JP2006241420A - Resin composition for destaticizing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin cured by active energy rays or heat, and having good destaticizing properties, transparency, weather resistance, flexibility of a coated film and heat resistance while keeping adhesion to a base material and strength of the coated film by using a resin composition for destaticizing, using a prepolymer of a specific polyisocyanate and a specified (meth)acrylate. <P>SOLUTION: The curable resin composition is obtained by compounding a reactive diluent having a (meth)acryloyl group or an epoxy resin, and a photopolymerization initiator or a curing agent with the resin composition for destaticizing, using the prepolymer obtained by reacting a specific trifunctional polyisocyanate with a specified hydroxy group-terminated polyalkylene glycol mono(meth)acrylate in an ratio of the equivalent of the isocyanate group/the equivalent of the hydroxy group regulated so as to be 0.8-1.2. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention provides an antistatic resin composition using a prepolymer of a specific trifunctional polyisocyanate and a specific (meth) acrylate, which is cured by active energy rays or heat, and has antistatic properties, The present invention provides a curable resin composition having good transparency, weather resistance, adhesion, coating film strength, coating film flexibility, and heat resistance.

  Plastic base materials are used in a wide range of fields such as automobile parts, optical parts, optical disks, and organic plate glass, but have a drawback that they are easily scratched and easily charged with dust. In order to improve these defects, various methods for forming a coating layer on the surface with a curable resin composition using active energy rays or heat have been studied. However, although this method greatly improves the scratch resistance, it is easily charged by friction or the like.

  Therefore, various methods for adding an antistatic agent to these resin compositions have been proposed in order to improve these defects. As a method of adding an antistatic agent to the active energy ray-curable resin composition, as an antistatic agent, a cationic system (for example, see Patent Documents 1 and 2), an anionic system, and a nonionic system (for example, see Patent Document 3). In the case of adding various surfactants such as, it is necessary to add a considerable amount in order to obtain sufficient antistatic properties. In this case, sufficient coating strength and scratch resistance cannot be obtained, the antistatic agent bleeds on the surface of the coating layer, and transparency and antistatic properties are significantly reduced over time under high humidity. It also has the disadvantage of.

  On the other hand, various methods for adding conductive fillers such as metal fine particles have been proposed (see, for example, Patent Documents 4 to 5). In this case, although it is excellent in antistatic property, it has the fault that transparency is impaired by a conductive filler. Therefore, a technique that satisfies the transparency and antistatic properties by reducing the addition amount of the conductive filler as much as possible is desired, but only insufficient performance is obtained.

JP 2000-282014 A (paragraph numbers [0039] to [0058]) JP 07-316467 A (paragraph numbers [0019] to [0023]) JP 2000-281736 A (paragraph numbers [0032] to [0043]) JP 2003-306561 A (paragraph numbers [0036] to [0048]) JP-A-10-231444 (paragraph numbers [0014] to [0032])

  The present invention has been made to solve the above-mentioned problems, and is cured by an active energy ray or heat to maintain the adhesion to the substrate and the coating film strength, and the surface by bleeding out of the antistatic agent. It is an object of the present invention to provide a curable resin composition having good antistatic properties, transparency, weather resistance, coating film flexibility, and heat resistance.

  As a result of intensive studies to achieve the above object, the present inventors have used a resin composition for antistatics using a prepolymer of a specific polyisocyanate and a specific (meth) acrylate, It has been found that a curable resin excellent in adhesion and coating film strength and excellent in antistatic properties and physical properties can be obtained, and has reached the present invention.

  That is, the present invention includes a hydroxyl group-containing (meth) containing 60 to 100 wt% of a trifunctional polyisocyanate represented by the following general formula (1) and a hydroxyl group-terminated polyalkylene glycol mono (meth) acrylate represented by the following general formula (4). A reactive diluent or epoxy having a (meth) acryloyl group to an antistatic resin composition using a prepolymer obtained by reacting acrylate with an isocyanate group equivalent / hydroxyl group equivalent of 0.8 to 1.2 When a resin composition comprising a resin, a photopolymerization initiator or a curing agent is used, adhesion to the base material and coating film strength are maintained, and antistatic properties, transparency, weather resistance, coating film are maintained. A curable resin excellent in flexibility and heat resistance can be obtained.

