JP4055823B1 - Antistatic agent and its use - Google Patents

Abstract

An antistatic agent having not only high antistatic ability but also transparency, solubility in a resin or solvent (compatibility), and heat resistance, and containing no metal or metal ion.
The antistatic agent is a boron salt of a low-molecular quaternary ammonium such as tetraethylammonium tetraphenylborate, octyltrimethylammonium tetraphenylborate, benzyltributylammonium tetrakis (pentafluorophenyl) borate.
[Selection] Figure 1

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. Has characteristics such as low compatibility with polymers.

  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.

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

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

  There is a demand for an antistatic agent having not only the original function as an antistatic agent, but also transparency, solubility in a resin or solvent (compatibility), and heat resistance.

 Furthermore, when a metal filler is used to provide an antistatic function, noble metals or heavy metals may be used. Precious metals are concerned about the problem of depletion of their resources and are expensive. As for heavy metals, there are big problems at the time of disposal, and there are concerns about safety to the human body. Therefore, a material containing no precious metal or heavy metal is desired.

 In the field of electronic products and electronic materials, 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 an electronic material or the like, not only the functions of the ions are deteriorated or destroyed, but also there is a risk of heat generation, ignition, and explosion due to the functions. From such a point of view, it is desirable that materials applied to electronic products and electronic parts do not contain metal ions.

  Therefore, the object of the present invention is to solve these problems, that is, not only high antistatic ability, but also transparency, solubility in resin and solvent (compatibility), heat resistance, moisture resistance, And an antistatic agent containing no metal ions. 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].

(Wherein R ^{1 to} R ⁸ are each independently a hydrogen atom,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium alkyl group which may have a substituent group is a group,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium alkenyl group which may have a substituent group is a group,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium alkynyl group which may have a substituent is a group,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium aryl group which may have a substituent group is a group,

Or, a halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino Group, alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamide group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group Cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, Other represents a heterocyclic group which may have a substituent is triphenyl phenacyl phosphonium group, R ⁵ to R ⁸ adjacent to each other may be bonded to each other to form a ring. )

R ^{1 to} R ⁴ are each independently preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, and each independently has a substituent. It is more preferable that it is a good aryl group. R ^{5 to} R ⁸ are preferably each independently an alkyl group which may have a substituent.

  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.

  Furthermore, other this invention relates to the resin molded article which has the antistatic ability using the said antistatic agent.

  The disclosure of the present application relates to the subject matter described in Japanese Patent Application No. 2007-061143 filed on March 12, 2007 and Japanese Patent Application No. 2007-136082 filed on May 23, 2007. Is hereby incorporated by reference.

  The present invention is characterized by being an antistatic agent comprising a compound represented by the following general formula [1].

(Wherein R ^{1 to} R ⁸ are each independently a hydrogen atom,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium alkyl group which may have a substituent group is a group,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium alkenyl group which may have a substituent group is a group,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium alkynyl group which may have a substituent is a group,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium aryl group which may have a substituent group is a group,

Or, a halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino Group, alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamide group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group Cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, Other represents a heterocyclic group which may have a substituent is triphenyl phenacyl phosphonium group, R ⁵ to R ⁸ adjacent to each other may be bonded to each other to form a ring. )

In the present invention, R ¹ to R ⁸ of the compound represented by the general formula [1] are each independently a hydrogen atom,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium alkyl group which may have a substituent group is a group,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium alkenyl group which may have a substituent group is a group,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium alkynyl group which may have a substituent is a group,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium aryl group which may have a substituent group is a group,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or May have a substituent is phenyl phenacyl phosphonium group represents a heterocyclic group.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3- Torofenashiru group, and the like.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthra Nyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Furthermore, the alkyl group which may have a substituent mentioned above, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, the aryl group and the substituent which may have a substituent The hydrogen atom of the heterocyclic group which may have may be further substituted with another substituent.

