JP2009179671A - Slightly water-soluble antistatic polymerizable compound, antistatic polymerizable composition containing the compound, and polymer having antistatic property - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new slightly water-soluble antistatic polymerizable compound which contains neither metal nor metal ion, excels in transparency, solubility in (compatibility with) resin or solvent, heat resistance and moisture resistance in itself or its polymer, hardly bleeds out, and can function as an antistatic agent. <P>SOLUTION: The slightly water-soluble antistatic polymerizable compound comprises a quaternary ammonium cation moiety having an ethylenically unsaturated double bond and an anion moiety selected from the group consisting of (C<SB>n</SB>F<SB>2n+1</SB>SO<SB>2</SB>)<SB>3</SB>C<SP>-</SP>, (C<SB>n</SB>F<SB>2n+1</SB>SO<SB>2</SB>)<SB>2</SB>N<SP>-</SP>, (C<SB>n</SB>F<SB>2n+1</SB>SO<SB>2</SB>)(C<SB>m</SB>F<SB>2m+1</SB>CO)N<SP>-</SP>, SCN<SP>-</SP>, R<SP>9</SP>SO<SB>3</SB><SP>-</SP>and R<SP>9</SP>OSO<SB>3</SB><SP>-</SP>(wherein R<SP>9</SP>represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a poorly water-soluble polymerizable compound that can function as an antistatic agent, an antistatic polymerizable composition containing the compound, and an antistatic property obtained by polymerizing the polymerizable compound as an essential component. It relates to a polymer having

  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 that are added in an amount of 0.5 to 5%, and are inexpensive and are used in various applications. However, they have a problem that they ooze out from the resin surface (bleed out) and contaminate 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.

  The compatibility between the antistatic agent and the resin is the largest factor affecting the migration rate of the antistatic agent to the surface. The better this compatibility is, the easier it is to knead into the resin, but the migration to the surface becomes worse, and even if it has an inherently excellent effect, its antistatic effect is reduced. On the other hand, if the compatibility is poor, the migration rate of the antistatic agent to the surface is too high and the bleed out is excessive, and there are problems of contamination such as surface stickiness and durability of the antistatic effect. That is, it is necessary to select an antistatic agent according to the target resin.

  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. However, when the moisture is absorbed, whitening may occur and transparency described later may be reduced. On the other hand, when the humidity is low, the effect is diminished, and eventually it 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.

Patent Document 4 describes that a film having an antistatic function can be formed using a monomer having a (meth) acryloyl group and a quaternary ammonium group.
JP-A-4-239565 Japanese Patent Laid-Open No. 4-7350 Japanese Patent Laid-Open No. 4-198239 JP-A 63-108040

  The object of the present invention is to contain no metal or metal ion, and the polymer itself or its polymer is excellent in transparency, solubility in a resin or solvent (compatibility), heat resistance, moisture resistance, etc., and is difficult to bleed out. An object of the present invention is to provide a novel polymerizable compound that can function as an antistatic agent.

The present invention relates to a quaternary ammonium cation moiety having an ethylenically unsaturated double bond, (C _n F _{2n + 1} SO ₂ ) ₃ C ⁻ , (C _n F _{2n + 1} SO ₂ ) ₂ N ⁻ , (C _n F _{2n + 1} SO ₂ ) (C _m F _{2m + 1} CO) N ⁻ , SCN ⁻ , R ⁹ SO ₃ ⁻ , and R ⁹ OSO ₃ ⁻ (wherein R ⁹ has a hydrogen atom and a substituent) An alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. The present invention relates to a poorly water-soluble antistatic polymerizable compound having an anion portion selected from the group consisting of a heterocyclic group. (However, (meth) and quaternary ammonium cation having an acryloyl _{group, CH 3 C 6 H 4 SO} 3 - excluding the compound composed of).

