JP2010150461A - Antistatic agent and use of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic agent which has not only high antistatic performance but also colorless transparency, solubility (compatibility) to resin and solvent and heat resistance, and does not contain metal and metal ion. <P>SOLUTION: The antistatic agent has a specified fundamental structure of a salt made of thiocyanate anion and amidinium cation such as the salt obtained from potassium thiocyanate and 2-chloro-1,3-dimethylimidazolium chloride and the salt obtained from potassium thiocyanate and (dimethylaminomethylene)dimethylammonium chloride. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antistatic agent and its use.

  From the viewpoint of high processability, light weight, and variety of materials, resin has become one of the materials that are indispensable in modern times. The general property is high insulation. Utilizing this characteristic, resins have been used as insulating sites for many electronic products and electronic parts. On the other hand, because of its high insulating property, it has a problem that it is easily charged by friction and peeling.

  Not only dust and debris adhere to the charged resin molding, but when applied to electronic products and electronic components, it may adversely affect the internal circuits, transistors, ICs, CPUs, etc., and may damage them. is there. In addition, there is a possibility of causing an explosion in places where electric shock is given to the human body or where flammable gas or dust is handled. Also, in clean rooms and medical institutions, dust and dust are disliked, so an interior material with antistatic performance is required.

  In the field of electronic materials used for electronic products and electronic parts, contamination by alkali metal ions such as sodium ions and potassium ions and alkaline earth metal ions is regarded as a problem. When these ions are mixed in the electronic material, not only the function of the electronic product or the electronic component is deteriorated or destroyed, but also there is a risk of heat generation, ignition, and explosion due to these. From such a point of view, it is desirable that materials applied to electronic products and electronic parts do not contain metal ions.

  In order to solve these problems, the resin is often treated with an antistatic agent. Treatment with an antistatic agent is roughly divided into surface treatment and internal treatment depending on how it is used.

  In the surface treatment, an antistatic agent is applied to the surface of a resin molding using a technique such as application, immersion, or spraying. A typical example is a water-soluble surfactant, but it has a drawback that its antistatic ability decreases with time.

  The internal treatment is a technique of adding an antistatic agent to the polymer during resin molding. Representative antistatic agents in this technique include conductive fine particles and surfactants.

  Examples of the conductive fine particles include metal powder, metal oxide fine particles such as ITO and ATO, and carbon. However, in order to impart antistatic ability to the resin using these materials, a considerable amount is not added. In addition, advanced technology is required to uniformly disperse them. Further, due to the large amount of addition, the original physical properties of the resin are greatly affected.

  Furthermore, many metal oxide fine particles contain metals such as antimony and indium. Among them, heavy metals such as antimony have a big problem at the time of disposal, and there are concerns about human health and environmental safety. Furthermore, noble metals such as indium have problems of depletion and high price.

  Surfactants include anionic, cationic, and nonionic surfactants, which are inexpensive and are used in various applications. However, they also have the problem of causing bleeding from the resin surface and contaminating the surroundings. In addition, anionic systems lack compatibility with polymers, are difficult to disperse uniformly, and have low heat resistance. Cationic systems have no problem with antistatic properties, but have low thermal stability. However, there are problems such as low compatibility with polymers.

  In addition, an antistatic agent having a metal ion such as sodium ion or potassium ion has a low compatibility with a polymer or an organic solvent, and is easily discolored.

  Furthermore, in these materials, the influence on the performance by the surrounding environment is large. In particular, it is said that the influence of humidity is great. In general, the antistatic effect is exhibited under high humidity conditions, but when the humidity is low, the effect diminishes and eventually may not function at all.

  In addition, when combined with a colorless and highly transparent resin, the antistatic agent is also required to have high colorless transparency so as not to lose its characteristics. Even if it is an application that does not require so much colorless transparency, it is desired that the colorless transparency is high due to problems in design and the like.

  In the market, an antistatic agent capable of comprehensively solving these problems is demanded. That is, an antistatic agent having not only high antistatic ability but also colorless transparency, solubility in a resin or solvent (compatibility), heat resistance, and moisture resistance and containing no metal or metal ion is required.

JP-A-4-239565 Japanese Patent Laid-Open No. 4-7350 Japanese Patent Laid-Open No. 4-198239

  The object of the present invention is to provide an antistatic agent that has not only high antistatic ability, but also colorless transparency, solubility in resins and solvents (compatibility), heat resistance and moisture resistance, and does not contain metal or metal ions. There is to do. Another object of the present invention is to provide a resin composition, a resin varnish, a polymerizable composition, a coating liquid using the antistatic agent, and a method for producing a resin shaped article having antistatic ability using these. It is to provide. Furthermore, the other object of this invention is to provide the resin molded article which has antistatic ability.

  The present invention relates to an antistatic agent comprising a compound represented by the following general formula [1].

General formula [1]

(Wherein R ¹ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a substituent; It may have an alkoxyl group that may have, an aryloxy group that may have a substituent, an alkylthio group that may have a substituent, an arylthio group that may have a substituent, or a substituent. Represents a good amino group.
R ^{2 to} R ⁵ are each independently a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an aryl group that may have a substituent, or Represents an acyl group which may have a substituent.
R ¹ and R ² , R ¹ and R ⁵ , R ² and R ³ , R ³ and R ⁴ , and R ⁴ and R ⁵ may be bonded to each other to form a ring structure. )

  Another aspect of the present invention relates to a resin composition comprising a resin and the antistatic agent. Preferably, the resin is a thermoplastic resin and / or a thermosetting resin.

  Another aspect of the present invention relates to a resin varnish comprising the resin composition and a solvent.

  Another aspect of the present invention relates to a polymerizable composition comprising a compound having a polymerizable functional group, a polymerization initiator, and the antistatic agent. Furthermore, other this invention has the antistatic ability manufactured by the manufacturing method of the resin hardened | cured material which has the antistatic ability which hardens the said polymeric composition by light irradiation, and the said manufacturing method. It relates to a cured resin.

  Another aspect of the present invention relates to a coating liquid comprising a solvent and an antistatic agent. Further, the present invention relates to a method for producing a resin shaped article having an antistatic ability, wherein the coating liquid is applied to the resin shaped article, and a resin shaped article having an antistatic ability produced by the production method. .

  Another aspect of the present invention relates to a resin shaped article having an antistatic ability, produced using the resin composition, the resin varnish, or the polymerizable composition.

  Another aspect of the present invention relates to a coating film having an antistatic ability, formed using the resin composition, the resin varnish, the polymerizable composition, or the coating liquid.

  Another aspect of the present invention relates to a resin shaped article having an antistatic ability, provided with the coating film on the surface.

  Another aspect of the present invention relates to a resin shaped article having an antistatic ability using the antistatic agent.

  The antistatic agent used in the present invention is a salt represented by the following general formula [1] and has a basic structure composed of a thiocyanate anion and an amidinium cation. By having a basic structure that combines these specific organic ions, it has not only high antistatic ability, but also colorless transparency, solubility in resins and solvents (compatibility), heat resistance, and moisture resistance. It is possible to provide an antistatic agent that does not contain metal ions, and in the range that does not impair the properties, by introducing an appropriate substituent into the molecule, solubility in the resin or solvent used together (compatibility) ) Can be used after adjustment.

General formula [1]

(Wherein R ¹ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a substituent; It may have an alkoxyl group that may have, an aryloxy group that may have a substituent, an alkylthio group that may have a substituent, an arylthio group that may have a substituent, or a substituent. Represents a good amino group.
R ^{2 to} R ⁵ are each independently a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an aryl group that may have a substituent, or Represents an acyl group which may have a substituent.
R ¹ and R ² , R ¹ and R ⁵ , R ² and R ³ , R ³ and R ⁴ , and R ⁴ and R ⁵ may be bonded to each other to form a ring structure. )

 The substituent in the general formula [1] will be described.

 Examples of the halogen atom in the present invention include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

 Examples of the alkyl group in the present invention include linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 30 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group. Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, t-butyl group, sec-pentyl group, t -Pentyl group, t-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like can be mentioned. Is not to be done.

 Examples of the alkenyl group in the present invention include straight-chain, branched-chain, monocyclic or condensed polycyclic alkenyl groups having 1 to 30 carbon atoms, which have a plurality of carbon-carbon double bonds in the structure. Specific examples include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3- Pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group Examples thereof include, but are not limited to, an enyl group and a cyclopentadienyl group.

  Examples of the aryl group in the present invention include a monocyclic or condensed polycyclic aryl group having 4 to 30 carbon atoms which may contain a hetero atom. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, 9 -Anthryl group, 9-phenanthryl group, 1-indenyl group, 9-fluorenyl group, 2-furyl group, 2-thienyl group, 2-indolyl group, 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, Examples thereof include, but are not limited to, a 2-carbazolyl group and a 3-carbazolyl group.

 Examples of the alkoxyl group in the present invention include a linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 30 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. , Pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, t- Butoxy group, sec-pentyloxy group, t-pentyloxy group, t-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbol Nyloxy group, boronyloxy Group, 4-decyl cyclohexyl group, 2-tetrahydrofuranyl group, 2-but-tetrahydropyranyl can be mentioned oxy group, but is not limited thereto.