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryl groups such as phenoxy group and p-tolyloxy group. Acyloxy such as alkoxycarbonyl groups such as oxy, methoxycarbonyl, butoxycarbonyl, aryloxycarbonyl such as phenoxycarbonyl, alkenyloxycarbonyl such as vinyloxycarbonyl, acetoxy, propionyloxy, benzoyloxy Group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, metoxalyl group and other acyl groups, methylsulfanyl group, tert-butylsulfanyl group and other alkylsulfanyl groups, phenylsulfanyl Arylsulfanyl groups such as p-tolylsulfanyl group, alkylamino groups such as methylamino group and cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, phenylamino group, p-tolylamino Aryl groups such as alkyl groups, alkyl groups such as methyl groups, ethyl groups, tert-butyl groups, dodecyl groups, aryl groups such as phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups Group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano group, trifluoro group Methyl group, trichloromethyl group, Trimethylsilyl group, a phosphinico group, a phosphono group, an alkylsulfonyl group, an arylsulfonyl group, trialkylammonium group, dimethylsulfoxide Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like. These substituents may be further substituted with a halogen group.

  Among such substituents, a preferred substituent is an electron-withdrawing substituent. By substitution with an electron-attracting substituent, the ionic compound is generally easily dissociated and the antistatic ability is enhanced.

  Such electron-attracting substituents are generic names for substituents that attract electrons from the other party by resonance effects and induced effects, and many of them have a positive value for the substituent constant σ in Hammett's rule. It is. These substituents are not particularly limited, and specific examples thereof include Chemical Review Vol. 91, Nos. 165 to 195. σp described in 1991 is greater than 0. More specifically, halogen group, cyano group, carboxyl group, nitro group, nitroso group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, amide group, perfluoro Examples thereof include an alkyl group, a perfluoroalkylthio group, a perfluoroalkylcarbonyl group, a sulfonamide group, and a 4-cyanophenyl group.

R ¹ to R ⁴ are preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, more preferably a substituent, in view of the stability of the compound. It is an aryl group that may have. From the viewpoint of antistatic ability, the substituent is preferably a halogen group.

R ⁵ to R ⁸ are preferably an alkyl group which may have a substituent in consideration of the stability of the compound. Further, from the viewpoint of compatibility with the resin and antistatic ability, R ⁵ to R ⁸ do not have a hydrophilic substituent such as a hydroxyl group, an alkoxy group, or an acyloxy group. In some cases, it may be preferable to have no group. When R ⁵ to R ⁸ have a substituent, a preferred example is a hydrophobic substituent.

  Although the representative example of a compound represented by General formula [1] of this invention is specifically illustrated below as exemplary compound (1)-(80), it is not restricted to these. In the exemplified compounds, Me is a methyl group, Et is an ethyl group, Pr is a normal propyl group, i-Pr is an isopropyl group, Bu is a normal butyl group, Hex is a normal hexyl group, c-Hex is a cyclohexyl group, and Oct is Octyl group, Cet represents cetyl group, and Ph represents phenyl group.

  The antistatic agent of this invention can be used individually or in combination of 2 or more types.

  As a method of applying the antistatic agent of the present invention to a resin molded article, a method of modeling a resin in which an antistatic agent is directly blended (kneaded), and a coating film (film) of the antistatic agent on the surface of the molded resin There are mainly two types of forming methods.

  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 resins that can be blended (kneaded) with the antistatic agent 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 of this invention can also be mix | blended with resin and a solvent, and can also be 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, 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 of this invention with these solvents is not specifically limited. However, when blended in a large amount, the viscosity of the coating liquid may become too high, or the coating liquid may be whitened. 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 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. 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-butylcyclohexyla Relate, 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. .

  As the polymerization initiator, Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure 149 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, 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 in the present invention, other antistatic agents, pigments, colorants, antioxidants, ultraviolet absorbers, reinforcing agents, weathering agents, lubricants, antiblocking agents, plasticizers, if necessary. Additives such as a fragrance, an inorganic electrolyte, a foaming agent, a flame retardant, a filler, and a surface conditioner can be blended at the same time.

  Other antistatic agents include glycerin mono fatty acid ester, polyglycerin fatty acid ester, diethanolamine fatty acid amide, polyalkylene glycol alkyl ether, N-alkyl ammonium chloride, metal fine particles, metal oxides (ITO, FTO, ATO, etc.), etc. Can be mentioned.

  Examples of pigments include inorganic pigments such as carbon black, iron oxide, calcium carbonate, titanium oxide, zinc oxide, cadmium yellow, nickel titanium yellow, strontium chromate and Prussian blue, azo pigments, indigo pigments, phthalocyanine pigments, quinophthalone pigments, Examples thereof include organic pigments such as indoline pigments, isoindolinone pigments, diketopyrrolopyrrole pigments, quinacridone pigments, perylene pigments, indanthrone pigments, perinone pigments, and dioxazine pigments.