  In the above invention, the quaternary ammonium cation moiety having an ethylenically unsaturated double bond is preferably a quaternary ammonium cation moiety having a structure represented by the following general formula (2):

（式中、Ｒ^５〜Ｒ^８は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、または、置換基を有してもよい複素環基を表すが、Ｒ⁵〜Ｒ⁸の少なくとも一つはエチレン性不飽和二重結合を有し、また、隣り合うＲ⁵〜Ｒ⁸は、互いに結合して環を形成してもよい。）

(In the formula, R ^{5 to} R ⁸ are each independently a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an alkynyl group that may have a substituent. , An aryl group that may have a substituent, or a heterocyclic group that may have a substituent, wherein at least one of R ^{5 to} R ⁸ has an ethylenically unsaturated double bond, Adjacent R ^{5 to} R ⁸ may be bonded to each other to form a ring.)

  Moreover, in the said invention, it is preferable that the quaternary ammonium cation part which has an ethylenically unsaturated double bond has a (meth) acryloyl group.

  Furthermore, the present invention provides a photopolymerization initiator, another compound having an ethylenically unsaturated double bond other than the poorly water-soluble antistatic polymerizable compound described in any of the above inventions, or an ethylenically unsaturated double bond. The present invention relates to an antistatic polymerizable composition comprising at least one of compounds having no bond and the poorly water-soluble antistatic polymerizable compound according to any one of the above inventions.

Furthermore, this invention relates to the polymer which has antistatic property characterized by polymerizing said antistatic polymerizable composition.

  The poorly water-soluble polymerizable compound of the present invention is excellent in transparency, solubility in a resin or solvent (compatibility), heat resistance, moisture resistance, etc., functions as an antistatic agent that hardly bleeds out.

The poorly water-soluble antistatic polymerizable compound of the present invention is a compound other than a compound consisting of a quaternary ammonium cation moiety having a (meth) acryloyl group and CH ₃ C ₆ H ₄ SO ₃ ^— , It has a quaternary ammonium cation part having a saturated double bond and an anion part described later.
Here, the solubility with respect to water means the amount of the compound that dissolves when the total amount of water and the compound is 100 parts by weight at room temperature (25 ° C.). That is, when 50 parts by weight of a compound is dissolved in 50 parts by weight of water, the solubility is 50% by weight. The poorly water-soluble in the present invention means a solubility of 50% by weight or less, preferably 1% by weight or less. When a compound having a solubility exceeding 50% by weight is used, the polymerized compound or a polymer thereof tends to bleed on the surface of the coating film or molded product when placed under high humidity. In particular, when used in applications where importance is placed on transparency which is difficult to whiten due to humidity, the solubility of the polymerizable compound of the present invention in water is more preferably 1% by weight or less, and 0.01% by weight or less. More preferably.

  The quaternary ammonium cation moiety having an ethylenically unsaturated double bond in the poorly water-soluble antistatic polymerizable compound of the present invention is specifically preferably represented by the general formula [2].

At least one of R ⁵ to R ⁸ is a group having an ethylenically unsaturated double bond, and examples of the group having an ethylenically unsaturated double bond include a vinyl group, a vinylidene group, a styrene group, an acryloyl group, Examples thereof include groups having a methacryloyl group, an acrylamide group, a methacrylamide group, and the like, and a highly polymerizable acryloyl group, methacryloyl group, methacryl group, acrylamide group, and methacrylamide group are preferable.

Of R ⁵ to R ⁸ , the other groups that do not have an ethylenically unsaturated double bond may each independently have a hydrogen atom, an alkyl group that may have a substituent, or a substituent. An alkenyl group, an alkynyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and adjacent R ^{5 to} R ⁸ May combine with each other to form a ring.
As other groups which do not have an ethylenically unsaturated double bond, an alkyl group which may have a substituent is preferable from the viewpoint of 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.

  Specific examples of the quaternary ammonium cation moiety having an ethylenically unsaturated double bond constituting the poorly water-soluble antistatic polymerizable compound of the present invention are specifically exemplified as (1) to (23) below. However, it is not limited to these.

