylamine, monocycloheptylamine, dicycloheptylamine; monomethanolamine, dimethanolamine, monoethanolamine, diethanolamine, triethanolamine, mono (n- Propanol) amine, di (n-propanol) amine, monoisopropanolamine, diisopropanolamine, monobutanolamine, dibutanolamine, monopentanolamine, dipentanolamine, tripentanolamine, monohexanolamine, dihexanolamine , Monomethylmonoethanolamine, monoethylmonoethanolamine (also known as N-ethylethanolamine), monoethylmonopropanolamine , Monoethylmonobutanolamine, monoethylmonopentanolamine, monopropylmonoethanolamine, monopropylmonopropanolamine, monopropylmonobutanolamine, monopropylmonopentanolamine, monobutylmonoethanolamine, monobutylmonopropanolamine Alkanolamines such as monobutylmonobutanolamine and monobutylmonopentanolamine are preferred. These amine compounds are excellent in the availability and the effect of improving the antistatic property of the resin composition.

  Among these, alkanolamine is preferably used because it is easy to improve the antistatic property of the resin composition.

(Anion (T ′) ⁻ )
In the formula (2), the anion ((T ′) ⁻ ) is a sulfate ester anion represented by the formula (t-1) and a phosphorus represented by the formula (t-2) according to the ion binding salt (1). Since it is the same as the acid ester anion or the sulfonate anion represented by the formula (t-3), detailed description thereof is omitted here.

In addition, when ion binding salt (2) comprises an ion binding salt composition with ion binding salt (1), from the viewpoint of improving the antistatic property of a resin composition, ion binding 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 mutual ion-binding salts is improved, so that the conductivity in the resin composition is likely to be uniform, and the antistatic property is easily improved.

(Method for producing ion-binding salt (2))
The method for producing the ion-binding salt (2) is not particularly limited as long as the ion-binding property having the structure of the formula (2) can be produced, and any method can be adopted. it can. For example, the method for producing the ion-binding salt (1) can be appropriately modified and changed for use. More specifically, the silane compound containing an amino group or imino group used in the production of the ion-binding salt (1) may be changed to a nitrogen-containing compound constituting the cation (Q ′) ⁺ . The reaction conditions during the production of the ion-binding salt (2) are not particularly limited and are substantially the same as those of the ion-binding salt (1), and thus detailed description thereof is omitted here.

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

[Ion-binding salt composition]
The composition ratio of the ion-binding salt (1) and the ion-binding salt (2) contained in the ion-binding salt composition according to the present invention is not particularly limited, but the ion-binding 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: 2 to 1:30 is particularly preferable.

  Furthermore, in the ion-binding salt composition of the present invention, the content ratio of the ion-binding salt (2) to the ion-binding salt (1) containing a cation derived from a silane compound containing an amino group or an imino group. It is preferable to increase the number. According to such an embodiment, the ion binding salt (2) is easily taken into the resin composition, and the ion binding salt (1) is easily dispersed on the surface of the resin composition. As a result, it is possible to further improve the conductivity of the ion-binding salt (1) dispersed on the surface of the resin composition by using a conductive path built inside the resin composition by the ion-binding salt (2). it can. In other words, if only the ion-binding salt (2) is added, the ion-binding salt (2) is not taken into the resin composition and cannot contribute to the improvement of the antistatic property. By adding the ion-binding salt (1) and dispersing it on the surface of the resin composition, the ion-binding salt (2) is greatly improved in antistatic properties starting from the ion-binding salt (1). It becomes possible to contribute.

  The ion-binding salt (1) and the ion-binding salt (2) may be used alone or in combination of two or more.

[Antistatic agent]
The ion-binding salt (1) according to the present invention or the ion-binding salt composition containing the same exhibits an extremely excellent effect as an antistatic agent such as a resin composition. That is, according to the 3rd form of this invention, the antistatic agent containing the said ion binding salt (1) or the said ion binding salt composition is provided.

  In particular, the ion-binding 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 a resin composition. Demonstrate the effect.

  Furthermore, the ion-binding salt (1) according to the present invention and the ion-binding salt composition containing the same are a resin composition to which a silicone compound or a fluorine compound is added (in particular, the silicone compound or fluorine compound is a resin surface). And the resin composition arranged in the same manner. Therefore, since it can be arranged on the surface of such a resin composition, the ion-binding salt (1) according to the present invention and the ion-binding salt composition containing the same have the antistatic property of the resin composition. Has the effect of improving.