  Examples of the antioxidant 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 include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 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-amylf Enyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- {2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimide) Methyl) -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-methoxybenzophenone, 2, '-Dihydroxy-4,4'-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenylmethane), phenyl salicylate, 4-t-butyl Salicylates such as phenyl salicylate and 4-octylphenyl salicylate; Cyanoacrylates such as ethyl-2-cyano-3,3-diphenyl acrylate and 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate; 2-ethoxy- Oxalic acid systems such as 2'-ethyl oxalic bisanilide, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6) -Tetramethyl-4-piperidyl) 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-butanetetra Carboxylate, (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-piperidyl / β, β, β ′, β'-te Lamethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethyl} -1,2,3,4-butanetetracarboxylate, 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-piperi Gin 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-tetra Methyl-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 monoethylate nickel complex, etc. Nickel-based light stabilizer; 2,4-di-t-butylphenyl-3,5'-di-t-butyl-4'-hydroxybenzoate And so on.

  Examples of the plasticizer include phthalic acid ester, phosphoric acid ester, polyester, trimellitic acid ester, chlorinated paraffin, dibasic acid ester, and epoxidized ester.

  Flame retardants include tetrabromobisphenol A, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) 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, red phosphorus, tin oxide, trioxide Nchimon, zirconium hydroxide, barium metaborate, zinc borate, aluminum hydroxide, magnesium hydroxide, nitrogenated guanidine, and the like.

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

  According to the present invention, there is provided an antistatic agent that has not only high antistatic ability, but also transparency, solubility in resin or solvent (compatibility), heat resistance, and moisture resistance, and does not contain metal or metal ions. It becomes possible.

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

  Next, although this invention is demonstrated using an Example, this 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 (9) 342 g of sodium tetraphenylborate was dissolved in 1 L of ion-exchanged water to obtain a sodium tetraphenylborate aqueous solution. To this aqueous solution, an aqueous tetraethylammonium bromide solution obtained by dissolving 210 g of tetraethylammonium bromide in 1 L of ion-exchanged water was gradually added. By filtering the precipitate, 403 g of compound (9) was obtained. Elemental analysis (MT-5, manufactured by Yanagimoto Seisakusho Co., Ltd., the same applies hereinafter) (Composition formula: C ₃₂ H ₄₀ BN Calculated value (%): C, 85.51; H, 8.97; N, 3.12 Actual value (%): C, 85.61; H, 8.85; N, 3.24).

<Synthesis Example 2> Synthesis of Compound (20) Compound (20) was obtained in the same manner as in Synthesis Example 1, except that octyltrimethylammonium bromide was used instead of tetraethylammonium bromide. Elemental analysis (Composition formula: C ₃₅ H ₄₆ BN Calculated value (%): C, 85.52; H, 9.43; B, 2.20; N, 2.85 Actual value (%): C, 85. 68; H, 9.36; N, 2.79).

<Synthesis Example 3> Synthesis of Compound (47) Synthesis was performed except that sodium tetrakis (pentafluorophenyl) borate was used instead of sodium tetraphenylborate and trimethylvinyloxycarbonylmethylammonium chloride was used instead of tetraethylammonium bromide. In the same manner as in Example 1, compound (47) was obtained. Elemental analysis (composition formula: C ₃₁ H ₁₄ BF ₂₀ NO ₂ calculated value (%): C, 45.23; H, 1.71; N, 1.70 actual value (%): C, 45.14; H , 1.78; N, 1.88).

<Synthesis Example 4> Synthesis of Compound (56) Compound (56) was obtained in the same manner as in Synthesis Example 3, except that allyltrimethylammonium bromide was used instead of trimethylvinyloxycarbonylmethylammonium chloride. Elemental analysis (composition formula: C ₃₀ H ₁₄ BF ₂₀ N calculated value (%): C, 46.24; H, 1.81; N, 1.80 actual value (%): C, 46.18; H, 1.74; N, 1.89).

<Synthesis Example 5> Synthesis of Compound (62) Compound (62) was obtained in the same manner as in Synthesis Example 3, except that tetrabutylammonium bromide was used instead of trimethylvinyloxycarbonylmethylammonium chloride. Elemental analysis (composition formula: C ₄₀ H ₃₆ BF ₂₀ N calculated value (%): C, 52.14; H, 3.94; N, 1.52 actual value (%): C, 52.00; H, 4.00; N, 1.66).