（Ｒ_１は下記一般式（２）、（３）で表される基を示す。）

（Ｒ_２は水素原子またはメチル基を示し、Ｒ_３は下記一般式（５）、（６）、（７）、（８）で表わされる基を示す。）

（ａは１〜１５の正数を示す。）

（ｂは１〜１５の正数を示す。）

（ｃ、ｄは１以上の正数を示す。）

（e、ｆは１以上の正数を示す。）

(R ₁ represents a group represented by the following general formulas (2) and (3).)

(R ₂ represents a hydrogen atom or a methyl group, and R ₃ represents a group represented by the following general formulas (5), (6), (7), (8)).

(A represents a positive number from 1 to 15.)

(B represents a positive number from 1 to 15.)

(C and d are positive numbers of 1 or more.)

(E and f are positive numbers of 1 or more.)

  The antistatic resin composition of the present invention can be applied to various uses. For example, as an active energy ray or thermosetting resin, applied to household electrical appliances, electronic components that are easily charged with static electricity, coating materials for substrates that do not like dust and dirt, UV curable paints, and materials for electronics such as dicing tape It can also be applied as an antistatic material by blending into a thermoplastic resin or thermosetting resin.

  In the present invention, a trifunctional polyisocyanate represented by the general formula (1) and a hydroxyl group-containing (meth) acrylate containing 60 to 100 wt% of a hydroxyl group-terminated polyalkylene glycol mono (meth) acrylate represented by the general formula (4), The antistatic resin composition using a prepolymer reacted with an isocyanate group equivalent / hydroxyl group equivalent at a ratio of 0.8 to 1.2 will be specifically described below.

  Examples of the trifunctional polyisocyanate represented by the general formula (1) in the present invention include a hexamethylene diisocyanate burette or nurate. Compared to other polyisocyanates, it is preferable from the viewpoints of transparency, weather resistance, adhesion, coating film flexibility, and heat resistance. You may use these individually or in mixture of 2 or more types.

  Examples of the hydroxyl-terminated polyalkylene glycol mono (meth) acrylate represented by the general formula (4) in the present invention include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, Examples thereof include polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, and the like. You may use these individually or in mixture of 2 or more types.

  As the hydroxyl group-containing (meth) acrylate in the present invention, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol hexa ( (Meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol Tri (meth) acrylate, tripentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, glycerin mono (meth) acrylate, hydroxyl group-containing alkylene oxide modified glycerin (meth) acrylate, hydroxyl group Containing alkylene oxide-modified polyglycerin (meth) acrylate, epoxy resin having two or more epoxy groups in one molecule (polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydro Diglycidyl phthalate, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, ethylene oxide modified Bi Toll polyglycidyl ether) and (meth) epoxy (meth) acrylate is a reaction product of acrylic acid. You may use these individually or in mixture of 2 or more types.

  The hydroxyl group-terminated polyalkylene glycol mono (meth) acrylate represented by the general formula (4) is preferably blended in an amount of 60 to 100 wt% in the hydroxyl group-containing (meth) acrylate from the viewpoint of antistatic properties. When it is less than 60 wt%, sufficient antistatic properties cannot be obtained.

  Obtained by reacting a trifunctional polyisocyanate represented by the general formula (1) with a hydroxyl group-containing (meth) acrylate containing 60 to 100 wt% of a hydroxyl-terminated polyalkylene glycol mono (meth) acrylate represented by the general formula (4). The prepolymer is preferably reacted at a ratio of isocyanate group equivalent / hydroxyl group equivalent of 0.8 to 1.2. When the isocyanate group equivalent / hydroxyl group equivalent is 1.2 or more, the antistatic property, transparency and coating strength are impaired. When the isocyanate equivalent / hydroxyl group equivalent is less than 0.8, adhesion and coating film flexibility are impaired.

  In the present invention, the trifunctional polyisocyanate represented by the general formula (1) and the hydroxyl group-containing (meth) acrylate containing 60 to 100 wt% of the hydroxyl group-terminated polyalkylene glycol mono (meth) acrylate represented by the general formula (4) are reacted. As a manufacturing method of the prepolymer obtained by making it react, it is preferable that reaction temperature exists in the range of room temperature-150 degreeC. Moreover, you may add a catalyst and a basic catalyst and an acidic catalyst can be used as a catalyst. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, and phosphines such as tributylphosphine and triphenylphosphine. Examples of the acidic catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, trititanium tetrabutoxide, zirconium tetrabutoxide, and other metal alkoxides, aluminum chloride and other Lewis acids, 2-ethylhexanetin, Examples include tin compounds such as octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate. Of these, acidic catalysts are preferred, and tin compounds are particularly preferred. Follow-up of the reaction confirms that the absorption specific to isocyanate groups disappears in IR analysis.