  As described above, the antistatic agent according to the present invention is particularly effective in improving the antistatic property of the resin composition containing a silicone compound or a fluorine-based compound among the resin compositions. Therefore, according to the 4th form of this invention, the antistatic agent for resin compositions containing a silicone compound or a fluorine-type compound is also provided.

  Since the ion binding composition (1) contains a silicon atom, it has a high affinity with a silicone 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 usage 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, in a form in which an antistatic agent is kneaded in the resin composition, or on the surface of the resin composition. It may be used in a form in which an inhibitor is applied, or may be 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. Preferably, however, the antistatic agent is dispersed in the resin composition. Is adopted. Such a form is preferable because the manufacturing process of the resin composition is simplified.

[Resin composition]
As described above, the antistatic agent containing the ion-binding salt (1) of the present invention can improve the antistatic property of the resin composition containing a silicone compound or a fluorine compound. Therefore, according to the 5th form of this invention, the resin composition containing the said antistatic agent, resin, and a silicone compound or a fluorine-type compound is also provided. In the above-mentioned form, “the resin composition contains an antistatic agent” also 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 includes a resin as a main component. The antistatic agent which concerns on this invention does not ask | require the kind of resin which can improve antistatic performance. Therefore, as the resin used in the resin composition according to the present invention, any of a thermosetting resin and a thermoplastic resin can be used.

  The thermosetting resin used in the present invention is not particularly limited, and examples thereof include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, urethane resin, and thermosetting polyimide resin. . These 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. For example, (meth) acrylic resin, styrene resin, polyester resin, polycarbonate resin, olefin resin (polyethylene, polypropylene, etc .; 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.

  The form of the copolymer when the thermosetting resin or the thermoplastic resin is a 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. Examples thereof include a high pressure radical polymerization method, a medium to low pressure polymerization method, a UV polymerization method, a solution polymerization method, a slurry polymerization method, a bulk polymerization method, an emulsion polymerization method, and a gas phase polymerization method. 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.

Furthermore, whether the ion-binding salt (1) contained in the resin composition contains a cation derived from the compound represented by the formula (q-1), and at least one of R ⁵ is substituted with a hydroxy group Or an 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 having 6 to 30 carbon atoms When it is an aryloxy group, it is preferable that the monomer compound used as the raw material of the resin has a hydroxy group. When at least one of the substituents (R ⁵ ) on the silicon atom in the formula (q-1) has a hydroxy group, an alkoxy group, a cycloalkoxy group, or an aryloxy group, these substituents constitute a resin. By reacting with the hydroxyl group of the monomer compound and crosslinking, the ion-binding salt (1) is more firmly incorporated into the resin composition, and the effect of improving the antistatic property is easily maintained.

  The content of the antistatic agent in the resin composition is not particularly limited, but in order to obtain sufficient antistatic properties, 0.01 to about 100 parts by mass of a resin (excluding a silicone compound and a fluorine-based compound). It 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. If it is 0.01 mass part or more, the improvement effect of the antistatic property by ion binding salt (1) can fully be acquired. On the other hand, if it is 100 parts by mass or less, a large amount of the antistatic agent is not added, and therefore, it can be sufficiently exerted without impairing the original characteristics of the resin composition. In addition, an antistatic agent can be used individually or in combination of 2 or more types.

  Further, the content of the ion-binding salt (1) in the resin composition is not particularly limited, but is 0.01 to 100 parts by mass with respect to 100 parts by mass of the resin (excluding the silicone compound and the fluorine compound). It is preferable, it is more preferable in it being 0.05-70 mass parts, it is still more preferable in it being 0.1-50 mass parts, and it is especially preferable in it being 0.1-10 mass parts. If it is the said range, while being able to fully improve the antistatic property of a resin composition, the original characteristic of a resin composition can fully be 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 and the like of the resin. Below, a silicone compound is demonstrated first.

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

Things as the silicone compound is not particularly limited, in view of easiness of handling, kinematic viscosity (25 ° C.) preferably when used as a 10 to 1000 mm ² / s, is 50 to 500 mm ² / s Is more preferable.