  Examples of the aryloxy group in the present invention include a monocyclic or condensed polycyclic aryloxy group having 4 to 30 carbon atoms which may contain a hetero atom, and specific examples include a phenoxy group, a 1-naphthyloxy group, and 2-naphthyloxy group. Group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9 -Fluorenyloxy group, 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyl Ruoxy group, 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group and the like. The present invention is not limited to, et al.

  Examples of the alkylthio group in the present invention include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 30 carbon atoms. Specific examples include a methylthio group, an ethylthio group, a propylthio group, and a butylthio group. Pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group, isopropylthio group, sec-butylthio group, t-butylthio group, cyclopentylthio group, cyclohexylthio group, adamantylthio group, norbornylthio group, etc. Although it is mentioned, it is not limited to these.

 Examples of the arylthio group in the present invention include a monocyclic or condensed polycyclic arylthio group having 4 to 30 carbon atoms which may contain a hetero atom, and specific examples include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, 9-anthrylthio group, 9-phenanthrylthio group, 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group Group, 3-carbazolylthio group, 4-carbazolylthio group and the like can be mentioned, but not limited thereto.

The amino group in the present invention, an amino group having a total carbon number of 0-50 is preferable, -NH _2, N- alkylamino group, N- arylamino group, N- acylamino group, N- sulfonylamino group, N, N -Dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like can be mentioned. More specifically, amino group, methylamino group, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, di (sec-butyl) amino group, di (tert-butyl) amino group , Dipentylamino group, diisopentylamino group, dineopentylamino group, di (tert-pentyl) amino group, dihexylamino group, diisohexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group Diundecylamino group, didodecylamino group, ditridecyl group, ditetradecylamino group, dipentadecylamino group, dihexadecylamino group, diheptadecylamino group, dioctadecylamino group, dinonadecylamino group, diphenyl Amino group, dipentalenylamino group, diindenylamino group Dinaphthylamino group, diazurenylamino group, diheptarenylamino group, difluorenylamino group, dianthrylamino group, diphenanthrylamino group, dipyrenylamino group, dinaphthacenylamino group, methylethylamino group , Methylpropylamino group, methylbutyl group, methylpentylamino group, methylhexylamino group, ethylpropylamino group, ethylbutylamino group, ethylpentylamino group, ethylhexylamino group, propylbutylamino group, propylpentylamino group, propylhexyl Amino group, butylheptylamino group, butylhexylamino group, pentylhexylamino group, phenylnaphthylamino group, phenylanthrylamino group, phenylphenanthrylamino group, naphthylanthrylamino group, naphthylphenane Tolylamino group, methylphenylamino group, methylnaphthylamino group, methylanthrylamino group, methylphenanthrylamino group, ethylphenylamino group, ethylnaphthylamino group, ethylanthrylamino group, ethylphenanthrylamino group, propyl Phenylamino group, propylnaphthylamino group, propylanthrylamino group, propylphenanthrylamino group, butylphenylamino group, butylnaphthylamino group, butylanthrylamino group, butylphenanthrylamino group, pentylphenylamino group, Pentylnaphthylamino group, pentylanthrylamino group, pentylphenanthrylamino group, hexylphenylamino group, hexylnaphthylamino group, hexylanthrylamino group, hexylphenanthrylamino group, Tilphenylamino group, heptylnaphthylamino group, heptylanthrylamino group, heptylphenanthrylamino group, octylphenylamino group, octylnaphthylamino group, octylanthrylamino group, octylphenanthrylamino group, etc. It is not limited to these.

  The acyl group in the present invention may contain a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 30 carbon atoms is bonded, or a hetero atom. Examples thereof include a carbonyl group to which a monocyclic or condensed polycyclic aromatic group having 4 to 18 carbon atoms is bonded, and they may have an unsaturated bond in the structure. Specific examples thereof include a formyl group, an acetyl group, Propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, Oleoyl group, benzoyl group, 1-naphthoyl group, 2 Naphthoyl group, cinnamoyl group, 3-furoyl, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, 9-Ansuroiru group, 5-Nafutasenoiru although groups include and the like, but is not limited thereto.

  The alkyl group, alkenyl group, aryl group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, amino group, and acyl group described above may be further substituted with one or more other substituents, Such substituents include hydroxyl group, mercapto group, cyano group, nitro group, halogen atom, alkyl group, alkenyl group, aryl group, acyl group, alkoxyl group, aryloxy group, amino group, alkylthio group, arylthio group. And an acyloxy group.

  The halogen atom, alkyl group, alkenyl group, aryl group, acyl group, alkoxyl group, aryloxy group, amino group, alkylthio group, and arylthio group mentioned here are the same as the substituents exemplified above. Can do.

  The acyloxy group is a hydrogen atom or a carbonyloxy group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 30 carbon atoms is bonded, or a carbon number which may contain a hetero atom. Examples thereof include a carbonyloxy group having 4 to 30 monocyclic or condensed polycyclic aromatic groups bonded thereto, and specific examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, and an isovaleryloxy group. Group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, Oreo Ruoxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group, 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anth Examples include a royloxy group and a 5-naphthacenoyloxy group.

Further, the substituents R ¹ and R ² , R ¹ and R ⁵ , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ in the general formula [1] are bonded to form a ring structure. May be.

 With the antistatic agent of the present invention, not only a high level of antistatic function, but also the mechanism that can be obtained in combination with colorless transparency, solubility in resins and solvents (compatibility), heat resistance and moisture resistance is completely clear However, the structure in which the charge is dispersed or delocalized in both the anion site and the cation site not only stabilizes, but also promotes dissociation and improves ionic conductivity, and high antistatic performance. I think it will lead to

In view of stability of the compound and ease of synthesis, the substituent R ¹ in the general formula [1] is preferably a hydrogen atom, a halogen atom, an alkoxyl group which may have a substituent, or a substituent. An aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, and an amino group which may have a substituent are preferable. Furthermore, from the viewpoint of obtaining high antistatic performance and heat resistance, an alkoxyl group which may have a substituent and an aryl which may have a substituent, which can disperse a cationic charge with an electron donating property. An oxy group, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, and an amino group which may have a substituent are most preferable.
Although the representative example of a compound represented by General formula [1] of this invention is illustrated below, this invention is not limited to the following representative examples.

  The antistatic agent of the present invention is characterized by comprising an amidinium cation and a thiocyanate anion, but the synthesis method is not particularly limited. Usually, a salt (A) consisting of an amidinium cation and an arbitrary anion and a salt (B) consisting of a thiocyanate anion and an arbitrary cation are separately synthesized and exchanged in water or an organic solvent. By doing so, it is possible to easily obtain the antistatic agent of the present invention.

 The synthesis method for obtaining the salt (A) comprising an amidinium cation and an arbitrary anion is not particularly limited, and any known method can be used. For example, the following documents can be cited.

 Journal of Organic Chemistry, 73 (7), 2731 (2008), Tetrahedron Letters, 49 (3), 449 (2008), Journal of Organic Chemistry, 73 (1), 133 (2008), Organic Letters, 9 (22) , 4475 (2007), Inorganic Chemistry Communications, 9 (10), 996 (2006), Journal of the American Chemical Society, 128 (43), 14185 (2006), Tetrahedron, 61 (51), 12033 (2005), PCT Int. Appl., 2005075413, 18 Aug 2005, Chemistry--A European Journal, 11 (6), 1833 (2005), PCT Int.Appl., 2005007634, 27 Jan 2005, Bioorganic & Medicinal Chemistry, 11 (19), 4179 (2003), Chemical Research in Chinese Universities, 20 (1), 46 (2004), Journal of the Indian Institute of Science, 81 (2), 111 (2001), Inorganic Chemistry, 40 (27), 6964 (2001) ), Synthetic Communications, 28 (7), 1223 (1998), Journal of the American Chemical Society, 117 (19), 5401 (1995), Tetrahedron, 42 (24), 6645 (1986), Zhurnal Organicheskoi Khimii, 17 ( 1), 180 (1981)