  After the completion of the reaction, the reactive diluent or epoxy resin having a (meth) acryloyl group described below may be diluted singly or in combination of two or more as long as the antistatic property of the prepolymer is not significantly impaired.

  The method for producing the antistatic resin composition of the present invention is not limited to the above-described method, and it goes without saying that a publicly known and commonly used method may be followed.

  Examples of the reactive diluent having a (meth) acryloyl group in the present invention include tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (Meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate Poly (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth), a reaction product of dirate erythritol and ε-caprolactone Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, and ε- Di (meth) acrylate of caprolactone adduct, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neo Nylglycol di (meth) acrylate, alkylene oxide modified polyglycerol poly (meth) acrylate, alkylene oxide modified glycerol poly (meth) acrylate, glycerol di (meth) acrylate, 1,4-butanediol (meth) acrylate, in molecule Epoxy resin having two or more epoxy groups (polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, trimethylolpropane Polyglycidyl ether, ethylene oxide-modified sorbitol polyglycidyl ether, etc.) and (meth) acrylic acid reaction product of epoxy (meth) acrylic acid Bifunctional or more reactive diluents such as glycerol, glycerin mono (meth) acrylate, imide acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenoxyethyl (meth) Acrylate, phenoxypolyethylene glycol (meth) acrylate, alkyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl ( (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate Rate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, vinyl caprolactone, ethylene oxide modified phosphate acrylate and ethylene oxide modified phosphate Examples thereof include monofunctional reactive diluents such as monomers containing a phosphate group such as methacrylate. You may use these individually or in mixture of 2 or more types. Of these reactive diluents, trifunctional or higher functional (meth) acrylates are preferred.

  From the viewpoint of workability, the reactive diluent having a (meth) acryloyl group is preferably used in an amount of 20 to 100 parts by weight with respect to 100 parts by weight of the antistatic resin composition.

  The epoxy resin in the present invention is not particularly limited. For example, as the glycidyl ether type epoxy resin, glycerin, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol, polyglycidyl ether such as sorbitol, and glycerin, di Polyglycidyl ethers of alkylene oxide adducts such as glycerin, polyglycerin, diethylene glycol, polyethylene glycol and sorbitol, trimethylolpropane polyglycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, polypropylene glycol diglycidyl ether, neopentyl glycol Diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6 Examples include hexanediol diglycidyl ether, hydrogenated bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, butyl glycidyl ether, and phenyl glycidyl ether. 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, and the like. You may use these individually or in mixture of 2 or more types.

  As a photoinitiator in this invention, a radical polymerization initiator and a cationic polymerization initiator can be mentioned.

  Examples of the radical polymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether, acetophenone, 2,2-diethoxy-2-phenylacetophenone, and 2,2-diethoxy- 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- (methylthio ) Acetophenones such as phenyl] -2-morpholinopropan-1-one, methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-chloroanthraquinone, 2-a Anthraquinones such as luanthraquinone, thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal Benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) -Phenylphosphine oxide and the like.

  You may use these individually or in mixture of 2 or more types. Furthermore, photopolymerization initiation assistants such as tertiary amines such as triethanolamine and methyldiethanolamine, benzoic acid derivatives such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, etc. You may use together.

  The cationic polymerization initiator is not particularly limited, and examples thereof include onium salts such as aromatic iodonium salts, aromatic sulfonium salts, diazonium salts, and organometallic complexes such as iron-allene complexes.

  Aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis ( To dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium Xafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliod Nitrohexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate, etc. Examples of the aromatic sulfonium salt include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (Diphenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfonio) phenyl] sulfidetetrakis (pentafluorophenyl) borate, diphenyl-4- (pheny Thio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) ) Borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- (di (4- (2-hydroxy Ethoxy)) phenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- ( Di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoro Examples thereof include borates, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, and aromatic diazonium salts include phenyldiazonium hexafluorophosphate. , Phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis (pentafluorophenyl) borate and the like. As the aromatic ammonium salt, 1-benzyl- -Cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1- (Naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate and the like, and (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe salt Are (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) hexafluorophosphate, (2,4-cyclopentadien-1-yl) [(1-methylethyl ) Benzene] -Fe (II) hexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) tetrafluoroborate, (2,4-cyclo And pentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) tetrakis (pentafluorophenyl) borate.

  The addition amount of the photopolymerization initiator is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the antistatic resin composition.

  Although it does not specifically limit as a hardening | curing agent in this invention, For example, as an amine compound, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine , Diethylaminopropylamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone, N-amino Ethyl piperazine, polyoxyethylene diamine, polyoxypropylene diamine, polyoxybutylene diamine, polyoxypentylene diamine, polyoxy Examples include tylene triamine, polyoxypropylene triamine, polyoxybutylene triamine, polyoxypentylene triamine, and derivatives thereof. Acid anhydrides include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methyltetrahydroanhydride. Examples include phthalic acid, maleic anhydride, succinic anhydride, dodecynyl succinic anhydride, methyl nadic anhydride, pyromellitic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride, and the like.

  You may use these individually or in mixture of 2 or more types. Furthermore, imidazoles such as 2-ethyl-4-methylimidazole, organic phosphine compounds such as tertiary amine and triphenylphosphine, tertiary amine salts, quaternary ammonium salts, metal salts such as octylate tin, phosphonium salts, etc. These curing accelerators may be used in combination.

  In the active energy ray or thermosetting resin composition of the present invention, fine particles composed of silica, alumina, titania, zirconia, etc., tin oxide, antimony-doped tin oxide (ATO), Transparent fine particles of conductive metal oxides such as indium tin oxide (ITO) and zinc antimonate can be arbitrarily blended. The conductive metal oxide can be easily obtained as an organosol dispersed in an organic solvent. Moreover, it can also be used by dispersing the conductive metal oxide powder in the active energy ray-curable resin composition. The particle size is not particularly limited as long as the primary particle size is in the range of 1 to 200 nanometers. However, when the conductive metal oxide is in powder form, the BET method calculated by the gas phase adsorption method is used. In the case where the conductive metal oxide is in an organosol form, the average particle size by dynamic light scattering is preferably 200 nanometers or less.

  If necessary, the curable resin composition of the present invention can be blended with known general paint additives within a range that does not significantly impair the purpose. For example, solvents, polymerization inhibitors, light stabilizers, antioxidants, ultraviolet absorbers, fillers, antifoaming agents, leveling, surface additives, silicone-based and fluorine-based additives can damage the cured film surface. In addition to being effective in prevention, when ultraviolet rays are used as an active energy ray, the inhibition of resin curing by oxygen can be reduced by bleeding to the air interface of the additive, under conditions of low irradiation intensity. Even in this case, an effective degree of curing can be obtained.

  As an active energy ray source used for curing the curable resin composition of the present invention, a light source such as a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, a gas laser, or a solid laser can be used. In general, a high-pressure mercury lamp is used for curing a clear coating film not containing a filler, and a metal halide lamp is used for curing a thick film when a filler is included.

  It is also possible to use an electron beam in a composition excluding a photopolymerization initiator. Specifically, it is a Cockloftwald type, a bandecraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type. It is preferable to use an electron beam emitted from various electron beam accelerators such as a high-frequency type.

  The curable resin composition of the present invention can be applied, for example, as a coating material for a household appliance, an electronic component that is easily charged with static electricity, a substrate that does not like dust or dirt, and the resin composition is applied onto the substrate and dried. After that, curing with excellent antistatic properties, transparency, weather resistance, coating flexibility, and heat resistance while maintaining adhesion and coating strength by irradiating active energy rays to form a cured coating A functional resin composition can be prepared.

  As the base material, polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), polysulfone (PSU) ), Polyacrylonitrile (PAN), triacetyl cellulose (TAC), transparent plastic resin films such as transparent styrenic resins (transparent ABS, ASA), wood, paper, glass and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following description examples unless it exceeds the gist.