The anion moiety constituting the poorly water-soluble antistatic polymerizable compound of the present invention is (C _n F _{2n + 1} SO ₂ ) ₃ C ⁻ , (C _n F _{2n + 1} SO ₂ ) ₂ N ⁻ , (C _n F _{2n + 1} SO ₂ ) (C _m F _{2m + 1} CO) N ⁻ , SCN ⁻ , R ⁹ SO ₃ ⁻ , and R ⁹ OSO ₃ ^— .
In said formula, it is preferable that it is n = 1-5 in order to form a slightly water-soluble polymerizable compound, and it is more preferable that it is n = 1-3.
In the above formula, R ⁹ has a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent. Represents an aryl group which may be substituted, or a heterocyclic group which may have a substituent.

  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-nitrophena Examples include a syl group.

  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 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. Oxy group, methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, vinyloxycarbonyl group, alkoxycarbonyl group such as aryloxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group An arylsulfuric group such as an acyl group such as an isobutyryl group, an acryloyl group, a methacryloyl group or a methoxalyl group, an alkylsulfanyl group such as a methylsulfanyl group or a tert-butylsulfanyl group, a phenylsulfanyl group or a p-tolylsulfanyl group Nyl group, alkylamino group such as methylamino group, cyclohexylamino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group Alkyl group such as ethyl group, tert-butyl group, dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group and other aryl groups, hydroxyl group, carboxyl Group, sulfonamido group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group , Phosphono group, alkylsulfonyl group, aryl Examples include a sulfonyl group, a trialkylammonium group, a dimethylsulfonyl group, and a triphenylphenacylphosphoniumyl group.

R ⁹ constituting the anion moiety preferably has an electron-withdrawing substituent as a substituent. The electron withdrawing substituent facilitates dissociation between the cation part and the anion part, and increases the antistatic ability.
The electron-withdrawing substituent is a general term for substituents that attract electrons from the other party by a resonance effect or an induced effect, and many of them have a positive value for the substituent constant σ in Hammett's rule. These substituents are not particularly limited, and specific examples thereof include Chemical Review Vol. 91, No. 165-195, which is larger than σp0 described in 1991. 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 compounds having an alkyl group, a perfluoroalkylthio group, a perfluoroalkylcarbonyl group, a sulfonamide group, a 4-cyanophenyl group, and the like.

  Although the representative example of the slightly water-soluble polymerizable compound of this invention is specifically illustrated in Tables 2-4 as exemplary compound (1)-(66), it is not restricted to these.

Next, how to use the poorly water-soluble antistatic polymerizable compound will be described.
The polymerizable composition containing the hardly water-soluble antistatic polymerizable compound can be used as the antistatic composition, or the polymerizable composition containing the hardly water-soluble antistatic polymerizable compound. A polymer obtained by polymerizing the compound with ultraviolet rays, electron beams or the like can also be used as an antistatic agent.

The polymerizable composition containing the poorly water-soluble antistatic polymerizable compound includes, in addition to the above-mentioned poorly water-soluble antistatic polymerizable compound, a photopolymerization initiator and the above-mentioned poorly water-soluble antistatic polymerizable compound. It is a composition containing at least any one of the other compound which has an ethylenically unsaturated double bond, or the compound which does not have an ethylenically unsaturated double bond. In the polymerizable composition, the poorly water-soluble polymerizable compound can be used alone or in combination of two or more.
After the polymerizable composition is applied to various substrates that require antistatic properties, it can be polymerized (cured) by irradiation with ultraviolet rays or electron beams to form an antistatic coating film. .
Alternatively, the polymerizable composition can be heat-kneaded to obtain an antistatic molded product such as a film, a container, or a casing.
Alternatively, the polymerizable composition can be polymerized (cured) by irradiating it with ultraviolet rays or an electron beam to obtain an antistatic polymer. The antistatic polymer can also be added as an antistatic imparting agent to paints and adhesives.