  Examples of the silicone compound used in the present invention include, for example, dimethyl silicone, methyl hydrogen silicone, methyl phenyl silicone, cyclic dimethyl silicone, amino-modified silicone, dimethyl silicone, a side chain or a part of the methyl group at the terminal is a hydroxy group. Organosilicon polymers such as organopolysiloxanes (also referred to herein as “hydroxysilicones”). In addition, 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 obtained and used.

  Among the above silicone compounds, dimethyl silicone, hydroxy silicone, and silicone-acrylic resin are preferably used from the viewpoints of availability, price, and the like, and easy improvement of the water repellency and oil repellency of the resin composition. Here, the hydroxy silicone preferably has a hydroxyl value in the range of 1 to 500 mgKOH / g, and more preferably in the range of 10 to 300 mgKOH / g. Here, the hydroxyl value means a value measured according to JIS-K-0070: 1992.

  Examples of commercially available dimethyl silicone include KM-780, KM-782, KM-785, KM-797, KM-9705, KM-860A, KM-862T, KS-702, KS-725, and KS-707 ( As described above, Shin-Etsu Chemical Co., Ltd.) can be used. Further, SR2462, SR2306, SR2316, dry seal S, 804RESIN, 840RESIN, SR2400, 220FLAKE, 233FLAKE, 249FLAKE, 52ADDITIVE (above, manufactured by Toray Dow Corning Co., Ltd.) can be used.

  Examples of commercially available hydroxysilicone products include X-21-5841, KF-9701, X-22-160AS, KF-6001, KF-6002, and KF-6003 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), PRX413. (Toray Dow Corning Co., Ltd.) 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 obtained sufficiently, but as a guideline, a resin (excluding silicone compounds and fluorine compounds) 100 It is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and particularly preferably 1 to 5 parts by mass with respect to parts by mass. If it is 0.1 mass part or more, the resin composition which has sufficient water repellency and oil repellency can be obtained. On the other hand, if it is 10 mass parts or less, the antistatic improvement effect by the antistatic agent of this invention can further be heightened.

  Further, 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, a resin (excluding silicone-acrylic resin and fluorine-based compound) It is preferable that it is 5-100 mass parts with respect to 100 mass parts, It is more preferable in it being 5-80 mass parts, It is especially preferable in it being 10-60 mass parts. If it is 5 mass parts or more, the resin composition which has sufficient water repellency and oil repellency can be obtained. On the other hand, if it 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 guideline, it is preferably 100 to 500 parts by mass, and 250 to 400 parts by mass with respect to 100 parts by mass of the silicone compound. Is more preferable. If it is the said range, the resin composition which has the especially outstanding antistatic property can be obtained. In addition, when a resin composition contains the fluorine-type compound explained in full detail below with a silicone compound, it is preferable when the total amount of these compounds is 100 mass parts and an antistatic agent is contained by the mass ratio similar to the above.

(Fluorine compounds)
The resin composition according to the present invention may contain a fluorine-based compound for the purpose of improving the water repellency and the like of the resin. In addition, you may use a fluorine-type compound with the said silicone compound.

  If the fluorine-type compound used by this invention is a silicone compound which can achieve the said objective, it will not restrict | limit in particular, A well-known thing can be used. Examples include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, chlorofluoroethylene / vinylidene fluoride copolymer, and the like. These fluorine compounds may be synthesized, or commercially available products may be obtained and 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, a resin (excluding silicone compounds and fluorine compounds) The amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and particularly preferably 1 to 5 parts by mass with respect to 100 parts by mass. If it is 0.01 mass part or more, the resin composition which has sufficient water repellency and oil repellency can be obtained. On the other hand, if it is 10 mass parts or less, the antistatic improvement effect by the antistatic agent of this invention can further be heightened.

  Further, the content of the antistatic agent with respect to the fluorine 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 compound, and 250 to 400 More preferably, it is part by mass. If it is the said range, the resin composition which has the especially outstanding antistatic property 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, UV absorbers, light stabilizers, foaming agents, waxes, crystal nucleating agents. , Release agents, hydrolysis inhibitors, antiblocking agents, radical scavengers, antifogging agents, antifungal agents, ion trapping agents, flame retardants, flame retardant aids, surfactants 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, (II) a kneading method, and (III) a coating method.