<Synthesis Example 1>
A flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 455.9 g of polyethylene glycol monoacrylate (Blemmer AE-400; manufactured by NOF Corporation, hydroxyl value 92), 0.6 g of methoquinone, and 0.06 g of dibutyltin dilaurate. , Heated to 80 ° C. and stirred. Thereafter, 124 g of a hexamethylene diisocyanate nurate (Duranate TPA-100; manufactured by Asahi Kasei Chemicals Co., Ltd., isocyanate content 23.1%) in such an amount that the isocyanate group equivalent / hydroxyl group equivalent is 0.9 was added dropwise. After dropping, the mixture was further stirred for 2 hours, and after confirming that the absorption specific to the isocyanate group disappeared in IR analysis, 30 g of polyethylene glycol monomethacrylate (Blenmer PE-350; manufactured by NOF Corporation) was added, A milky white antistatic resin composition was obtained. Hereinafter, this is referred to as an antistatic resin composition 1.

<Synthesis Example 2>
A flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 304 g of polyethylene glycol monoacrylate (Blemmer AE-400; manufactured by NOF Corporation, hydroxyl value 92), 0.6 g of methoquinone, 0.06 g of dibutyltin dilaurate, 80 Heated to ° C and stirred. Thereafter, 107 g of hexamethylene diisocyanate nurate (Duranate TPA-100; manufactured by Asahi Kasei Chemicals Corporation, isocyanate content 23.1%) was dropped and reacted for 1 hour, and then polyoxyethylene sorbitol polyglycidyl ether (SR -SEP (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) and 22 g of epoxy acrylate (reaction product of acrylic acid equivalent / epoxy equivalent = 0.75), which is a reaction product of acrylic acid, was added dropwise, and isocyanate group equivalent / hydroxyl group equivalent was about 0 The reaction was carried out in an amount of .9. Thereafter, the mixture was further stirred for 2 hours, and after confirming that the absorption specific to the isocyanate group disappeared in IR analysis, 23 g of polyethylene glycol monomethacrylate (Blenmer PE-350; manufactured by NOF Corporation) was added to give a milky white color. A liquid antistatic resin composition was obtained. Hereinafter, this is referred to as an antistatic resin composition 2.

<Synthesis Example 3>
A flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 360 g of polyethylene glycol monoacrylate (Blemmer AE-400; manufactured by NOF Corporation, hydroxyl value 92), 0.6 g of methoquinone, 0.06 g of dibutyltin dilaurate, 80 Heated to ° C and stirred. Thereafter, 117 g of hexamethylene diisocyanate nurate (Duranate TPA-100; manufactured by Asahi Kasei Chemicals Corporation, isocyanate content 23.1%) was dropped and reacted for 1 hour, and then a hydroxyl group-containing propylene oxide-modified diglycerin acrylate ( Hydroxyl value 157) 40 g was added dropwise, and the reaction was carried out in such an amount that the isocyanate group equivalent / hydroxyl group equivalent was about 0.9. Thereafter, the mixture was further stirred for 2 hours, and after confirming that the absorption specific to the isocyanate group disappeared in IR analysis, 27 g of polyethylene glycol monomethacrylate (Blenmer PE-200; manufactured by Nippon Oil & Fats Co., Ltd.) was added to give a milky white color. A liquid antistatic resin composition was obtained. Hereinafter, this is referred to as an antistatic resin composition 3.

<Synthesis Example 4>
A flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 303.9 g of polypropylene glycol monoacrylate (Blenmer AP-400; manufactured by NOF Corporation, hydroxyl value 120), 0.6 g of methoquinone, and 0.06 g of dibutyltin dilaurate. , Heated to 80 ° C. and stirred. Thereafter, 107 g of a hexamethylene diisocyanate nurateate (Duranate TPA-100; manufactured by Asahi Kasei Chemicals Co., Ltd., isocyanate content 23.1%) having an isocyanate group equivalent / hydroxyl group equivalent of 0.9 was added dropwise. After the addition, the mixture was further stirred for 2 hours, and after confirming that the absorption specific to the isocyanate group disappeared in IR analysis, 176 g of methoxypolyethylene glycol monoacrylate (Blemmer AME-400; manufactured by NOF Corporation) was added. A transparent liquid antistatic resin composition was obtained. Hereinafter, this is referred to as an antistatic resin composition 4.