 Pharmaceutical Chemistry Journal, 39 (9), 476 (2005), Synthesis, (6), 917 (2008), Tetrahedron Letters, 48 (48), 8526 (2007), Bulletin of the Chemical Society of Japan, 80 (6) , 1187 (2007), European Journal of Organic Chemistry, (22), 3746 (2007), Faming Zhuanli Shenqing Gongkai Shuomingshu, 1974547, 06 Jun 2007, Transition Metal Chemistry (Dordrecht, Netherlands), 31 (5), 611 (2006 ), PCT Int. Appl., 2005075413, 18 Aug 2005, Inorganic Chemistry, 44 (6), 1704 (2005), Faming Zhuanli Shenqing Gongkai Shuomingshu, 1491939, 28 Apr 2004, Green Chemistry, 5 (3), 347 (2003) ), Tetrahedron Letters, 45 (9), 2013 (2004), Inorganic Chemistry, 41 (23), 6118 (2002), Tetrahedron Letters, 42 (14), 2735 (2001), Journal of Organic Chemistry, 65 (23) , 7770 (2000), Journal of Organic Chemistry, 62 (12), 4200 (1997), Liebigs Annalen der Chemie, (9), 1804 (1985), Liebigs Annalen der Chemie, (1), 108 (1984)

e-EROS Encyclopedia of Reagents for Organic Synthesis, No pp. given; 2001, Journal of Organic Chemistry, 73 (7), 2731 (2008), European Journal of Organic Chemistry, (22), 3746 (2007), Tetrahedron, 56 (43), 8567 (2000), Liebigs Annalen der Chemie, (12), 2123 (1986)
Chemistry of Heterocyclic Compounds (New York, NY, United States), 42 (8), 1078 (2006), Journal of Organic Chemistry, 72 (13), 5001 (2007), Organometallics, 25 (7), 1831 (2006) , Tetrahedron, 57 (47), 9607 (2001), Letters in Peptide Science, 7 (5), 291 (2001), Russian Journal of General Chemistry (Translation of Zhurnal Obshchei Khimii), 71 (11), 1759 (2001) , Zhurnal Obshchei Khimii, 62 (7), 1498 (1992), USSR, 1100882, 30 Aug 1985, Archiv der Pharmazie (Weinheim, Germany), 319 (5), 451 (1986), Zhurnal Organicheskoi Khimii, 21 (7) , 1513 (1985), Khimiya Geterotsiklicheskikh Soedinenii, (8), 1044 (1983), Khimiya Geterotsiklicheskikh Soedinenii, (7), 917 (1981), Archiv der Pharmazie (Weinheim, Germany), 314 (5), 413 (1981) Tetrahedron, 36 (18), 2675 (1980), Bulletin de la Societe Chimique de France, (3-4, Pt. 2), 165 (1979)

 In addition to the above-mentioned documents, it is possible to obtain a large number of documents related to synthesis by searching chemical databases such as STN. A salt (A) consisting of the anion can be obtained.

 The synthesis method for obtaining a salt (B) comprising a thiocyanate anion and an arbitrary cation is not particularly limited. As an inexpensive reagent, it can be easily obtained in the form of sodium salt, potassium salt or the like.

  The antistatic agent represented by the general formula [1] of the present invention can be used alone or in combination of two or more.

  As a method of applying the antistatic agent represented by the general formula [1] of the present invention to a resin molded article, a method of molding a resin in which an antistatic agent is directly blended (kneaded), and an antistatic agent on the surface of the molded resin There are two main methods for forming a coating film (film) of the agent.

  First, a method for modeling a resin in which an antistatic agent is directly blended (kneaded) will be described. For modeling, a resin composition containing an antistatic agent and a resin, a resin varnish containing a resin composition (an antistatic agent and a resin) and a solvent, or the like can be used.

  Examples of the resin that can be blended (kneaded) with the antistatic agent represented by the general formula [1] of the present invention include thermoplastic resins, thermosetting resins, fluororesins, and polymer rubbers.

  Examples of the thermoplastic resin include polyolefin, polyhaloolefin, polystyrene, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyhexamethylene terephthalate, polyamide resin, polyvinyl alcohol, polyetherimide resin, polyarylate resin, polysulfone resin, Polyamideimide resin, polyvinyl butyral, acrylic resin, methacrylic resin, norbornene resin, polyimide resin, polyether ether ketone, ketone resin, polycarbonate, polyvinyl formal, polymethyl methacrylate, polyphenylene ether resin, polyvinyl acetate, polyacetal resin, polyphenylene sulfide resin , Ethylene-vinyl alcohol copolymer, acrylonitrile-styrene copolymer (A ), Ethylene - vinyl acetate copolymer (EVA), acrylonitrile - butadiene - styrene copolymer (ABS) and the like.

  Examples of the polyolefin include low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), ethylene-propylene copolymer, polybutadiene, polyisoprene and the like.

  Examples of the polyhaloolefin include polyvinyl chloride (PVC), polychloroprene, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, vinyl chloride-vinylidene chloride copolymer, and the like.

  Thermosetting resins include silicone resin, melamine resin, phenol resin, polyurethane resin, furan resin, diallyl phthalate resin, urea resin, rosin modified maleic acid resin, rosin modified phenolic resin, epoxy resin, xylene resin, polylactic acid resin, Examples include guanamine resins, vinyl ester resins, polyimide resins, unsaturated polyester resins, and the like.

  Examples of the fluororesin include tetrafluoroethylene, polyvinylidene fluoride, and trifluoroethylene.

  Examples of the polymer rubber include natural rubber (NR), styrene butadiene rubber (SBR), ethylene-propylene-diene rubber (EPDM), polyisoprene rubber, chloroprene rubber, polybutadiene rubber, butyl rubber, acrylonitrile-butadiene rubber, and silicone rubber. It is done.

  Furthermore, what is called a polymer alloy combining these resins may be used.

  Moreover, as a method of kneading these, any commonly used method can be used. For example, it is possible to knead by roll kneading, bumper kneading, an extruder or a kneader.

  By shaping the kneaded resin composition into an arbitrary shape, a resin shaped product having antistatic ability can be produced.

  The antistatic agent represented by the general formula [1] of the present invention can be blended with a resin and a solvent and used as a resin varnish. In this case, the above-mentioned resins can be used as the resin. Preferably, acrylic resin, methacrylic resin, polyimide resin, polyamide resin, polyacrylate resin, unsaturated polyester resin, polyester acrylate resin, polyepoxy acrylate resin, polyurethane acrylate resin, polyether acrylate resin, polyol acrylate Resin, cellulose acetate resin, nitrocellulose resin, styrene (co) polymer, polyvinyl butyral resin, amino alkyd resin, polyester resin, amino resin modified polyester resin, polyurethane resin, acrylic polyol urethane Resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, hydroxyethyl cellulose, styrene Water-soluble salts of acrylate-based copolymers, water-soluble salts of (meth) acrylic ester-based (co) polymers, water-soluble amino alkyd resins, water-soluble amino polyester resins, water-soluble polyamide resins, petroleum Resins, alkyd resins, soybean oil, tung oil, and linseed oil can be used. Furthermore, these can be used individually or in combination of 2 or more types.

  As the solvent in the varnish, various solvents can be used in accordance with the properties of the resin such as a high boiling point petroleum solvent, an aliphatic hydrocarbon solvent, an alcohol solvent, and an aqueous solvent. Commonly used solvents include methyl ethyl ketone (MEK), dimethylformamide (DMF), N-methylpyrrolidone (NMP), methoxypropanol, toluene, water and the like. Further, these solvents can be arbitrarily used alone or in combination of two or more.

  For example, a resin shaped article having an antistatic ability can also be produced by applying the resin varnish on an appropriate support and drying it.

  Drying and curing of the applied resin varnish is appropriately selected depending on the solvent to be combined and can be dried at room temperature, but usually it is often performed using a heating and drying furnace. The drying furnace is preferably filled with air, an inert gas (nitrogen, argon, etc.), or the inert gas is preferably flowed into the drying furnace. The drying and curing temperatures are appropriately selected according to the boiling point of the solvent, but are preferably in the range of 60 ° C to 600 ° C. In addition, it is preferable to raise the temperature stepwise because a molded resin product having a uniform film thickness and excellent dimensional stability can be obtained without causing problems such as foaming and crushed skin. The drying and curing time is appropriately selected depending on the thickness of the resin molded product to be formed, the solid content concentration of the resin varnish, and the type of the solvent, and is preferably about 0.05 to 500 minutes.

  In the resin composition and the resin varnish, the amount of the antistatic agent added to the resin is not particularly limited. However, if blended in a large amount, it may affect the original physical properties of the resin, such as a decrease in physical properties such as mechanical strength, and if the blended amount is small, the antistatic effect may be insufficient. Therefore, the preferable blending amount is 0.01 to 30% by weight, more preferably 0.02 to 25% by weight, and most preferably 0.02 to 20% by weight based on the resin.

  Next, a method for forming a coating film of an antistatic agent on the surface of the shaped resin will be described. For forming the coating film, a coating liquid containing an antistatic agent and a solvent can be used in addition to the resin composition and the resin varnish.

  For example, in the case of using a coating liquid, as a coating method for forming a coating film on the surface of a molded resin, a solution, dispersion, or emulsion containing the antistatic agent according to the present invention is immersed, spin-coated, sprayed. There are methods using various means such as a method, a roller coating method, a gravure coating method, a die coating method, a comma coating method, a roll coating method, a curtain coating method, and a bar coating method. These methods can be appropriately used depending on the thickness, viscosity, and the like to be applied.

  The solvent used at this time is not particularly limited as long as it can dissolve or disperse the antistatic agent, but ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; ethylene glycol monomethyl (Poly) alkylene glycol monoalkyl ether acetates such as ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether Ter, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di Propylene glycol mono-n-butyl ether, (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and tripropylene glycol monoethyl ether; ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, ethyl butyrate, isopropyl butyrate , Butyl butyrate, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-oxypropion Acid methyl, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-oxyp Methyl lopionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropion Ethyl acetate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-methoxy-2-methylpropionate, methyl pyruvate , Esters such as ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene, N-methylpyrrolidone, N , N-dimethylacetamide, etc. And the like.