(I) Dispersion method The ion-binding salt (1) of the present invention, the monomer compound used as the raw material for the resin, the silicone compound, and the catalyst and other additives added as necessary are dispersed in the system. And a method of polymerizing the monomer compound by solution polymerization or ultraviolet polymerization to obtain a resin composition. At this time, if necessary, an ion-binding salt (2) may also be added (in this case, it is synonymous with the addition of the ion-binding salt composition to the system). By adopting 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 modified depending on the type of resin.

(II) Kneading method Another method includes a method of melt-kneading the ion-binding salt (1), the resin, the silicone compound, and other additives added as necessary. At this time, if necessary, an ion-binding salt (2) may also be added (in this case, it is synonymous with the addition of the 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 heat roll, a Banbury mixer, a Henschel mixer, a tumbler mixer, or various kneaders is adopted. be able to.

(III) Coating Method As yet another method, a solution (coating solution) of the ion-binding salt (1) may be prepared, and the coating solution may be applied to the surface of the kneaded resin and silicone compound. At this time, the said coating liquid may also contain the ion binding salt (2) as needed (in this case, it is synonymous with apply | coating the said ion binding salt composition).

[Other uses of ion-binding salt (1) and ion-binding salt composition]
As described above, the ion-binding salt (1) and the ion-binding salt composition according to the present invention act as an antistatic agent. On the other hand, besides these, it can be used as a treating agent that exerts a physical action or a chemical action on a gas such as plastic, metal, CO ₂ or the like. More specifically, the ion-binding 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 acidic gas absorbent, and a wastewater treatment agent. It can also act as a synthetic catalyst, drug delivery system (DDS), metal processing, polymer processing, weathering agent. Among the above, other typical uses of the ion-binding salt (1) and the ion-binding salt composition include use as a dispersant / emulsifier, in particular.

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

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not restrict | limited at all by the following Example. In the following description, “part” or “%” may be used, but “part by mass” or “% by mass” is indicated unless otherwise specified.

(Synthesis Example 1: Synthesis of [APM-Si] [EHDG-S]; Synthesis of ion-binding salt (1))
150.0 parts by mass of toluene was added to 150.0 parts by mass of diethylene glycol mono-2-ethylhexyl ether (trade name: 2-ethylhexyl diglycol, abbreviation: EHDG, manufactured by Nippon Emulsifier Co., Ltd.), 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 to obtain a toluene solution of diethylene glycol mono 2-ethylhexyl ether sulfate ammonium salt (abbreviation: EHDG-SF; ammonium ion is NH ₄ ⁺ ).

To 100.0 parts by mass of the 50% toluene solution of EHDG-SF obtained above, 42. 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903, abbreviation: APM-Si) is obtained. 7 parts by mass was added and reacted at 120 ° C. for 3 hours. (EHDG-SF and 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 vacuum: 1.33 kPa (10 mmHg)), and the desired ion-binding salt (1) (abbreviation: [APM- Si] [EHDG-S]; 72.3 parts by mass of the compound represented by the chemical formula (101) was obtained.

The NMR spectrum data of the obtained [APM-Si] [EHDG-S] are shown below. ¹ H-NMR (CDCl ₃ , 400 MHz) δ 0.65-0.75 (t, 2H), 0.83-0.90 (m, 6H), 1.27-1.42 (m, 8H), 1.47-1.53 (m, 1H), 1.77- 1.86 (m, 2H), 2.96-3.05 (m, 2H), 3.30-3.36 (m, 2H), 3.56 (s, 11H), 3.62-3.65 (t, 2H), 3.73-3.75 (t, 2H), 4.25-4.28 (t, 2H).

(Synthesis Example 2: Synthesis of [MEM] [EHDG-S]; Synthesis of Ion Binding Salt (2))
The target ionic bond is similar to Synthesis Example 1 except that N-ethylethanolamine (Nippon Emulsifier Co., Ltd., trade name: aminoalcohol MEM, abbreviation: MEM) is used instead of APM-Si. Salt (2) (abbreviation: [MEM] [EHDG-S]; compound represented by the chemical formula (201)) was obtained. At this time, the EHDG-SF and MEM molar ratio was 1: 1.5.