  Examples of other compounds having an ethylenically unsaturated double bond, that is, monomers having a polymerizable functional group, having a relatively low molecular weight include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethoxylated 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 Acrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, dimethylol tricyclodecane diacrylate, hydroxypivalate neopentyl glycol diacrylate, 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, hydroxy Pivalic acid trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate Ethoxylated phosphate triacrylate, ethoxylated tripropylene glycol diacrylate, neopentyl glycol modified trimethylolpropane diacrylate, stearic acid modified pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylolpropane triacrylate, tetramethylolmethane Triacrylate, pentaerythritol tetraacrylate, caprolactone-modified trimethylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, tri (2-hydroxyethyl isocyanurate) triacrylate, propoxylate glyceryl triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol Tetraacrylate, ditrimethyl Roll propane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1, 6-hexanediol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, 2-phenoxyethyl acrylate, acryloylmorpholine, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t- Butyl acrylate, isooct Acrylate, isobornyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, benzyl acrylate, ethoxyethoxyethyl acrylate, butoxyethyl Acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, methylphenoxyethyl acrylate, dipropylene glycol acrylate, β-carboxylethyl acrylate, phenoxydiethylene glycol acrylate, vinyl caprolactam, vinyl pyrrolidone, N-vinylformamide, ethyl diglycol acrylate, Limethylolpropane formal monoacrylate, 4-t-butylcyclohexyl acrylate, tri (meth) allyl isocyanurate, imide acrylate, isoamyl acrylate, ethoxylated succinic acid acrylate, caprolactone modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tri Examples thereof include bromophenyl acrylate, trifluoroethyl acrylate, and ω-carboxypolycaprolactone 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 other compounds having an ethylenically unsaturated double bond, that is, oligomers and prepolymers having a certain molecular weight among monomers having a polymerizable functional group, include “Ebecryl 230, 244, 245, 270 manufactured by Daicel UCB Co., Ltd.” 280 / 15IB, 284, 285, 4830, 4835, 4858, 4883, 8402, 8803, 8800, 254, 264, 265, 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, 8 80,657,800,805,808,810,812,1657,1810, IRR302,450,670,830,835,870,1830,1870,2870, 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, IRR419, manufactured by Sartomer "CN104, CN120, CN124, CN136, CN151, CN2270, CN2271E, CN435, CN454, CN970, CN97, CN97, CN97 , CN9782, CN981, CN9873, CN991 "," Laromar EA81, LR8713, LR8765, LR8986, PE56F, PE44F, LR8800, PE46T, LR8907, PO43F, PO77F, PE55F, R89967, LR889 , LR8985, LR8987, UP35D, UA19T, LR900 , PO83F, PO33F, PO84F, PO94F, LR8863, LR8869, LR8889, LR8997, LR8996, LR9013, LR9019, PO9026V, PE9027V, “Photomer 3005, 3015, 3016, 3072, 3982, 3215, 5010, 5429, 54 , 5432, 5622, 5806, 5930, 6008, 6010, 6019, 6184, 6210, 6217, 6230, 6891, 6892, 6893-20R, 6363, 6572, 3660 "," Art Resin UN-9000HP, 9000PEP " 9200A, 7600, 5200, 1003, 1255, 3320HA, 3320HB, 3320HC, 3320HS, 901T, 1200 "PK, 6060PTM, 6060P", manufactured by Nippon Synthetic Chemical Co., Ltd. 7605B, 7610B, 7620EA, 7630B, 7640B, 2000B, 2010B, 2250EA, 2750B ”,“ Kayarad R-280, R-146, R131, R-205, EX2320, R190, R130, R-300, manufactured by Nippon Kayaku Co., Ltd. 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. .