  These solvents can be used alone or in admixture of two or more.

  Furthermore, the quantity which mix | blends the antistatic agent shown by General formula [1] of this invention with these solvents is not specifically limited. However, when blended in a large amount, the viscosity of the coating solution may become too high, or the coating solution may be whitened or colored. Therefore, a preferable blending amount is 0.01 to 30% by weight, more preferably 0.02 to 15% by weight, and most preferably 0.02 to 10% by weight with respect to the entire coating liquid.

  The antistatic agent represented by the general formula [1] of the present invention, a compound having a polymerizable functional group (monomer, oligomer or prepolymer) and a polymerization initiator can be mixed and used as a polymerizable composition. It is. As a method of using the polymerizable composition, according to the form of the polymerizable composition, a method for producing a resin shaped article by polymerizing the polymerizable composition, and using the polymerizable composition on the surface of the shaped resin Both methods of forming an antistatic agent coating film can be taken. That is, when the polymerizable composition is applied to a resin substrate or the like and cured, it corresponds to the latter method, and when it is cured with the polymerizable composition alone, it corresponds to the former method.

  The polymerizable composition comprises at least an antistatic agent, a monomer, oligomer or prepolymer having a polymerizable functional group, and a polymerization initiator.

  Examples of monomers having a polymerizable functional group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethoxylation 1 , 6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol Diacrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl 1,3-propanediol diacrylate, dimethyloltricyclodecane diacrylate, neopentyl glycol diacrylate hydroxypivalate, 1,3-butylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, Propoxylated bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol dicyclopentane diacrylate, trimethylolpropane triacrylate, hydroxypivalic acid trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, Propoxylated trimethylolpropane triacrylate, ethoxylated phosphate triacrylate, ethoxylated tripropylene glycol diacrylate Acrylate, neopentyl glycol modified trimethylolpropane diacrylate, stearic acid modified pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylolpropane triacrylate, tetramethylol methane triacrylate, pentaerythritol tetraacrylate, caprolactone modified trimethylolpropane triacrylate, Ethoxylated isocyanuric acid triacrylate, tri (2-hydroxyethyl isocyanurate) triacrylate, propoxylate glyceryl triacrylate, tetramethylol methane tetraacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate Dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylol Propane oligoacrylate, pentaerythritol oligoacrylate, 2-phenoxyethyl acrylate, acryloylmorpholine, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, isobol Nyl acrylate, cyclohexyl acrylate, 2-methyl Xylethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, benzyl acrylate, ethoxyethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, methyl Phenoxyethyl acrylate, dipropylene glycol acrylate, β-carboxyl ethyl acrylate, phenoxy diethylene glycol acrylate, vinyl caprolactam, vinyl pyrrolidone, N-vinyl formamide, ethyl diglycol acrylate, trimethylolpropane formal monoacrylate, 4-t-butylcyclohexyl Chryrate, tri (meth) allyl isocyanurate, imide acrylate, isoamyl acrylate, ethoxylated succinic acid acrylate, caprolactone modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, trifluoroethyl acrylate, ω-carboxypoly Examples include caprolactone monoacrylate. Furthermore, edited by Shinzo Yamashita et al., "Crosslinking agent handbook" (1981, Taiseisha), Kiyoto Kato, "UV / EB curing handbook (raw material)", (1985, Polymer publication society), Radtech. Study Group, “Application and Market of UV / EB Curing Technology”, Item 79, (1989, CMC), Akamatsu Kiyoshi, “Practical Technology of New Photosensitive Resin”, (1987, CMC), Commercially available products described in Teiyama Shinichiro, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun) or cross-linkable monomers known in the industry can be mentioned, but the present invention is not limited thereto.

  Examples of oligomers and prepolymers include “Ebecryl 230, 244, 245, 270, 280 / 15IB, 284, 285, 4830, 4835, 4858, 4883, 8402, 8803, 8800, 254, 264, 265, manufactured by Daicel UCB. 294 / 35HD, 1259, 1264, 4866, 9260, 8210, 1290, 1290K, 5129, 2000, 2001, 2002, 2100, KRM7222, KRM7735, 4842, 210, 215, 4827, 4849, 6700, 6700-20T, 204, 205, 6602, 220, 4450, 770, IRR567, 81, 84, 83, 80, 657, 800, 805, 808, 810, 812, 1657, 1810, IRR302, 450, 670, 30, 835, 870, 1830, 1870, 2870, IRR267, 813, IRR483, 811, 436, 438, 446, 505, 524, 525, 554W, 584, 586, 745, 767, 1701, 1755, 740 / 40TP, 600, 601, 604, 605, 607, 608, 609, 600 / 25TO, 616, 645, 648, 860, 1606, 1608, 1629, 1940, 2958, 2959, 3200, 3201, 3404, 3411, 3412, 3415, 3500, 3502, 3600, 3603, 3604, 3605, 3608, 3700, 3700-20H, 3700-20T, 3700-25R, 3701, 3701-20T, 3703, 3702, RDX63182, 6040, IR 419 ”, manufactured by Sartomer“ CN104, CN120, CN124, CN136, CN151, CN2270, CN2271E, CN435, CN454, CN970, CN971, CN972, CN9782, CN981, CN9873, CN991 ”L871 , LR8986, PE56F, PE44F, LR8800, PE46T, LR8907, PO43F, PO77F, PE55F, LR8967, LR8981, LR8982, LR8992, LR9004, LR8956, LR8985, LR8987, UP35D, UA19T, F83L63 , LR8869, LR8889, LR8997, R8996, LR9013, LR9019, PO9026V, PE9027V, manufactured by Cognis, "Photomer 3005, 3015, 3016, 3072, 3982, 3215, 5010, 5429, 5430, 5432, 5662, 5806, 5930, 6008, 6010, 6019, 6184, 6210, 6217, 6230, 6891, 6892, 6893-20R, 6363, 6572, 3660, manufactured by Negami Kogyo Co., Ltd., "Art Resin UN-9000HP, 9000PEP, 9200A, 7600, 5200, 1003, 1255, 3320HA, 3320HB, 3320HC, 3320HS, 901T, 1200TPK, 6060PTM, 6060P ", manufactured by Nippon Synthetic Chemical Co., Ltd.," purple light UV-6630B, 7000B, 7510B, 746 " 1TE, 3000B, 3200B, 3210EA, 3310B, 3500BA, 3520TL, 3700B, 6100B, 6640B, 1400B, 1700B, 6300B, 7550B, 7605B, 7610B, 7620EA, 7630B, 7640B, 2000B, 2010B, 2250EA, 2750B, Nippon Kayaku “Kayarad R-280, R-146, R131, R-205, EX2320, R190, R130, R-300, C-0011, TCR-1234, ZFR-1122, UX-2201, UX-2301, UX3204, UX-3301, UX-4101, UX-6101, UX-7101, MAX-5101, MAX-5100, MAX-3510, UX-4101 "and the like. The present invention is not limited to these.

  The compounds having a polymerizable functional group can be used alone or in combination of two or more. The compounding amount of the compound having a polymerizable functional group is preferably 70 to 99.5% by weight, more preferably 75 to 99% by weight, and most preferably 80 to 99% by weight with respect to the entire polymerizable composition. .

  Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure Cure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, Irgacure 261, Irgacure OXE-01 (CGI124), CGI242 (Ciba Specialty Chemicals), Adekaoptomer N1414, Adekaoptomer N1717 (Asahi) Denka), Esacure 1001M (Lamberti), Lucillin TPO (BASF), DidoCure 174 (Daido Kasei), Special public Triazine derivatives described in Japanese Patent Publication Nos. 59-1281, 61-9621 and 60-60104, and organic peroxides described in Japanese Patent Publication Nos. 59-1504 and 61-243807. JP-A-43-23684, JP-B-44-6413, JP-B-47-1604, and US Pat. No. 3,567,453, diazonium compound gazettes, USP 2,848,328, USP 2,852,379. And organic azide compounds described in US Pat. No. 2,940,853, ortho-quinonediazides described in Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37-13109, Japanese Patent Publication No. 38-18015, and Japanese Patent Publication No. 45-9610. JP-B-55-39162, JP-A-59- Various onium compounds including iodonium compounds described in Japanese Patent No. 40203 and “MACROMOLECULES”, Vol. 10, page 1307 (1977), azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 1099851, European Patent No. 126712, “Journal of Imaging Science (J. IMAGE. SCI.)”, Volume 30, page 174 ( 1986), titanocenes described in JP-A-61-151197, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, pages 85-277 (1988) and Transition metal complexes containing a transition metal such as ruthenium described in Kaihei 2-182701, aluminate complexes described in JP-A-3-209477, borate compounds described in JP-A-2-157760, and JP 2,4,5-triarylimidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5 ′ described in JP-A No. 55-127550 and JP-A-60-202437 -Tetraphenyl-1,1'-biimidazole, carbon tetrabromide and organic halogen compounds described in JP-A-59-107344, JP-A-5-213861, JP-A-5-255347, JP-A-5 JP-A-255421, JP-A-6-157623, JP-A-2000-344812, JP-A-2002-265512, and Japanese Patent Application 2004. -053009 and the sulfonium complex or oxosulfonium complex described in Japanese Patent Application No. 2004-263413, JP-A-2001-264530, JP-A-2001-261661, JP-A-2000-80068, JP-A-2001-2001 No. 233842, USP 3558309 (1971), USP 4202697 (1980), JP-A-61-2558, JP-T 2004-534797, and JP-A 2004-359639 Examples thereof include ester compounds and bifunctional photoinitiators described in JP-T-2002-530372, but the present invention is not limited thereto. A polymerization initiator can be used individually or in combination of 2 or more types.