<Synthesis Example 6> Synthesis of Compound (64) Compound (64) was obtained in the same manner as in Synthesis Example 3, except that benzyltributylammonium chloride was used instead of trimethylvinyloxycarbonylmethylammonium chloride. Elemental analysis (composition formula: C ₄₃ H ₃₄ BF ₂₀ N calculated value (%): C, 54.05; H, 3.59; N, 1.47 actual value (%): C, 54.2.14; H, 5.66; N, 1.68).

<Other Synthesis Examples> Compounds (1) to (8), (10) to (19), (21) to (46), (48) to (55), (57) to (61), (63) Synthesis of (65) to (80) According to Synthesis Example 1, sodium, potassium, lithium or magnesium halide salt of borate corresponding to the target compound and bromide, chloride or iodide of ammonium salt corresponding to the target compound The compound was synthesized by salt exchange with. The raw materials were purchased from reagent manufacturers such as Aldrich, Tokyo Kasei, Nacalai Tesque and Merck.

  As for borates which are difficult to obtain, JP-A-62-213293, JP-A-62-277307, JP-A-6-247980, JP-A-6-247981, JP-A-8-311074. JP-A-10-330281, JP-A-10-310589, JP-A-11-292893, JP-A-2000-143671, JP-A-2003-238572, JP-A-2003-335786, JP 2004-43435, U.S. Pat. No. 398236, U.S. Pat. No. 5,473,036, Journal of Organometallic Chemistry, Vol. 1964, Vol. 245, Journal of Organic Chemistry, 1967. Synthesis was performed with reference to Vol.

  Table 1 shows elemental analysis values of typical compounds synthesized.

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 (resin ratio 2%) of the compound (1) 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). 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 80
The surface resistance value of the cured coating film was measured in the same manner as in Example 1 except that the compound (2) to the compound (80) were used instead of the compound (1).

Examples 81-160
The surface resistance value of the cured coating film was measured in the same manner as in Examples 1 to 80 except that 0.075 g (resin ratio 5%) of compound (1) to compound (80) was used.

Comparative Example 1
The surface resistance value of the cured coating film was measured 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 (1).

Comparative Example 2
The surface resistance value of the cured coating film was measured in the same manner as in Example 81 except that the commercially available antistatic agent light ester DQ-100 (manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of the compound (1).

Comparative Example 3
The surface resistance value of the cured coating film was measured 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 (1).

Comparative Example 4
The surface resistance value of the cured coating film was measured in the same manner as in Example 81 except that the commercially available antistatic agent Sanconol A400-50R (manufactured by Sanko Chemical Co., Ltd.) was used instead of the compound (1).

  Table 2 shows the results of Examples 1 to 160 and Comparative Examples 1 to 4.

Table 2

  When the antistatic agent of the present invention was used, a sufficient antistatic effect was obtained regardless of the amount added. Furthermore, even when the values of 2% and 5% were compared, there was no significant difference, and even a small amount was sufficiently effective. On the other hand, in the commercially available antistatic agent, the surface resistance of the cured coating film exceeded the measurement range, and did not function as an antistatic agent.

  The total light transmittance of the PET film of the substrate was 89.80%, and when the antistatic agent of the present invention was used, it showed almost the same value. The antistatic agent of the present invention is a highly transparent material. Moreover, in Comparative Example 3 and Comparative Example 4, the coating film was observed due to the low compatibility of the antistatic agent. The total light transmittance showed a low value because the scattering component by them increased.

Example 161
5 g of the compound (1) was added to 100 g of Aqua 48E (water-soluble alkyd resin manufactured by Showa Varnish Co., Ltd.) and mixed uniformly to prepare a resin varnish. 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 30 minutes. Table 3 shows the results of measuring the surface resistance value of the coating film as an evaluation of the antistatic ability.

Example 162-Example 201
The surface resistance value of the coating film was measured in the same manner as in Example 161 except that the compounds listed in Table 3 were used instead of the compound (1). The results are shown in Table 3.

Comparative Example 5
The surface resistance value of the coating film was measured in the same manner as in Example 161 except that the commercially available antistatic agent Light Ester DQ-100 (manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of the compound (1). The results are shown in Table 3.