(Synthesis Example 3: Synthesis of [APE-Si] [EHDG-S]; Synthesis of ion-binding salt (1))
Synthesis Example 1 except that 52.7 parts by mass of 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903, abbreviation: APE-Si) was used instead of APM-Si Similarly, a target ion-binding salt (abbreviation: [APE-Si] [EHDG-S]; compound represented by the above chemical formula (102)) was obtained.
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), 1.77- 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]; Synthesis of Ion Binding Salt (1))
In the same manner as in Synthesis Example 1 except that 34.6 parts by mass of N- (trimethylsilyl) diethylamine (Tokyo Chemical Industry Co., Ltd., abbreviation: MSi-N (Et) ₂ ) was used instead of APM-Si. A target ion-binding salt (abbreviation: [MSi-N (Et) ₂ ] [EHDG-S]; a compound represented by the above chemical formula (113)) was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 0.08 (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-binding salt (1))
Cumene sulfonic acid (o-, m-, p-cumene sulfonic acid isomer mixture) (manufactured by Teika Co., Ltd., trade name: Teikatox 500, abbreviation: Cum-SO ₃ H) APM-Si 179 in 200.3 parts by mass After adding 3 parts by mass, the reaction is performed for 1 hour, and the target ionic liquid (abbreviation: [APM-Si] [Cum-SO ₃ ]; compound represented by the chemical formula (107)) 379.6 parts by mass Got.
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))
80% methanol solution of ammonium polyoxyethylene tridecyl ether sulfate (abbreviation: 1305-SF; ammonium ion is NH ₄ ⁺ ) synthesized by a conventionally known method instead of the 50% toluene solution of EHDG-SF in Synthesis Example 1 The target ion-binding salt (abbreviation: [APM-Si] [1305-S]; represented by the above chemical formula (111)) is the same as Synthesis Example 1 except that 102.7 parts by mass is used. Compound) was obtained.
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))
An autoclave was charged with 200.0 parts by mass of dioctyl fumarate, 116.4 parts by mass of a 50% aqueous solution of ammonium hydrogen sulfite, 37.0 parts by mass of methanol, and 15.6 parts by mass of water. It was. The maximum pressure at this time was 0.25 MPa.

30.4 parts by mass of MEM was added to 140.0 parts by mass of ammonium dioctylsulfosuccinate (abbreviation: DOSS-NH ₄ ) obtained above (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 MEM were distilled off under reduced pressure (temperature: 125 ° C., degree of vacuum: 1.33 kPa (10 mmHg)), and the desired ionic liquid (abbreviation: [MEM] [DOSS]; 115.0 parts by mass of a compound represented by the chemical formula (211) was obtained.

(Reference Example 1)
A rotor is put into a 20 ml glass bottle, and ACRICID BU-955 (acrylic polyol, manufactured by DIC Corporation, solid content 59.9%) 83.47 parts by mass, dibutyltin dilaurate 0.06 parts by mass (based on resin solids) 0.1% by mass), 30.0 parts by mass of toluene, and 3.97 parts by mass of [MEM] [EHDG-S] obtained in Synthesis Example 2 (7% by mass with respect to the solid content of the resin) were added. 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 apply | coated with the film thickness of 75 micrometers on the glass plate, and it dried for 30 minutes with a 110 degreeC dryer, and obtained the test piece.

(Comparative Example 1)
In Reference Example 1 above, 1.13 parts by mass of dehydrated product of KM-860A (chain dimethylsilicone compound, manufactured by Shin-Etsu Chemical Co., Ltd.) 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) was further added.

Example 1
In Comparative Example 1 above, instead of [MEM] [EHDG-S] 3.97 parts by mass, [APM-Si] [EHDG-S] 0.57 parts by mass (in terms of resin solids) obtained in Synthesis Example 1 above. 1% by mass) and [MEM] [EHDG-S] obtained in Synthesis Example 2 3.40 parts by mass (6% by mass with respect to resin solids) were added, as in Comparative Example 1. Thus, a test piece was obtained.

(Example 2)
In Example 1 above, the addition amount of [APM-Si] [EHDG-S] and [MEM] [EHDG-S] was changed to 1.14 parts by mass (2% by mass relative to the resin solids) and A test piece was obtained in the same manner as in Example 1 except that the amount was changed to 2.83 parts by mass (5% by mass with respect to the resin solid content).