  In addition, by adding a sensitizer that absorbs ultraviolet to near-infrared light to the polymerizable composition, the activity for light from the ultraviolet to the near-infrared region is increased, and an extremely sensitive polymerizable composition. Can be a product.

  Examples of such sensitizers include benzophenones, unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, and fluorene derivatives. , Naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives , Indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, Trabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, Spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes and the like. Other specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al. Examples include, but are not limited to, the dyes and sensitizers described in “Chemicals of Functional Dyes” (1981, CMC), edited by Tadaburo Ikemori, “Special Functional Materials” (1986, CMC). Not shall. Other examples include dyes and sensitizers that absorb light in the ultraviolet to near infrared region. Two or more of these may be used in any ratio as required. Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-bis. (Diethylamino) benzophenone and the like can be mentioned. Examples of coumarins include coumarin 1, coumarin 338 and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylamino). Marine) and the like can be mentioned, but not limited thereto.

  The blending amount of the polymerization initiator and the sensitizer used in the present invention is not particularly limited, but the total amount thereof is preferably 0 to 20% by weight of the whole polymerizable composition, more preferably 0.1%. It is in the range of ˜15% by weight.

  The amount of the antistatic agent of the present invention blended in the polymerizable composition is not particularly limited. However, if blended in a large amount, it may take a long time to cure, and may affect curing properties such as being unable to cure completely. Therefore, the preferable blending amount is 0.01 to 30% by weight based on the entire polymerizable composition, more Preferably it is 0.02-25 weight%, Most preferably, it is 0.02-20 weight%.

  In addition, a polymerization inhibitor can be added to the polymerizable composition of the present invention for the purpose of preventing polymerization during storage.

  Specific examples of the polymerization inhibitor that can be added include hydroquinone, N-nitroso-N-phenylhydroxylamine aluminum, cuperone, p-methoxyphenol, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, phenothiazine, and the like. . The addition amount of the polymerization inhibitor is not particularly limited, but is preferably used in the range of 0.01 to 5% by weight in the polymerizable composition.

  Furthermore, in the polymerizable composition of the present invention, a polymerization accelerator represented by amine, thiol, disulfide or the like or a chain transfer catalyst can be added for the purpose of further promoting the polymerization.

  Specific examples of the polymerization accelerator and chain transfer catalyst that can be added to the polymerizable composition of the present invention include, for example, trimethylamine, methyldimethanolamine, N-phenylglycine, triethanolamine, N, N-diethylaniline and the like. Amines, thiols described in USP No. 4414312 and JP-A 64-13144, disulfides described in JP-A-2-291561, USP 3558322 and JP-A 64-17048 And the O-acylthiohydroxamates and N-alkoxypyridinethiones described in JP-A-2-291560. The addition amount of the polymerization accelerator and the chain transfer catalyst is not particularly limited, but is preferably used in the range of 0.001 to 5% by weight in the polymerizable composition.

  The polymerizable composition in the present invention can be polymerized by applying energy by ultraviolet rays, visible rays, near infrared rays, electron beams or the like to obtain a desired polymer. The definitions of ultraviolet rays, visible rays, near-infrared rays and the like in this specification are based on “Iwanami Rikagaku Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

  Therefore, the polymerizable composition of the present invention includes a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an argon ion laser, a helium cadmium laser, and helium. Neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, plasma light source, electron beam, gamma ray, ArF excimer laser, KrF excimer laser, F2 laser, etc. A polymer (cured product) can be obtained.

  When using the antistatic agent represented by the general formula [1] in the present invention, other antistatic agents, pigments, colorants, antioxidants, ultraviolet absorbers, reinforcing agents, weathering agents, lubricants are used as necessary. It is also possible to simultaneously add additives such as an antiblocking agent, a plasticizer, a fragrance, an inorganic electrolyte, a foaming agent, a flame retardant, a filler, and a surface conditioner.

  Other antistatic agents that may be incorporated in the present invention include glycerin monofatty acid ester, polyglycerin fatty acid ester, diethanolamine fatty acid amide, polyalkylene glycol alkyl ether, N-alkyl ammonium chloride, metal fine particles, metal oxide (ITO , FTO, ATO, etc.) and the like, and the addition of an antistatic agent represented by the following general formula [2] is particularly preferable.

General formula [2]

(In the formula, each of R ^{11 to} R ¹⁴ may independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Represents an aryl group, and R ^{11 to} R ¹⁴ may combine with each other to form a ring, and A ⁺ represents an onium cation.)
Here, the alkyl group which may have a substituent, the alkenyl group which may have a substituent, and the aryl group which may have a substituent are represented by R ^{1 to} R ⁵ in the general formula [1]. It is synonymous with what has been described.

  The onium cation is not particularly limited, but ammonium, quinolinium, isoquinolinium, pyridinium, imidazole, thiazole, oxazole, benzimidazole, benzothiazole, benzoxazole, phosphonium, sulfonium, sulfoxonium, iodonium, iodoxonium, Examples include oxonium, pyrylium, pyrazinium, and the like, which may have a substituent.

  Representative examples of the antistatic agent represented by the general formula [2] are specifically exemplified as exemplified compounds (101) to (182) below, but are not limited thereto. In the exemplified compounds, Me represents a methyl group, Et represents an ethyl group, Pr represents a normal propyl group, Bu represents a normal butyl group, Hex represents a normal hexyl group, Cet represents a normal cetyl group, and Ph represents a phenyl group.

 The addition amount of the antistatic agent represented by the general formula [2] is preferably 1 part by weight to 5000 parts by weight with respect to 100 parts by weight of the antistatic agent represented by the general formula [1] of the present invention. .

  Examples of pigments that may be blended in the present invention include carbon black, iron oxide, calcium carbonate, titanium oxide, zinc oxide, cadmium yellow, nickel titanium yellow, strontium chromate, Prussian blue, and other inorganic pigments, azo pigments, and indigo pigments. Organic pigments such as phthalocyanine pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, diketopyrrolopyrrole pigments, quinacridone pigments, perylene pigments, indanthrone pigments, perinone pigments and dioxazine pigments.

  Examples of the antioxidant that may be blended in the present invention include 2,6-di-tert. -Butylphenol (hereinafter, tert.-butyl is abbreviated as "t-butyl"), 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol 2,4-dimethyl-6-tert-butylphenol, 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4 , 4'-bis (2-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-) Butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-isopropylidenebis (2,6-di-tert-butylphenol), 2,2′-methylenebis ( -Methyl-6-cyclohexylphenol), 2,2'-methylenebis (4-methyl-6-nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,6-bis (2 '-Hydroxy-3'-t-butyl-5'-methylbenzyl) 4-methylphenol, 3-t-butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole, 3- (4-hydroxy -3,5-di-t-butylphenyl) stearyl propionate, oleyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-3,5-di-) -T-butylphenyl) dodecylpropionate, octyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, tetrakis {3- ( -Hydroxy-3,5-di-t-butylphenyl) propionyloxymethyl} methane, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid glycerin monoester, 3- (4-hydroxy -3,5-di-t-butylphenyl) propionic acid and glycerol monooleyl ether, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid butylene glycol ester, 3- ( 4-hydroxy-3,5-di-t-butylphenyl) propionic acid thiodiglycol ester, 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-thiobis (2-methyl) -6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl Til-α-dimethylamino-p-cresol, 2,6-di-t-butyl-4 (N, N′-dimethylaminomethylphenol), bis (3,5-di-t-butyl-4-hydroxybenzyl) ) Sulfide, tris {(3,5-di-t-butyl-4-hydroxyphenyl) propionyl-oxyethyl} isocyanurate, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, 1, 3,5-tris (3 ′, 5′-di-t-butyl-4-hydroxybenzoyl) isocyanurate, bis {2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl ) Sulfide, 1,3,5-tris (4-di-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetraph Royl-di (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl sulfide), 6- (4-hydroxy-3,5-di-tert-butylanilino) -2,4-bis (octylthio)- 1,3,5-triazine, 2,2-thio- {diethyl-bis-3- (3,5-di-tert-butyl-4-hydroxyphenyl)} propionate, N, N'-hexamethylenebis (3 , 5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxy-benzyl-phosphate diester, bis (3-methyl-4-hydroxy-5-t- Butylbenzyl) sulfide, 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8, 1 -Tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6- Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis {3,3′-bis- (4′-hydroxy-3′-tert-butylphenyl) butyric acid} glycol ester, tri Phenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4,4-butylidenebis (3-methyl-6-t-butylphenyl diisotridecyl) phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol di Phosphite, Tris (nonylphenyl) phosphite, Tris (Dinoni Phenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4 , 6-Di-tert-butylphenyl) octyl phosphite, 1,1,3-butyridine tris (3-methyl-6-tert-butylphenyldiisotridecyl) phosphite, 2,2-propylidenebis (3-methyl) -6-tert-butylphenyldiisotridecyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4-biphenylene-diphosphonite, 9,10-dihydro-9-oxa-10-phospha Phenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, dioctylthiodipropionate, didecylthiodipropionate, dilauryl Thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl-β, β'-thiodibutyrate, (3-octylthiopropionic acid) pentaerythritol tetraester (3-decylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) pentaerythritol tetraester, (3-stearylthiopropionic acid) pentaerythritol tetraester, (3-o (Railthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) -4,4′-thiodi (3-methyl-5-tert-butyl-4-phenol) ester, 2-mercaptobenzimidazole, 2- Examples include mercaptomethylbenzimidazole, 2-benzimidazole disulfide, dilauryl sulfide, amylthioglycol and the like.