Comparative Example 6
The surface resistance value of the coating film was measured in the same manner as in Example 161 except that the commercially available antistatic agent Dasper 125B (manufactured by Miyoshi Resin Co., Ltd.) was used instead of the compound (1). The results are shown in Table 3.

Comparative Example 7
The surface resistance value of the coating film was measured in the same manner as in Example 161 except that the commercially available antistatic agent Emulgen 105 (manufactured by Kao Corporation) was used instead of the compound (1). The results are shown in Table 3.

Table 3

  As can be seen from the results of Example 161 to Example 201, the antistatic agent of the present invention was evenly dispersed and exhibited sufficient antistatic ability even when blended in an aqueous varnish. On the other hand, the comparative example showed a lower surface resistance value than when the antistatic agent of the present invention was used. Particularly in Comparative Example 7, the antistatic agent could not be uniformly dispersed in the aqueous varnish, and the coating film was whitened.

Example 202
100 g of high-density polyethylene (manufactured by Aldrich) and 5 g of compound (1) were kneaded at 150 ° C. for 5 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. Table 4 shows the results of measuring the surface resistance of the resin plate as an evaluation of the antistatic ability. Moreover, the presence or absence of discoloration of the resin plate was also evaluated.

Example 203 to Example 243
The surface resistance value of the resin plate was measured in the same manner as in Example 202 except that the compounds listed in Table 4 were used instead of the compound (1). The results are shown in Table 4.

Comparative Example 8
The surface resistance value of the resin plate was measured in the same manner as in Example 202 except that the commercially available antistatic agent dodecylpyridinium chloride (DPC: manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the compound (1). The results are shown in Table 4.

Comparative Example 9
The surface resistance value of the resin plate was measured in the same manner as in Example 202 except that the commercially available antistatic agent Dasper 125B (manufactured by Miyoshi Resin Co., Ltd.) was used instead of the compound (1). The results are shown in Table 4.

Comparative Example 10
The surface resistance value of the resin plate was measured in the same manner as in Example 202 except that the commercially available antistatic agent Emulgen 105 (manufactured by Kao Corporation) was used instead of the compound (1). The results are shown in Table 4.

Table 4

  As can be seen from the results of Examples 202 to 243, the antistatic agent of the present invention obtained a high antistatic effect even when kneaded with a thermoplastic resin at a high temperature of 150 ° C. for 5 hours. Furthermore, no yellowing was observed in the resin plate using the antistatic agent of the present invention.

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

Example 244
0.5 g of compound (1) 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 80 ° C. for 1 minute to form a coating film. Table 5 shows the results of measuring the surface resistance value of the coating film as an evaluation of the antistatic ability.

Example 245 to Example 290
The surface resistance value of the coating film was measured in the same manner as in Example 244 except that the compounds listed in Table 5 were used instead of the compound (1). The results are shown in Table 5.

Comparative Example 11
The surface resistance value of the coating film was measured in the same manner as in Example 244 except that the commercially available antistatic agent dodecylpyridinium chloride (DPC: manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the compound (1). The results are shown in Table 5.

Comparative Example 12
The surface resistance value of the coating film was measured in the same manner as in Example 244 except that the commercially available antistatic agent Dasper 125B (manufactured by Miyoshi Resin Co., Ltd.) was used instead of the compound (1). The results are shown in Table 5.

Table 5

  As is clear from the results in Table 5, the antistatic agent of the present invention exhibited a lower surface resistance value than the general-purpose antistatic agent.

In order to confirm thermal stability, TG / DTA (TG / DTA6200 manufactured by SII) was measured. Table 6 shows 5% of compound (1), compound (5), compound (9), compound (18), compound (29), compound (51), compound (62), compound (66) and compound (74). The temperature at the time of weight reduction (T _5% ) and the temperature at the time of 10% weight reduction (T _10% ) are shown.

  Furthermore, in FIG.1 and FIG.2, the TG / DTA analysis result of a compound (9) and a compound (62) is shown.

Table 6

  As can be seen from the results in Table 6, the antistatic agent of the present invention had a temperature at 5% weight loss of around 300 ° C. or higher. In other words, it is possible to set the heating temperature range sufficiently high when kneading with a thermoplastic resin, curing a thermosetting resin, and further drying the resin. The effect of shortening can be expected.

Example 291 to Example 302
Table 8 summarizes the solubility of some of the antistatic agents of the present invention in water, organic solvents, and UV curable monomers.