<Examples 1-4, Comparative Examples 1-2>
The active energy ray-curable resin composition weighed in the proportions shown in Table 1 below (values represent parts by weight) is about 10 to 100 μm in film thickness on a base material (about 100 μm) PET resin film. Using a high pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., 80 W / cm) as a light source, light irradiation was performed so that the integrated light amount was 400 mJ / cm ² (365 nm) (conditions: room temperature in air, About the coating film obtained by carrying out the irradiation of all wavelengths, the evaluation test of the following item was done. The evaluation test results are shown in Table 2.

<Example 5, Comparative Example 3>
The thermosetting resin composition weighed in the proportions shown in Table 1 below (values represent parts by weight) was placed on a base (about 100 μm) PET resin film so that the film thickness was about 10 to 1000 μm. About the coating film obtained by coating with a coater and heating at 60 ° C. for 6 hours, the following evaluation tests were performed. The evaluation test results are shown in Table 2.

<Evaluation method>
(1) Adhesion: Evaluated according to JIS-K5400, and makes 100 grids by making 11 vertical and horizontal cuts at 1 mm intervals on the surface of the coating film. After the cellophane tape was brought into close contact with the surface, when the cellophane tape was peeled off at once, the remaining squares were evaluated. (A sample that was not peeled off at all was rated as “◯”, a sample that was partially peeled off was “Δ”, and a sample that was partially peeled off was marked “x”).
(2) Appearance of coating film: Surface cracks, whitening, cloudiness, and the like were evaluated by visual observation (“Good” indicates “good”, and “B” indicates poor).
(3) Transparency: The total light transmittance was evaluated in accordance with JIS-K7105 (“○” indicates that the transmittance is 90% or more and “×” indicates that the transmittance is 90% or less) .
(4) Coating film hardness: Evaluated according to pencil hardness test JIS-K5400. The pencil was scratched at an angle of 45 degrees by applying a load of 1 kg from above and scratched for about 5 mm, and the degree of damage was confirmed.
(5) Heat resistance: The state after being left in a dryer at 130 ° C. for 2 hours was evaluated. (No change, crack or discoloration was indicated with “◯”, and one with deformation or discoloration was indicated with “X”).
(6) Weather resistance: The state after the coating film was exposed outdoors for half a year was evaluated. (The case where appearance discoloration is hardly seen is indicated by “◯”, and the case where appearance discoloration is observed is indicated by “X”).
(7) Surface resistance value: Evaluation was made using a SM-10E type ultra-insulation meter (manufactured by Toa Radio).

  As described above, the active energy ray or thermosetting resin composition of the present invention is cured by the active energy ray or heat, maintains the adhesion to the substrate and the coating film strength, and also by bleed-out of the antistatic agent. A cured resin having no surface contamination and good antistatic properties, transparency, weather resistance, film flexibility and heat resistance can be obtained.

The active energy ray-curable resin composition of the present invention is, for example, as a coating material for image display bodies such as home appliances, mobile phones, LCDs (liquid crystal displays), PDPs (plasma displays), CRTs, ELs, etc. Application as electronics materials such as UV curable paints and dicing tape applications is possible.

Claims (3)

A trifunctional polyisocyanate represented by the following general formula (1) and a hydroxyl group-containing (meth) acrylate containing 60 to 100 wt% of a hydroxyl group-terminated polyalkylene glycol mono (meth) acrylate represented by the following general formula (4): An antistatic resin composition using a prepolymer reacted at a ratio of 0.8 to 1.2 in terms of group equivalent / hydroxyl equivalent.

(R ₁ represents a group represented by the following general formulas (2) and (3).)

(R ₂ represents a hydrogen atom or a methyl group, and R ₃ represents a group represented by the following general formulas (5), (6), (7), (8)).

(A represents a positive number from 1 to 15.)

(B represents a positive number from 1 to 15.)

(C and d are positive numbers of 1 or more.)

(E and f are positive numbers of 1 or more.)   An active energy ray-curable resin composition comprising a reactive diluent having a (meth) acryloyl group or an epoxy resin and a photopolymerization initiator in the antistatic resin composition according to claim 1. The thermosetting resin composition formed by mix | blending the reactive diluent which has a (meth) acryloyl group, an epoxy resin, and a hardening | curing agent with respect to the resin composition for antistatics of Claim 1.