  Examples of the ultraviolet absorber that may be blended in the present invention include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-5′-t-butylphenyl) benzo Triazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) benzotriazole, 2- {2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl} benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl)- 5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy- 3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- {2′-hydroxy-3 ′-(3 ″, 4 ", 5", 6 "-tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole, 2,2-methylenebis {4- (1,1,3,3-tetramethylbutyl) -6- (2H- Benzotriazol-2-yl) phenol}, 2- (2′-hydroxy-5′-methacryloxyphenyl) -2H-benzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy -4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4- Toxibenzophenone, 2,2′-dihydroxy-4,4′-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenylmethane), phenyl salicylate , Salicylates such as 4-t-butylphenyl salicylate and 4-octylphenyl salicylate; cyanoacrylates such as ethyl-2-cyano-3,3-diphenyl acrylate and 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate System; oxalic acid systems such as 2-ethoxy-2′-ethyl oxalic acid bisanilide, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2) , 2,6,6-tetramethyl-4-piperidi ) Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1 , 2,3,4-butanetetracarboxylate, (mixed-2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (mixed -1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed- {2,2,6,6-tetramethyl-4- Pipette Lysyl / β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethyl} -1,2,3,4-butane Tetracarboxylate, mixed- {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10- Tetraoxaspiro [5,5] undecane) diethyl} -1,2,3,4-butanetetracarboxylate, poly {6- (1,1,3,3, -tetramethylbutyl) imino-1,3 5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino} Dimethyl succinate / 4-hydroxy-2,2,6 6-tetramethyl-1-piperidine ethanol polymer, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, ethylene bis (2, 2,6,6-tetramethyl-3-oxa-4-piperidine), {2,2′-thiobis (4-t-octylphenolate)}-2-ethylhexylamine nickel (II), nickel dibutyldithiocarbamate, {2,2′-thiobis (4-t-octylphenolate)}-2-butylamine nickel (II), nickel bis (octylphenyl) sulfide, 3,5-di-t-butyl-4-hydroxybenzyl phosphate Nickel-based light stabilizers such as monoethylate nickel complex; 2,4-di-t-butylphenyl-3,5′-di-t-butyl 4'-hydroxybenzoate and the like.

  Examples of the plasticizer that may be blended in the present invention include phthalic acid ester, phosphoric acid ester, polyester, trimellitic acid ester, chlorinated paraffin, dibasic acid ester, and epoxidized ester.

  Examples of the flame retardant that may be blended in the present invention include tetrabromobisphenol A, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, and 2,2-bis (4-hydroxyethoxy-3,5-dibromo. Phenyl) propane, decabromodiphenyl oxide, hexabromocyclodecane, tetrabromophthalic anhydride, chlorinated polyethylene, chlorinated paraffin, perchlorocyclopentadecane, chlorendic acid, tetrachlorophthalic anhydride, ammonium phosphate, tricresyl phosphate , Triethyl phosphate, tris (β-chloroethyl) phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate DOO, red phosphorus, tin oxide, antimony trioxide, zirconium hydroxide, barium metaborate, zinc borate, aluminum hydroxide, magnesium hydroxide, nitrogenated guanidine, and the like.

  As the surface conditioner that may be blended in the present invention, BYK-300 "BYK-300, 302, 306, 307, 310, 315, 320, 322, 323, 325, 330, 331, 333, 337, 340, 344, 370, 375, 377, 350, 352, 354, 355, 356, 358N, 361N, 357, 390, 392, UV3500, UV3510, UV3570, manufactured by Tego Chemie “Tegorad-2100, 2200, 2250, 2500, 2700” Or the like. These surface conditioners may be used alone or in combination of two or more as required.

  In the present invention, the resin molded product includes various films for FPD, conductive rubber, antistatic coating, electronic component package, and the like.

  Next, the present invention will be specifically described using examples, but the present invention is not limited to these examples.

  First, the synthesis example of the compound in this invention is shown below.

Synthesis Example 1 Synthesis of Compound (2) In acetone, 7.40 g of potassium thiocyanate and 10.00 g of (dimethylaminomethylene) dimethylammonium chloride were mixed and stirred at room temperature for about 24 hours. This slurry was filtered, and the solvent of the obtained filtrate was distilled off, followed by drying under reduced pressure to obtain 11.50 g of Compound (2) (yield 98%). Table 1 shows the results of elemental analysis of compound (2) (MT-5 manufactured by Yanagimoto Seisakusho Co., Ltd., the same applies hereinafter).

Synthesis Example 2 Synthesis of Compound (13) In acetone, 5.75 g of potassium thiocyanate and 10.00 g of 2-chloro-1,3-dimethylimidazolinium chloride were mixed and stirred at room temperature for about 24 hours. The slurry was filtered, and the solvent of the obtained filtrate was distilled off, followed by drying under reduced pressure to obtain 10.43 g of Compound (13) (yield 92%). The results of elemental analysis of the compound (13) are shown in Table 1.

Synthesis Example 3 Synthesis of Compound (30) In acetone, 2.14 g of potassium thiocyanate and 10.00 g of 1,1,3,3-tetrabutyl-2-propylisouronium iodide were mixed and about 24 hours at room temperature. Stir. This slurry was filtered, and the solvent of the obtained filtrate was distilled off and dried under reduced pressure to obtain 7.64 g of Compound (30) (yield 90%). The results of elemental analysis of the compound (30) are shown in Table 1.

Synthesis Example 4 Synthesis of Compound (53) In acetone, 2.71 g of potassium thiocyanate and 10.00 g of 4- (methylthio (morpholino) methylene) morpholine-4-ium iodide were mixed and stirred at room temperature for about 24 hours. . This slurry was filtered, and the solvent of the obtained filtrate was distilled off and dried under reduced pressure to obtain 7.11 g of Compound (53) (yield 88%). The results of elemental analysis of the compound (53) are shown in Table 1.

Synthesis Example 5 Synthesis of Compound (57) In acetone, 2.26 g of sodium thiocyanate and 10.00 g of N- (1,3-dimethylimidazolidin-2-ylidene) -N-isopropylbenzeneaminium iodide were mixed. And stirred at room temperature for about 24 hours. This slurry was filtered, and the solvent of the obtained filtrate was distilled off and dried under reduced pressure to obtain 5.66 g of Compound (57) (yield 70%). The results of elemental analysis of the compound (57) are shown in Table 1.

Other Synthesis Examples By carrying out a salt exchange reaction between the corresponding amidinium salt and thiocyanate salt in substantially the same manner as in Synthesis Examples 1 to 5, compounds (3) and (6) which are antistatic agents of the present invention ), (28), (37), (47), (54) and (70) could be obtained. The results of elemental analysis of these compounds are shown in Table 1.

    The amidinium salt used as the raw material for the ion exchange reaction was synthesized with reference to the literature on the synthesis method described above.

Table 1

Example 1
As a UV curable monomer, 1.5 g of purple light UV1700B (manufactured by Nippon Synthetic Chemical Co., Ltd.), as a polymerization initiator, 0.15 g of DidoCure 174 (manufactured by Daido Kasei), and 3 g of PGME (propylene glycol monomethyl ether) as a diluting solvent As an antistatic agent, 0.03 g of compound (2) (resin ratio: 2% by weight) was weighed, mixed, and stirred so that the mixed solution became uniform.

Using the bar coater # 12, the mixed solution was applied onto a PET substrate to form a coating film, and then dried at 100 ° C. for 1 minute. The film was cured by light irradiation (640 mW / cm ² ) using a metal halide lamp. The antistatic ability was evaluated by measuring the surface resistance value of the cured coating film (R8340A manufactured by Advantest Corporation). Thereafter, the surface resistance value (Ω / □) is 10 ¹⁰ units Ω / □ or less, ◎ 10 ¹¹ units Ω / □ value is ○, 10 ¹² units Ω / □ value is △, 10 ¹³ units Ω The value of / □ is shown as ▽, 10 ¹⁴ or more as x. Moreover, it measured also about the total light transmittance (Huga-2B by Suga Test Instruments Co., Ltd.) of the cured coating film.