  Examples of the photopolymerization initiator include Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, IRGACURE 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), Lucyrin TPO (BASF), Dido Cure 174 (Daido Kasei), Special Triazine derivatives described in JP-A-59-1281, JP-B-61-9621 and JP-A-60-60104, organic peroxidation described in JP-A-59-1504 and JP-A-61-243807 Japanese Patent Publication No. 43-23684, Japanese Examined Publication No. 44-6413, Japanese Examined Publication No. 47-1604, and USP 3,567,453, the diazonium compound publication, USP 2,848,328, USP 2,852,379. And organic azide compounds described in U.S. Pat. No. 2,940,853, ortho-quinonediazide described in JP-B 36-22062, JP-B 37-13109, JP-B 38-18015 and JP-B 45-9610 Japanese Patent Publication No. 55-39162, JP 59 140203 and “Macromolecules”, Vol. 10, page 1307 (1977) and various onium compounds including 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 No. 61-151197, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, 85-277 (1988) Transition metal complexes containing transition metals such as ruthenium described in JP-A-2-182701, aluminate complexes described in JP-A-3-209477, borate compounds described in JP-A-2-157760, JP 2,4,5-triarylimidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5 described in JP-A-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 JP-A-5-255421, JP-A-6-157623, JP-A-2000-344812, JP-A-2002-265512, and Japanese Patent Application No. 200. 4-053009 and the sulfonium complex or oxosulfonium complex described in Japanese Patent Application No. 2004-263413, JP-A No. 2001-264530, JP-A No. 2001-261661, JP-A No. 2000-80068, JP-A No. 2001 No. 233842, USP 3558309 (1971), USP 4202697 (1980), JP-A 61-24558, JP-T 2004-534797, and JP-A 2004-359639 Examples include oxime 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.

  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.

By using the hardly water-soluble antistatic polymerizable compound, antistatic molded products such as various films, containers, and housings can be obtained. These antistatic molded products can be applied to various films for FPD, conductive rubber, and electronic component packages.
Examples of the resin used as a compound having no ethylenically unsaturated double bond when obtaining an antistatic molded product 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, in order to promote polymerization by roll kneading, bumper kneading, an extruder or a kneader, it is preferable to heat knead in the range of 60 ° C to 600 ° C.

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

Among the antistatic polymerizable compositions of the present invention, used as a compound having no ethylenically unsaturated double bond in the case of obtaining an antistatic polymerizable composition to be used by being applied like a paint or an adhesive. Examples of the resin that can be used include the following.
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-maleic acid Water-soluble salts of tellurium-based copolymers, water-soluble salts of (meth) acrylic acid ester-based (co) polymers, water-soluble amino alkyd resins, water-soluble amino polyester resins, water-soluble polyamide resins, petroleum resins, alkyds Resin, soybean oil, tung oil, and linseed oil can be used. Furthermore, these can be used individually or in combination of 2 or more types.

In the case of obtaining an antistatic polymerizable composition to be applied and used like a paint or an adhesive, a solvent can be further used.
As the solvent, various solvents such as a high boiling point petroleum solvent, an aliphatic hydrocarbon solvent, an alcohol solvent, and an aqueous solvent can be used according to the properties of the resin. 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.

  An antistatic polymerizable composition that is applied and used as a paint or adhesive is applied onto a suitable substrate, dried as necessary, and polymerized as necessary to prevent it from being charged onto the substrate. Ability can be granted.

Drying and polymerization of the applied antistatic polymerizable composition may be appropriately selected depending on the solvent to be combined and may be dried at room temperature, but is often performed using a heating and drying furnace in order to accelerate the polymerization. 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, but is preferably about 0.05 to 500 minutes.
For example, in the case of using a coating liquid, as a coating method for forming a coating film on the surface of a molded resin, a solution, dispersion, or emulsion containing the antistatic agent according to the present invention is immersed, spin-coated, sprayed. There are methods using various means such as a method, a roller coating method, a gravure coating method, a die coating method, a comma coating method, a roll coating method, a curtain coating method, and a bar coating method. These methods can be appropriately used depending on the thickness, viscosity, and the like to be applied.

  The solvent used at this time is not particularly limited as long as it is a solvent that can dissolve or disperse the poorly water-soluble polymerizable compound, but ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl 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, 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 tellurium, tripropylene glycol monomethyl ether, 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 -Methyl oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2 -Methyl oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Ethyl ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-methoxy-2-methylpropionate, pyrubin Esters such as methyl acid, 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-dimethylacetoa Examples thereof include amides such as amide.