(Example 3)
In Example 1 above, the addition amount of [APM-Si] [EHDG-S] and [MEM] [EHDG-S] was changed to 0.285 parts by mass (0.5% by mass relative to the resin solid content). ) And 3.68 parts by mass (6.5% by mass based on the resin solid content), and a test piece was obtained in the same manner as in Example 1.

Example 4
In Example 1 above, the addition amount of [APM-Si] [EHDG-S] and [MEM] [EHDG-S] was changed to 0.057 parts by mass (0.1% by mass relative to the resin solid content). ) And 3.90 parts by mass (6.9% by mass relative to the resin solid content), and a test piece was obtained in the same manner as in Example 1.

(Comparative Example 2)
In Reference Example 1 above, 1.13 parts by mass of KF-6003 (hydroxysilicone compound, manufactured by Shin-Etsu Chemical Co., Ltd.) (2 relative to the 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 the addition amount of Duranate TPA-100 (isocyanate, manufactured by Asahi Kasei Chemicals Corporation) was changed to 6.75 parts by mass. In addition, in the above, KF-6003 as a silicone compound contains a hydroxyl group 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 [MEM] [EHDG-S] 3.97 parts by mass, [APM-Si] [EHDG-S] 1.14 parts by mass obtained in Synthesis Example 1 (in terms of resin solids) Comparative Example 2 except that 2% by mass) and 2.83 parts by mass of [MEM] [EHDG-S] obtained in Synthesis Example 2 (5% by mass with respect to the resin solid content) were added. Thus, a test piece was obtained.

(Reference Example 2)
A rotator is placed in a 20 ml glass bottle, Dianal LR-186 (acrylic resin, manufactured by Mitsubishi Rayon Co., Ltd., solid content: 46.3%) 64.73 parts by mass, Cymac US-350 (silicone-acrylic resin, Toagosei Co., Ltd.) Manufactured, 32.3% solid content) 65.02 parts by mass and 2-butanone 25.2 parts by mass were added and mixed for 10 minutes. The obtained mixed solution was applied on a glass plate with 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)
Test piece 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 (4.1% by mass with respect to the resin solid content) was further added. Got.

(Example 6)
[MEM] [EHDG-S] Instead of 2.10 parts by mass, 0.42 parts by mass of [APM-Si] [EHDG-S] obtained in Synthesis Example 1 above (0.8% by mass relative to the resin solid content) ) And [MEM] [EHDG-S] 2.10 parts by mass (4.1% by mass with respect to the resin solid content) obtained in Synthesis Example 2 were added, and the test was conducted in the same manner as in Comparative Example 3. I got a piece.

(Example 7)
[MEM] [EHDG-S] Instead of 2.10 parts by mass, 0.42 parts by mass of [APM-Si] [Cum-SO ₃ ] obtained in Synthesis Example 5 above (0.8 parts by mass relative to the resin solid content) %) And [MEM] [EHDG-S] 2.10 parts by mass (4.1% by mass with respect to the resin solid content) obtained in Synthesis Example 2 were added in the same manner as in Comparative Example 3. A specimen was obtained.

(Example 8)
[MEM] [EHDG-S] Instead of 2.10 parts by mass, 0.42 parts by mass of [APM-Si] [1305-S] obtained in Synthesis Example 6 above (0.8% by mass relative to the resin solid content) ) And [MEM] [EHDG-S] 2.10 parts by mass (4.1% by mass with respect to the resin solid content) obtained in Synthesis Example 2 were added, and the test was conducted in the same manner as in Comparative Example 3. I got a piece.

Example 9
[MEM] [EHDG-S] Instead of 2.10 parts by mass, 0.42 parts by mass of [APE-Si] [EHDG-S] obtained in Synthesis Example 3 above (0.8% by mass relative to the resin solid content) ) And [MEM] [EHDG-S] 2.10 parts by mass (4.1% by mass with respect to the resin solid content) obtained in Synthesis Example 2 were added, and the test was conducted in the same manner as in Comparative Example 3. I got a piece.