Comparative Example 13 to Comparative Example 16
Table 8 summarizes the solubility of the antistatic agents shown in Table 7 in water, organic solvents, and UV curable monomers.

Table 7

Table 8

  The antistatic agents shown in Table 8 were highly soluble in organic solvents and UV curable monomers. On the other hand, the antistatic agent of the comparative example has 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. The antistatic agents shown in Table 8 are much more compatible with organic materials than the comparative compounds. It can be considered that the low compatibility between the comparative compound and the organic material is largely due to the fact that the comparative compound is formed from an organic anion and a metal cation.

  In addition, since the antistatic agent of this invention is excellent in the dispersibility, as shown in Example 161-Example 202, it can apply preferably also to an aqueous varnish.

Example 303
As a UV monomer, 5 g of purple light UV1700B (manufactured by Nippon Synthetic Chemical), as a polymerization initiator, 0.5 g of DidoCure 174 (manufactured by Daido Kasei), 15 g of ethyl acetate as a diluting solvent, 0.5 g of compound (1) (Resin ratio 5%) 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 (640 mW / cm ² ) using a metal halide lamp. Table 9 shows the results of measuring the haze value of the cured coating film immediately after curing and the haze value of the cured coating film after standing for one week (23 ° C., 55% RH).

Example 304 to Example 314, Comparative Example 17 to Comparative Example 20
A cured coating film was prepared and the haze value was measured in the same manner except that the compounds shown in Table 9 were used instead of the compound (1). The results are shown in Table 9.

Table 9

  Immediately after curing, all the cured coating films had low haze values and high transparency. However, in the cured coating film stored at 23 ° C. and 55% RH for one week, when the antistatic agent of the present invention was used, although it showed almost the same value as that immediately after curing, the antistatic of the comparative example When the agent 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. Presumably, the comparison compound in the coating film is not compatible with the cured resin, so that it may be presumed that it has been crystallized.

Example 315
As a UV curable monomer, 5 g of Aronix M408 (manufactured by Toagosei Co., Ltd.), 0.5 g of DidoCure 174 (manufactured by Daido Kasei Co., Ltd.) as a polymerization initiator, 15 g of ethyl acetate as a diluting solvent, 0 of compound (1) 0.5 g (resin ratio 5%) was 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. The results are shown in Table 10.

Example 316 to Example 326, Comparative Example 21 to Comparative Example 24
Surface resistance values were measured in the same manner except that the compounds shown in Table 10 were used instead of the compound (1). The results are shown in Table 10.

Table 10

When the antistatic agent of the present invention was used, the surface resistance value hardly changed even when the humidity was changed. However, when the antistatic agent of the comparative example was used, the surface resistance value increased as the humidity decreased, and at 35% RH, the value became 10 ¹⁴ Ω / □ or more, and the antistatic effect was lost.

Example 327
10 g of Aronics M402 (manufactured by Toagosei Co., Ltd.) as a UV monomer, 0.5 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a polymerization initiator, and 15 g of ethyl acetate as a diluting solvent were weighed, mixed, and stirred. . A methanol (5 g) solution of 0.1 g of compound (1) (resin ratio 1%) was added to the obtained mixed solution, and the mixture was stirred so as to be uniform.

Using a spin coater, the mixture was applied onto a glass substrate to form a coating film, and then dried at 100 ° C. for 1 minute. Light irradiation (730 mW / cm ² ) was performed using a high-pressure mercury lamp, and the coating film was cured. The surface resistance value of the cured coating film was measured by changing the humidity conditions. The results are shown in Table 11.

Example 328 to Example 350, Comparative Example 25 to Comparative Example 50
Surface resistance values were measured in the same manner except that the compounds shown in Table 11 were used instead of the compound (1). The results are shown in Table 11. In the table, Me represents a methyl group, Et represents an ethyl group, Bu represents a normal butyl group, Ph represents a phenyl group, Tol represents a p-tolyl group, c-Hex represents a cyclohexyl group, and Bn represents a benzyl group.

Table 11

The antistatic agent shown in Table 11 hardly changed its surface resistance value even when the humidity was changed. However, in the compound shown in the comparative example, the surface resistance value decreased by an order of magnitude under the humidity of 55% RH. Further, as the humidity decreased, the surface resistance value increased, and at 35% RH, the value became 10 ¹⁴ Ω / □ or more, and the antistatic effect was lost. Since many of the compounds shown in the comparative examples have high solubility in water, it can be assumed that the influence of humidity is large.