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

The amount of the poorly water-soluble antistatic polymerizable compound contained in the antistatic polymerizable composition is not particularly limited. However, if the amount is small, the antistatic effect cannot be expected so much. On the other hand, the higher the amount of the poorly water-soluble antistatic polymerizable compound, the more the antistatic performance is not improved. In the case of an antistatic polymerizable composition for forming a molded article, if a poorly water-soluble antistatic polymerizable compound is contained in a large amount, physical properties such as mechanical strength of the molded article tend to be lowered. In addition, in the case of an antistatic polymerizable composition for coating, if a poorly water-soluble antistatic polymerizable compound is contained in a large amount, the viscosity of the coating liquid becomes too high, or the whitening of the coating liquid occurs. Sometimes.
Therefore, the preferable blending amount of the poorly water-soluble antistatic polymerizable compound is 0.01 to 30% by weight, more preferably 0.02 to 25% by weight, and most preferably 0.02% with respect to the entire polymerizable composition. -20% by weight. When importance is attached to transparency, it is preferably 0.02 to 15% by weight, and more preferably 0.02 to 10% by weight.

  When using the poorly water-soluble polymerizable compound in the present invention, other antistatic agents, pigments, colorants, antioxidants, ultraviolet absorbers, reinforcing agents, weathering agents, lubricants, antiblocking agents, if necessary. Additives such as a plasticizer, 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.

  As described above, the polymerizable composition of the present invention is polymerized (cured) by irradiation with ultraviolet rays or electron beams to obtain an antistatic polymer, and the antistatic polymer is further added to an antistatic agent. It can also be added to paints and adhesives, and various molded products can be obtained by heat-kneading with a thermoplastic resin or the like as an antistatic agent.

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 1 287 g of lithium bis (trifluoromethanesulfone) imide shown in Table 5 was dissolved in 1 L of ion-exchanged water to obtain a lithium bis (trifluoromethanesulfone) imide aqueous solution. To this aqueous solution, a diallyldimethylammonium chloride aqueous solution obtained by dissolving 161 g of diallyldimethylammonium chloride in 1 L of ion-exchanged water was gradually added. By filtering the precipitate, 398 g of Compound 1 was obtained. Table 6 shows the results obtained by confirming the obtained compound 1 by elemental analysis (MT-5 manufactured by Yanagimoto Seisakusho Co., Ltd.).

Moreover, the compound 1 was added to distilled water at room temperature 25 degreeC, the density | concentration was adjusted so that it might become 1 weight% and 50 weight%, and it evaluated in the following three steps. The results are shown in Table 7.
A: 1% by weight, white turbid or precipitated and not dissolved ○: 50% weight, white turbid or precipitated and not dissolved ×: 50% weight, dissolved and transparent

<Synthesis Example 2> Synthesis of Compound 3 As shown in Table 5, Compound 3 was obtained in the same manner as in Synthesis Example 1 except that methacryloyloxyethyltrimethylammonium chloride was used instead of diallyldimethylammonium chloride. Table 6 shows the results obtained by confirming the obtained compound 3 by elemental analysis (MT-5 manufactured by Yanagimoto Seisakusho Co., Ltd.). Table 7 shows the solubility in water.

<Synthesis Example 3> Synthesis of Compound 26 As shown in Table 5, Compound 26 was obtained in the same manner as Synthesis Example 2 except that potassium thiocyanate was used instead of lithium bis (trifluoromethanesulfone) imide. Table 6 shows the results obtained by confirming the obtained compound 26 by elemental analysis (MT-5 manufactured by Yanagimoto Seisakusho Co., Ltd.). Table 7 shows the solubility in water.

<Synthesis Example 4> Synthesis of Compound 47 As shown in Table 5, compound 47 was prepared in the same manner as in Synthesis Example 1 except that sodium p-toluenesulfonate was used instead of lithium bis (trifluoromethanesulfone) imide. Obtained. Table 6 shows the results obtained by confirming the obtained compound 47 by elemental analysis (MT-5 manufactured by Yanagimoto Seisakusho Co., Ltd.). Table 7 shows the solubility in water.