(Example 10)
Instead of [MEM] [EHDG-S] 2.10 parts by mass, [MSi-N (Et) ₂ ] [EHDG-S] 0.42 parts by mass (0 with respect to the resin solid content) obtained in Synthesis Example 4 above. 0.8 mass%) and [MEM] [EHDG-S] 2.10 parts by mass (4.1 mass% based on the resin solid content) obtained in Synthesis Example 2 above, and Comparative Example 3 A test piece was obtained in the same manner.

(Example 11)
[MEM] [EHDG-S] Instead of 2.10 parts by mass, 0.42 parts by mass of [APM-Si] [EHDG-S] obtained in Synthesis Example 1 above (0.8% by mass relative to the resin solid content) ) And 2.10 parts by mass of [MEM] [DOSS] obtained in Synthesis Example 7 (4.1% by mass with respect to the resin solid content) were added in the same manner as in Comparative Example 3 to obtain a test piece. Obtained.

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

(Example 12)
[MEM] [EHDG-S] Instead of 2.10 parts by mass, 0.42 parts by mass of [APM-Si] [Cum-SO ₃ ] obtained in Synthesis Example 5 above (0.8 parts by mass relative to the resin solid content) %) And [MEM] [EHDG-S] obtained in Synthesis Example 2 1.68 parts by mass (3.3% by mass with respect to the resin solid content) were added in the same manner as in Comparative Example 3. A specimen was obtained.

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

(Comparative Example 6)
A rotor is put into a 20 ml glass bottle, Byron 20SS (polyester resin, manufactured by Toyobo Co., Ltd., solid content 35.6%) 117.98 parts by mass, Cymac US-350 (silicone-acrylic resin, manufactured by Toagosei Co., Ltd., solid) Min. 32.3%) 65.02 parts by mass, 2-butanone 25.2 parts by mass, 1.26 parts by mass of [MEM] [EHDG-S] obtained in Synthesis Example 2 (4. 1% by mass) and mixed for 10 minutes. The obtained mixed solution was applied on a glass plate with a film thickness of 75 μm and dried for 10 minutes with a dryer at 110 ° C. to obtain a test piece.

(Example 13)
[APM-Si] [EHDG-S] obtained in Synthesis Example 1 was added in the same manner as Comparative Example 6 except that 0.42 parts by mass (0.8% by mass relative to the resin solid content) was further added. A specimen was obtained.

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

≪Evaluation≫
The antistatic property, durability and contact angle of the resin compositions obtained in the above Reference Examples, Examples and Comparative Examples were evaluated by the following methods. The measurement results are shown in Tables 1 to 3. In addition, “-” in the table indicates that the evaluation item is not evaluated.

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

[Measurement of surface resistivity after water washing (durability test)]
Washing water with 5 drops of neutral detergent added to 1 L of water and moistening the sponge with this sponge, rubbing the test piece (only the test piece of Example 1) 10 times, rinsing tap water followed by ion-exchanged water, And then dried at 110 ° C. for 10 minutes. The surface resistivity of the test piece after this process was repeated three times was measured. The measurement was performed in the same manner as the above [Measurement of surface resistivity].

[Measurement of contact angle]
The contact angle of water droplets in the test piece after fabrication was measured by using a contact angle measuring device CA-XP type (manufactured by Kyowa Interface Science Co., Ltd.) and dropping the water droplets from a microsyringe and measuring the contact angle with water 30 seconds later. It was evaluated by doing. In addition, if the measured value of a contact angle is 90 degrees or more, it means that water repellency is sufficiently imparted to the resin.

  First, it is understood from the comparison between Reference Example 1 and Comparative Example 1 in Table 1 that the antistatic property of the resin composition containing a silicone compound is extremely lowered. On the other hand, as a result of comparison between Comparative Example 1 and Examples 1 to 4, the result that the antistatic property was greatly improved by adding the ion binding salt (1) was obtained. In particular, as Example 3, the ion-binding salt (1) was 6.5% by mass with respect to the resin (the urethane resin produced by the polymerization reaction of polyol and isocyanate) (ion-binding property with respect to 100 parts by mass of the resin). When 6.5 parts by mass of salt (1) was added, the antistatic property of the resin composition was most improved.