Example 351
Using a tablet molding machine, pellets of compound (1) were prepared, and the surface resistance value was measured by changing the humidity conditions. The results are shown in Table 12.

Example 352 to Example 384, Comparative Example 51 to Comparative Example 80
Surface resistance values were measured in the same manner except that the compounds shown in Table 12 were used instead of the compound (1). The results are shown in Table 12. In the table, Me represents a methyl group, Et represents an ethyl group, Bu represents a normal butyl group, Ph represents a phenyl group, Tol represents a p-tolyl group, c-Hex represents a cyclohexyl group, and Bn represents a benzyl group.

Table 12

  The antistatic agents shown in Table 12 were not affected at all by the humidity, and the surface resistance value was almost the same under any humidity condition. In comparison, the effect of humidity was noticeable in the compound of the comparative example. Furthermore, the surface resistance value became very large under the condition where the humidity was 35% RH.

  Considering the results of Example 291 to Example 384 and Comparative Example 13 to Comparative Example 79 comprehensively, the compound group listed in the Comparative Example is characterized by high solubility in water. This is probably because many of the comparative compounds are composed of an organic cation (ammonium) and an inorganic anion. 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, the antistatic agents listed in the examples have low solubility in water, and the surface resistance value was not affected by humidity under various conditions.

  Judging comprehensively from these examples, 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 transparency and solubility in a resin and a solvent ( (Compatibility), heat resistance, and moisture resistance, and has the characteristics of not containing precious metals, heavy metals, and metal ions. The antistatic agent of the present invention exhibits excellent antistatic ability particularly in an environment with low humidity.

FIG. 1 shows a TG / DTA analysis result of the compound (9). FIG. 2 shows the TG / DTA analysis result of the compound (62).

Claims (17)

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

(Wherein R ^{1 to} R ⁸ are each independently a hydrogen atom,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium alkyl group which may have a substituent group is a group,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium alkenyl group which may have a substituent group is a group,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium alkynyl group which may have a substituent is a group,

Halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, Alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano Group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, or Phenyl phenacyl phosphonium aryl group which may have a substituent group is a group,

Or, a halogen group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, acyloxy group, acyl group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, dialkylamino group, arylamino Group, alkyl group, aryl group, hydroxyl group, carboxyl group, amide group, sulfonamide group, formyl group, mercapto group, alkylthio group, sulfone group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group Cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinyl group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium group, Other represents a heterocyclic group which may have a substituent is triphenyl phenacyl phosphonium group, R ⁵ to R ⁸ adjacent to each other may be bonded to each other to form a ring. ) The antistatic agent according to claim 1, wherein R ^{1 to} R ⁴ are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent. The antistatic agent according to claim 1 or 2, wherein R ^{1 to} R ⁴ are each independently an aryl group which may have a substituent. The antistatic agent according to any one of claims 1 to 3, wherein R ^{5 to} R ⁸ are each independently an alkyl group which may have a substituent.   A resin composition comprising a resin and the antistatic agent according to claim 1.   The resin composition according to claim 5, wherein the resin is a thermoplastic resin and / or a thermosetting resin.   A resin varnish comprising the resin composition according to claim 5 and 6 and a solvent.   A polymerizable composition comprising a compound having a polymerizable functional group, a polymerization initiator, and the antistatic agent according to any one of claims 1 to 4.   A method for producing a cured resin having antistatic ability, wherein the polymerizable composition according to claim 8 is cured by light irradiation.   A cured resin product having an antistatic ability produced by the production method according to claim 9.   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 which apply | coats the coating liquid of Claim 11 to a resin molded product.   A resin shaped article having antistatic ability, produced by the production method according to claim 12.   A resin shaped article having antistatic ability, produced using the resin composition according to claim 5 or 6, the resin varnish according to claim 7, or the polymerizable composition according to claim 8.   An antistatic ability coating formed using the resin composition according to claim 5 or 6, the resin varnish according to claim 7, the polymerizable composition according to claim 8, or the coating liquid according to claim 11. film.   A resin shaped article having an antistatic ability, wherein the coating film according to claim 15 is provided on the surface.   A resin shaped article having an antistatic ability, wherein the antistatic agent according to any one of claims 1 to 4 is used.

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