Examples 2 to 12
The surface resistance value and total light transmittance of the cured coating film were measured in the same manner as in Example 1 except that the compounds shown in Table 2 were used instead of the compound (2).

Example 13
As a UV curable monomer, 1.5 g of purple light UV1700B (manufactured by Nippon Synthetic Chemical Co., Ltd.), as a polymerization initiator, 0.15 g of DidoCure 174 (manufactured by Daido Kasei), and 3 g of PGME (propylene glycol monomethyl ether) as a diluent solvent As an antistatic agent, 0.0297 g of compound (2) and 0.0003 g of compound (109) were weighed and mixed, and stirred so that the mixture became uniform. The surface resistance value and total light transmittance of the film were measured.

Example 14
The surface resistance value and total light transmittance of the cured coating film were measured in the same manner as in Example 13 except that 0.027 g of compound (2) and 0.003 g of compound (109) were used as the antistatic agent.

Example 15
The surface resistance value and total light transmittance of the cured coating film were measured in the same manner as in Example 13 except that 0.024 g of compound (2) and 0.006 g of compound (109) were used as the antistatic agent. .

Example 16
The surface resistance value and total light transmittance of the cured coating film were measured in the same manner as in Example 13 except that 0.015 g of compound (2) and 0.015 g of compound (109) were used as the antistatic agent.

Examples 17-20
The surface resistance value and total light transmittance of the cured coating film were measured in the same manner as in Examples 13 to 16 except that the compound (13) was used instead of the compound (2).

Examples 21-24
The surface resistance value and total light transmittance of the cured coating film were measured in the same manner as in Examples 13 to 16 except that the compound (30) was used instead of the compound (2).

Examples 25-28
The surface resistance value and the total light transmittance of the cured coating film were measured in the same manner as in Examples 13 to 16 except that the compound (53) was used instead of the compound (2).

Examples 29-32
The surface resistance value and total light transmission of the cured coating film were the same as in Examples 13 to 16, except that the compound (57) was used instead of the compound (2) and the compound (101) was used instead of the compound (109). The rate was measured.

Examples 33-44
The surface resistance value and the total light transmittance of the cured coating film were measured in the same manner as in Examples 1 to 12 except that 0.075 g (resin ratio: 5% by weight) of the compound shown in Table 2 was used.

Comparative Example 1
The surface resistance value and the total light transmittance of the cured coating film were determined in the same manner as in Example 1 except that the commercially available antistatic agent light ester DQ-100 (manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of the compound (2). It was measured.

Comparative Example 2
The surface resistance value and total light transmittance of the cured coating film were determined in the same manner as in Example 33 except that a commercially available antistatic agent Light Ester DQ-100 (manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of the compound (2). It was measured.

Comparative Example 3
The surface resistance value and total light transmittance of the cured coating film were determined in the same manner as in Example 1 except that the commercially available antistatic agent Sanconol A400-50R (manufactured by Sanko Chemical Co., Ltd.) was used instead of the compound (2). It was measured.

Comparative Example 4
The surface resistance value and the total light transmittance of the cured coating film were determined in the same manner as in Example 33 except that the commercially available antistatic agent Sanconol A400-50R (manufactured by Sanko Chemical Co., Ltd.) was used instead of the compound (2). It was measured.

  Tables 2 and 3 show the results of Examples 1-44 and Comparative Examples 1-4.

Table 2

Table 3

  When the antistatic agent of this invention was used, sufficient antistatic effect was acquired compared with the commercial item. It was found that even when the values of 2% by weight and 5% by weight were compared, there was no great difference, and even a small amount was effective. When a commercially available antistatic agent was used, the surface resistance of the cured coating film was high, and it did not function as an antistatic agent.

  The total light transmittance of the PET film of the substrate is 89.80%, and when the antistatic agent of the present invention is used, it shows a similar value, so that the material is very transparent. Recognize. On the other hand, in Comparative Example 1 and Comparative Example 2, irregularities considered to be due to the low compatibility of the antistatic agent were observed, and the total light transmittance showed a low value because the scattering component due to them increased.

  When the antistatic agent represented by the general formula [1] in the present invention and the antistatic agent represented by the general formula [2] are mixed, a sufficient antistatic effect is obtained and transparency is maintained. Rather, there was a tendency that transparency was slightly increased by adding a small amount of the general formula [2].

Example 45
A resin varnish was prepared by adding 5 g of the compound (2) as an antistatic agent to 100 g of Aqua 48E (water-soluble alkyd resin manufactured by Showa Varnish Co., Ltd.) and mixing the mixture uniformly. This resin varnish was applied onto a glass substrate using a bar coater # 15 to form a coating film, and dried by heating at 100 ° C. for 45 minutes. As an evaluation of the antistatic ability, the surface resistance value of the coating film was measured.

Examples 46-56
The surface resistance value of the coating film was measured in the same manner as in Example 45 except that the compounds listed in Table 4 were used instead of the compound (2).

Example 57
4.9 g of compound (2) and 0.1 g of compound (109) as antistatic agents are added to 100 g of Aqua 48E (water-soluble alkyd resin manufactured by Showa Varnish Co., Ltd.), and mixed uniformly to obtain a resin varnish. Made. This resin varnish was applied onto a glass substrate using a bar coater # 15 to form a coating film, and dried by heating at 100 ° C. for 45 minutes. As an evaluation of the antistatic ability, the surface resistance value of the coating film was measured.

Example 58
The surface resistance of the coating film was measured in the same manner as in Example 57 except that 4.5 g of compound (2) and 0.5 g of compound (109) were used as the antistatic agent.

Example 59
The surface resistance value of the coating film was measured in the same manner as in Example 57 except that 2.5 g of the compound (2) and 2.5 g of the compound (109) were used as the antistatic agent.

Example 60
The surface resistance value of the coating film was measured in the same manner as in Example 57 except that 0.5 g of compound (2) and 4.5 g of compound (109) were used as the antistatic agent.

Example 61
The surface resistance value of the coating film was measured in the same manner as in Example 57 except that 0.1 g of compound (2) and 4.9 g of compound (109) were used as the antistatic agent.

Examples 62-66
The surface resistance value of the coating film was measured in the same manner as in Examples 57 to 61 except that the compound (13) was used instead of the compound (2).

Comparative Example 5
The surface resistance value of the coating film was measured in the same manner as in Example 45 except that the commercially available antistatic agent Light Ester DQ-100 (manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of the compound (2).

Comparative Example 6
The surface resistance value of the coating film was measured in the same manner as in Example 45 except that the commercially available antistatic agent Dasper 125B (manufactured by Miyoshi Resin Co., Ltd.) was used instead of the compound (2).

Comparative Example 7
The surface resistance value of the coating film was measured in the same manner as in Example 45 except that the commercially available antistatic agent Emulgen 105 (manufactured by Kao Corporation) was used instead of the compound (2).

  The results of Examples 45 to 66 and Comparative Examples 5 to 7 are shown in Table 4.

Table 4

  As can be seen from the results of Table 4, the antistatic agent represented by the general formula [1] of the present invention and the mixture of the general formula [1] and the general formula [2] is blended with an aqueous varnish, It was uniformly dispersed, the surface resistance value was low, and a high antistatic effect was obtained. On the other hand, in the comparative example, the surface resistance value was higher than that in the case of using the antistatic agent of the present invention. Particularly in Comparative Example 7, the antistatic agent could not be uniformly dispersed in the aqueous varnish, and the coating film was whitened.

Example 67
100 g of high density polyethylene (manufactured by Aldrich) and 5 g of compound (2) as an antistatic agent were kneaded at 130 ° C. for 8 hours using a kneader manufactured by Inoue Seisakusho. Further, the kneaded product was extruded using an extrusion molding machine to form a resin plate having a thickness of 5 mm. As an evaluation of the antistatic ability, the surface resistance value of the resin plate was measured. Further, the yellowing of the resin plate was visually evaluated.

Examples 68-78
Instead of the compound (2), the surface resistance value of the resin plate was measured in the same manner as in Example 67 except that the compounds described in Table 5 were used, and yellowing was evaluated.

Comparative Example 8
The surface resistance value of the resin plate was measured in the same manner as in Example 67 except that a commercially available antistatic agent dodecylpyridinium chloride (DPC: manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the compound (2). evaluated.

Comparative Example 9
The surface resistance value of the resin plate was measured in the same manner as in Example 67 except that the commercially available antistatic agent Dasper 125B (manufactured by Miyoshi Resin Co., Ltd.) was used instead of the compound (2), and yellowing was evaluated. .

Comparative Example 10
Instead of the compound (2), the surface resistance value of the resin plate was measured in the same manner as in Example 67 except that a commercially available antistatic agent Emulgen 105 (manufactured by Kao Corporation) was used, and yellowing was evaluated.

  The results of Examples 67 to 78 and Comparative Examples 8 to 10 are shown in Table 5.