  Further, in Example 1 above, the antistatic property of the test piece that had been washed three times with water was also evaluated, but the antistatic property did not substantially decrease even after the water washing, indicating that it has good durability. It was done. This result shows that the ion-binding salt (1) according to the present invention improves the antistatic property while maintaining good affinity with the resin composition containing the silicone compound. In particular, since the ion-binding 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, as described above. It is presumed that the effect (durability) for maintaining good antistatic properties is high.

  Furthermore, 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 from the result of Example 5, even if it is a case where a hydroxy silicone compound is used as a silicone compound contained in a resin composition, antistatic property can be improved by the ion-binding salt (1) of the present invention. Was confirmed.

  As shown in Tables 2 and 3, resins other than urethane resin (in Table 2, a mixture of acrylic resin and silicone-acrylic resin, in Table 3, a mixture of polyester resin and silicone-acrylic resin) are used. It was confirmed that the effect of improving the antistatic property was exhibited in the same manner as in Table 1 even when the ionic bond salt (1) had various structures. As shown in Tables 2 and 3, even when the ion binding salt according to the present invention is blended, the contact angle is maintained at a sufficiently large value. It has also been confirmed that the addition has no possibility of adversely affecting the water repellency, which is the original purpose when adding a silicone compound or a fluorine-based compound.

  As described above, by using the ion-binding salt (1) of the present invention (or an ion-binding salt composition further containing an ion-binding salt (2) as necessary), an expensive conductive polymer, It was shown that the antistatic property 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 the antistatic property is excellent in durability.

Claims (10)

Ion-binding salt represented by the following formula (1):
In the above formula (1),
Q ⁺ is a cation derived from a silane compound containing an amino group or an imino group;
In the above formula (1), T ⁻ represents 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 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 from 0 to 50,
Sulfate anion represented by
Following formula (t-2):
In the above formula (t-2),
R ² and R ³ are each independently a hydrogen atom, 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 group, 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 Is not a hydrogen atom at the same time,
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;
A phosphate ester anion represented by
The following formula (t-3):
In the above formula (t-3),
R ⁴ represents 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 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 from 0 to 50,
It is a sulfonate anion shown by. In the above formula (1),
Q ⁺ represents the following formula (q-1):
In the above formula (q-1),
X is —CH ₂ — or an oxygen atom (—O—);
Y is -NH-,
Z is —N (R ⁶ ) ₂ or —N═C (R ⁶ ) ₂ ;
R ⁵ each independently represents a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms. Groups, substituted or unsubstituted cycloalkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkoxy groups having 3 to 20 carbon atoms, substituted or unsubstituted carbon atoms An 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 carbon atom; Represents 6 to 30 aryl groups),
R ⁶ each independently represents 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, substituted Substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, substituted or unsubstituted 6 to 6 carbon atoms 30 aryl groups, or substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms (-OR ⁸ , wherein R ⁸ is substituted or unsubstituted carbon atoms having 6 to 30 carbon atoms. Represents an aryl group of
m is an integer from 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: 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 group The ion-binding salt according to claim 2, which is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. In the formula (q-1),
X is —CH ₂ —;
Z is —N (R ⁶ ) ₂ ;
R ⁵ each independently represents a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cyclohexane 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 from 0 to 3,
n is 0;
q is 0 or 1;
The ion-binding salt according to claim 2 or 3, wherein r is 0. An ion-binding salt composition comprising the ion-binding salt according to any one of claims 1 to 4 and an ion-binding salt represented by the following formula (2):
In the above formula (2),
(Q ′) ⁺ is ammonium ion, imidazolium ion, pyridinium ion, pyrrolidinium ion, pyrrolium ion, pyrazinium ion, pyrimidinium ion, triazolium ion, triazinium ion, quinolinium ion, isoquinolinium And at least one selected from the group consisting of ions, indolinium ions, quinoxalinium ions, piperazinium ions, oxazolinium ions, thiazolinium ions, and morpholinium ions, and the above formula (1) ) In the structure different from Q ⁺
(T ′) ⁻ represents a sulfate ester anion represented by the above formula (t-1), a phosphate ester anion represented by the above formula (t-2), or a sulfonate anion represented by the above formula (t-3). It is.   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.   The antistatic agent according to claim 6, which is an antistatic agent for a resin composition containing a silicone compound or a fluorine-based compound. An antistatic agent according to claim 6;
Resin,
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 or 9, 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.