<Synthesis Examples 5-6> Synthesis of Compounds 57 and 65 As shown in Table 5, instead of lithium bis (trifluoromethanesulfone) imide, lithium trisfluoromethanesulfonylmethide, lithium bistrifluoropropanesulfonimide, lithium trifluoromethanesulfone Compounds 53, 57, 65, and 67 were obtained in the same manner as in Synthesis Example 2, except that narate was used. Table 6 shows the results obtained by confirming the obtained compounds 53, 57, 65 and 67 from elemental analysis (MT-5 manufactured by Yanagimoto Seisakusho Co., Ltd.). Table 7 shows the solubility in water.

<Comparative Synthesis Examples 1 and 2> Synthesis of Comparative Compounds 1 and 2 As shown in Table 5, synthesis examples except that lithium trifluoromethanesulfonate and sodium benzoate were used instead of lithium bis (trifluoromethanesulfone) imide. After compounding in the same manner as in No. 2, the inorganic ion component was removed using an ion permeable membrane and dried to obtain Comparative Compounds 1 and 2. Table 6 shows the results of confirming the obtained compounds 1 and 2 by elemental analysis (MT-5 manufactured by Yanagimoto Seisakusho Co., Ltd.). Table 7 shows the solubility in water.

<Other Synthesis Examples> Synthesis of Compounds 2, 4 to 25, 27 to 46, 48 to 56, 58 to 64, 66 According to Synthesis Example 1, sodium, potassium, lithium having an anion moiety corresponding to the target compound or Each compound shown in Table 2 was synthesized by salt exchange between a magnesium halide salt and a bromide, chloride or iodide of an ammonium salt corresponding to the target compound. The raw materials were purchased from reagent manufacturers such as Aldrich, Tokyo Kasei, Nacalai Tesque and Merck.

  Regarding anion components such as lithium trisfluoromethanesulfonylmethide and lithium bistrifluoropropanesulfonimide, which are difficult to obtain, WO92 / 02966, Inorg. Chem., 1988, 27, 2135., J. Chem. Soc. Faraday Trans., 1993, 89, 355, USP 5446134, JP-A-8-81436, and JP-A 2000-226392 were used for the synthesis.

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 diluent solvent As an antistatic agent, 0.075 g (resin ratio 5% by weight) of Compound 1 was weighed, mixed, and stirred so that the mixed solution became uniform.

The above mixture was applied onto a polyethylene terephthalate (hereinafter referred to as PET) substrate using a bar coater # 12 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 following items were evaluated. The results are shown in Table 7.

Surface resistance value The surface resistance value was measured by measurement (R8340A manufactured by Advantest Corporation). Depending on the level of surface resistance (Ω / □), it is evaluated as follows.

10 Less than ¹⁰ units ◎
10 ¹¹ platform Ω / □ value ○
10 ¹² Ω / □ value △
10 ¹³ Ω / □ or more ×

Total light transmittance Total light transmittance was measured for HGM-2B manufactured by Suga Test Instruments Co., Ltd.
(Substrate PET: 89.80%)
89.00 or more: ○
Less than 89.00: ×

Humidity test After leaving the sample for 10 days under conditions of 40 ° C. and 95 RH%, the appearance of the coating film was visually observed and compared with the coating film appearance immediately after curing, and evaluated in the following three stages;
A: No change
○: Slightly bleed material is observed, but appearance is good.
Moreover, the change of the contact angle of the wet heat coating film surface was observed, and compared with the coating film immediately after hardening, it evaluated in the following two steps.
A: Change less than ± 1 degree.
○: Change of ± 1 or more and less than 10 degrees.
X: Change of ± 10 or more.

Example 2 to Example 66
Evaluation was performed in the same manner as in Example 1 except that Compound 2 to Compound 66 were used instead of Compound 1.

Comparative Example 1
Evaluation was conducted in the same manner as in Example 1 except that tetrabutylammonium tetraphenylborate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the compound (1).

Comparative Example 2
Evaluation was conducted in the same manner as in Example 1 except that methacryloyloxyethyltrimethylammonium chloride was used in place of the compound (1).