Table 5

  As can be seen from the results of Examples 67 to 78, the antistatic agent represented by the general formula [1] of the present invention is highly antistatic even when kneaded with a thermoplastic resin at a high temperature of 130 ° C. for 8 hours. It was found to show the ability. In the resin plate using the antistatic agent represented by the general formula [1] of the present invention, no yellowing was observed.

  On the other hand, in Comparative Examples 8 to 10 tested with a general-purpose antistatic agent, the antistatic effect was not obtained, and yellowing was also observed due to kneading at a high temperature for a long time. In particular, Comparative Example 8 had an unpleasant odor. Gas chromatographic analysis confirmed the odor caused by pyridine, which is a constituent of the antistatic agent.

Example 79
0.5 g of compound (2) was dissolved in 10 g of PGME (propylene glycol monomethyl ether), and the solution was applied onto a 100 μm PET film using a spin coater and dried at 100 ° C. for 1 minute to form a coating film. As an evaluation of the antistatic ability, the surface resistance value of the coating film was measured.

Examples 80-90
The surface resistance value of the coating film was measured in the same manner as in Example 79 except that the compounds listed in Table 6 were used instead of the compound (2).

Comparative Example 11
The surface resistance value of the coating film was measured in the same manner as in Example 79 except that a commercially available antistatic agent dodecylpyridinium chloride (DPC: manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the compound (2).

Comparative Example 12
The surface resistance value of the coating film was measured in the same manner as in Example 79 except that the commercially available antistatic agent Dasper 125B (manufactured by Miyoshi Resin Co., Ltd.) was used instead of the compound (2).

  Table 6 shows the results of Examples 79 to 90 and Comparative Examples 11 to 12.

Table 6

  As is clear from the results in Table 6, the antistatic agent represented by the general formula [1] in the present invention exhibited a low surface resistance value compared to a general-purpose antistatic agent.

Example 91
As a UV monomer, 5 g of purple light UV1700B (manufactured by Nippon Synthetic Chemical Co., Ltd.), as a polymerization initiator, 0.5 g of DidoCure 174 (manufactured by Daido Kasei), 15 g of ethyl acetate as a diluting solvent, and 0.25 g of compound (2) (Resin ratio 5 wt%) Weighed, mixed and stirred.

Using a bar coater # 12, the mixture was applied onto a PET substrate to form a coating film, and then dried at 100 ° C. for 1 minute. The film was cured by light irradiation using a metal halide lamp (640 mW: cm ² ). The haze value of the cured coating film immediately after curing and the haze value of the cured coating film after storage for one week (25 ° C., 60% RH) were measured.

Examples 92-102
A cured coating film was prepared and the haze value was measured in the same manner as in Example 91 except that the compound shown in Table 7 was used instead of the compound (2).

Comparative Examples 13-15
A cured coating film was prepared and the haze value was measured in the same manner as in Example 91 except that the thiocyanate alkali metal salt compound shown in Table 7 was used instead of the compound (2).

  The results of Examples 91 to 102 and Comparative Examples 13 to 15 are shown in Table 7.

Table 7

  Immediately after curing, all the cured coating films had low haze values and high transparency. However, the cured coating film stored at 25 ° C. and 60% RH for one week showed a value almost equal to that immediately after curing when the antistatic agent represented by the general formula [1] of the present invention was used. On the other hand, when the antistatic agent of the comparative example was used, the haze value increased. When the cured coating film was observed in detail, it was possible to observe irregularities in the cured coating film of the comparative example. Probably, the comparison compound in the coating film is not compatible with the cured resin, so that it may be crystallized.

Example 103
5 g of Aronix M408 (manufactured by Toagosei Co., Ltd.) as the UV curable monomer, 0.5 g of DidoCure 174 (manufactured by Daido Kasei) as the polymerization initiator, 15 g of ethyl acetate as the diluting solvent, and 0 of compound (2) .25 g (resin ratio: 5% by weight) were weighed, mixed and stirred.

Using the bar coater # 12, the mixed solution was applied onto a PET substrate to form a coating film, and then dried at 100 ° C. for 1 minute. The film was cured by light irradiation (640 mW / cm ² ) using a metal halide lamp. The surface resistance value of the cured coating film was measured by changing the humidity conditions.

Examples 104-114
Surface resistance values were measured in the same manner as in Example 103 except that the compounds shown in Table 8 were used instead of the compound (2).

Comparative Examples 16-18
Surface resistance values were measured in the same manner as in Example 103 except that the compounds shown in Table 8 were used instead of the compound (2).

  The results of Examples 103 to 114 and Comparative Examples 16 to 18 are shown in Table 8.

Table 8

When the antistatic agent represented by the general formula [1] of the present invention was used, almost no change in the surface resistance value due to humidity was observed. However, when the antistatic agent of the comparative example was used, the surface resistance value increased as the humidity decreased, and the value was 10 ¹⁴ Ω / □ or more at 35% RH, and did not function as an antistatic agent. .

Example 115
Using a tablet molding machine, pellets of compound (2) were prepared, and the surface resistance value was measured by changing the humidity conditions.

Examples 116-126, Comparative Examples 19-21
The surface resistance value was measured in the same manner as in Example 115 except that the compound shown in Table 9 was used instead of the compound (2).

  The results of Examples 115 to 126 and Comparative Examples 19 to 21 are shown in Table 9.

Table 9

  In the antistatic agent of the present invention shown in Table 9, the surface resistance value was not affected by humidity at all, and showed a favorable value of almost the same in any humidity condition. However, the compound of the comparative example was significantly affected by humidity. Furthermore, the surface resistance value became very large under the condition where the humidity was 35% RH, and it did not function as an antistatic agent.

Examples 127-131
Some of the antistatic agents of the present invention shown in Table 10 were subjected to solubility tests in organic solvents and UV curable monomers.

Comparative Example 22
A solubility test of a commercially available antistatic agent light ester DQ-100 (manufactured by Kyoeisha Chemical Co., Ltd.) in an organic solvent and a UV curable monomer was performed.

  The results of Examples 127 to 131 and Comparative Example 22 are shown in Table 10.

Table 10

  The antistatic agents of the present invention shown in Table 10 were highly soluble in organic solvents and UV curable monomers. On the other hand, the antistatic agent of the comparative example had high solubility in water, low solubility in organic solvents and UV curable monomers, and exhibited almost the opposite properties to the antistatic agent of the present invention.

  Considering the above results comprehensively, the compound group listed in the comparative example is characterized by being easily yellowed. This is thought to be due to the fact that it is composed of organic cations and inorganic anions. Furthermore, since the compound group mentioned in the comparative example has a high surface resistance value and low antistatic ability under low humidity conditions, it is considered that water is greatly involved in the static elimination mechanism. However, since the antistatic agent of the present invention is a salt between organic substances, it is difficult to yellow, and the surface resistance value was not affected by humidity under various conditions.

  Judging from these examples comprehensively, the antistatic agent comprising a combination of a specific cation and a specific anion of the present invention has not only high antistatic ability, but also colorless transparency and solubility in resins and solvents. It is an excellent antistatic agent that has both (compatibility), heat resistance and moisture resistance, has no characteristics of precious metals, heavy metals and metal ions and is colorless even when dissolved in a solvent or resin. It can be said that there is.

Claims (13)

An antistatic agent comprising a compound represented by the following general formula [1].
General formula [1]

(Wherein R ¹ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a substituent; It may have an alkoxyl group that may have, an aryloxy group that may have a substituent, an alkylthio group that may have a substituent, an arylthio group that may have a substituent, or a substituent. Represents a good amino group.
R ^{2 to} R ⁵ are each independently a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an aryl group that may have a substituent, or Represents an acyl group which may have a substituent.
R ¹ and R ² , R ¹ and R ⁵ , R ² and R ³ , R ³ and R ⁴ , and R ⁴ and R ⁵ may be bonded to each other to form a ring structure. )   A resin composition comprising a resin and the antistatic agent according to claim 1.   The resin composition according to claim 2, wherein the resin is a thermoplastic resin and / or a thermosetting resin.   A resin varnish comprising the resin composition according to claim 2 or 3 and a solvent.   A polymerizable composition comprising a compound having a polymerizable functional group, a polymerization initiator, and the antistatic agent according to claim 1.   A method for producing a cured resin having antistatic ability, wherein the polymerizable composition according to claim 5 is cured by light irradiation.   A cured resin product having an antistatic ability produced by the production method according to claim 6.   A coating liquid comprising a solvent and the antistatic agent according to claim 1.   The manufacturing method of the resin molded product which has the antistatic ability formed by apply | coating the coating liquid of Claim 8 to a resin molded product.   A resin shaped article having antistatic ability, produced by the production method according to claim 9.   A resin shaped article having antistatic ability, produced using the resin composition according to claim 2 or 3, the resin varnish according to claim 4, or the polymerizable composition according to claim 5.   An antistatic ability formed by using the resin composition according to claim 2 or 3, the resin varnish according to claim 4, the polymerizable composition according to claim 5, or the coating liquid according to claim 8. Paint film.   A resin shaped article having an antistatic ability, wherein the coating film according to claim 12 is provided on the surface.