Comparative Example 3
Evaluation was conducted in the same manner as in Example 1 except that Comparative Compound 1 was used instead of Compound (1).

Comparative Example 4
Evaluation was conducted in the same manner as in Example 1 except that Comparative Compound 2 was used instead of Compound (1).

  Table 7 shows the results of Examples 1 to 66 and Comparative Examples 1 to 4.

When the poorly water-soluble polysynthetic compound of the present invention was used, a sufficient antistatic effect was obtained.
When the antistatic agent of the present invention was used, there was no change in the appearance of the coating film even after the moisture resistance test, and no significant change in the contact angle was observed. In Comparative Example 1, the contact angle was greatly changed from that immediately after the coating film due to bleed-out after the moisture resistance test. Moreover, the comparative examples 2-4 were whitened and the external appearance was impaired after the heat-and-moisture resistance test.

Example 67
After mixing 100 g of high density polyethylene (manufactured by Aldrich) and 5 g of Compound 1, the mixture was 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 8 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 67 to Example 133
The surface resistance value of the resin plate was measured in the same manner as in Example 67 except that compound 2 to compound 66 were used instead of compound 1. The results are shown in Table 8.

Comparative Example 5
The surface resistance value of the resin plate was measured in the same manner as in Example 67 except that methacryloyloxyethyltrimethylammonium chloride was used in place of Compound 1. The results are shown in Table 8.

Comparative Example 6
The surface resistance value of the resin plate was measured in the same manner as in Example 67 except that Comparative Compound 2 was used instead of Compound 1. The results are shown in Table 8.

  As can be seen from the results of Examples 67 to 133, the poorly water-soluble antistatic polymerizable compound of the present invention is highly antistatic even when kneaded with a thermoplastic resin at a high temperature of 150 ° C. for 5 hours. The effect was obtained. Furthermore, no yellowing was observed in the resin plate using the poorly water-soluble antistatic polymerizable compound of the present invention.

Claims (5)

A quaternary ammonium cation moiety having an ethylenically unsaturated double bond, (C _n F _{2n + 1} SO ₂ ) ₃ C ⁻ , (C _n F _{2n + 1} SO ₂ ) ₂ N ⁻ , (C _n F _{2n + 1} SO ₂ ) (C _m F _{2m + 1} CO) N ⁻ , SCN ⁻ , R ⁹ SO ₃ ⁻ , and R ⁹ OSO ₃ ⁻ (wherein R ⁹ may have a hydrogen atom or a substituent. An alkyl group, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent; selected from the group consisting of representing) having an anion portion, poorly water-soluble antistatic polymerizable compound (however, (meth) and quaternary ammonium cation having an acryloyl _{group, CH 3 C 6 H 4 SO} 3 - and Excluding compounds consisting of: The poorly water-soluble charge according to claim 1, wherein the quaternary ammonium cation moiety having an ethylenically unsaturated double bond is a quaternary ammonium cation moiety having a structure represented by the following general formula (2). Inhibiting polymerizable compounds.

(In the formula, R ^{5 to} R ⁸ are each independently a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an alkynyl group that may have a substituent. , An aryl group that may have a substituent, or a heterocyclic group that may have a substituent, wherein at least one of R ^{5 to} R ⁸ has an ethylenically unsaturated double bond, Adjacent R ^{5 to} R ⁸ may be bonded to each other to form a ring.)   3. The poorly water-soluble antistatic polymerizable compound according to claim 1, wherein the quaternary ammonium cation moiety having an ethylenically unsaturated double bond has a (meth) acryloyl group.   A photopolymerization initiator, another compound having an ethylenically unsaturated double bond other than the poorly water-soluble antistatic polymerizable compound according to any one of claims 1 to 3, or a compound having no ethylenically unsaturated double bond An antistatic polymerizable composition comprising at least one of the above and the poorly water-soluble antistatic polymerizable compound according to claim 1.   An antistatic polymer obtained by polymerizing the antistatic polymerizable composition according to claim 1.