JP2014091786A - Radiation-curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-curable composition capable of easily yielding a film meeting both fingerprint wipe-off and recoatability demands and having excellent durability.SOLUTION: The provided radiation-curable composition includes: a curable resin including a (meth)acryloyl group-containing urethane oligomer possessing, as constituent units, hydrogenated MDI and/or hydrogenated XDI and a hydroxyl group-containing (meth)acrylate; and a polyoxyalkylene compound expressed by the formula (1) and/or a reaction product of this polyoxyalkylene compound and a diisocyanate: {H-(OX)ni-}mQ (1): Q is a reactive residue obtained by excluding hydrogen atoms from m-pieces of primary hydroxyl groups of a non-reducible di- or trisaccharide; OX is an oxyalkylene; ni is 0 to 100; m is 2 to 4; i is 1 to m.

Description

  The present invention relates to a radiation curable composition.

  For the purpose of providing an optical film with excellent water / oil repellency, antifouling properties, scratch resistance, hydrolysis resistance, and coating liquid leveling, a hard coat layer is provided on at least one surface of the transparent substrate film. In the optical film, the hard coat layer contains an active energy ray curable resin as a main component, and the hard coat layer contains (meth) acrylate containing a fluorinated alkyl group with respect to the active energy ray curable resin. An “optical film comprising 0.02% by weight or more and 30% by weight or less” is known (Patent Document 1).

JP 2009-104054 A

However, the conventional radiation curable composition has a problem that recoatability on the surface of the cured film is extremely poor, and printing on the surface of the cured coating film and multilayer coating cannot be performed.
That is, an object of the present invention is to provide a radiation curable composition that can easily obtain a film having excellent wiping property and recoating property and excellent durability.

The radiation-curable composition of the present invention is characterized by 4,4′-dicyclohexylmethane diisocyanate and / or bis (isocyanatomethyl) cyclohexane and a hydroxy group-containing (meth) acrylate as structural units. A curable resin (A) containing a urethane oligomer (A1);
The gist is that the polyoxyalkylene compound (B1) represented by the general formula (1) and / or the polyoxyalkylene compound (B1) and a reaction product (B2) of diisocyanate are contained.

  The feature of the plastic film of the present invention is that it is obtained by coating the radiation curable composition on a plastic base film and curing it.

The radiation curable composition of the present invention is excellent in durability, fingerprint wiping property and recoating property.
Therefore, when the radiation curable composition of the present invention is used, a film having both excellent wipeability and recoatability and excellent durability can be easily obtained.

  Since the above-mentioned radiation curable composition is used for the plastic film of the present invention, both the wiping property of fingerprints and the recoating property are compatible, and the durability is excellent.

  In the present invention, “(meth) acrylate” means acrylate and / or methacrylate, and “(meth) acryloyl group” means acryloyl group and / or methacryloyl group.

<Curable resin (A)>
The curable resin (A) means a substance that is cured by radiation (preferably ultraviolet rays and electron beams, more preferably ultraviolet rays). In addition to the (meth) acryloyl group-containing urethane oligomer (A1), (meth) acrylate It is preferable that (A2) and / or a photoinitiator (A3) etc. are included.

As the (meth) acryloyl group-containing urethane oligomer (A1), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) and / or bis (isocyanatomethyl) cyclohexane (hydrogenated XDI) and hydroxy group-containing (meth) acrylate As a structural unit, a diol and / or a trihydric or higher polyol may be included as a structural unit.
The (meth) acryloyl group-containing urethane oligomer (A1) is obtained by reacting hydrogenated MDI, hydrogenated XDI and / or these isocyanate-modified products with a hydroxy group-containing (meth) acrylate, and this reaction is a known method. {For example, the method described in JP 2007-204567 A} can be applied.

  Isocyanate-modified products include hydrogenated MDI or hydrogenated XDI nurate, burette or adduct, etc .; urethane prepolymer obtained from the reaction of hydrogenated MDI or hydrogenated XDI with a trivalent or higher polyol and / or diol Hydrogenated MDI, hydrogenated XDI, these nurate bodies, burette bodies or adduct bodies, and monoisocyanates produced by reaction of monoalcohols and / or polyols (including diols and trivalent or higher polyols). Can be mentioned.

  Examples of the trivalent or higher polyol include polyhydric alcohols having 3 to 15 carbon atoms (such as glycerin, trimethylolpropane, dimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol) and polyhydric alcohols having 3 to 15 carbon atoms. Of alkylene oxide (2 to 3 carbon atoms) adduct (3 to 100 mol adduct of glycerin ethylene oxide, 3 to 100 mol adduct of propylene oxide of glycerin, 3 to 100 mol adduct of ethylene oxide of trimethylolpropane, trimethylolpropane Propylene oxide 3 to 100 mol adduct, Ditrimethylolpropane ethylene oxide 4 to 100 mol adduct, Dimethylolpropane propylene oxide 4 to 100 mol adduct, Pentaerythritol ethylene oxide 4 100 mol adduct, propylene oxide 4-16 mol adduct of pentaerythritol, ethylene oxide 6-100 mol adduct of dipentaerythritol, propylene oxide 4-100 mol adduct of dipentaerythritol, ethylene oxide 8-100 of tripentaerythritol Mole adduct, propylene oxide 8 to 100 mol adduct of tripentaerythritol, ethylene oxide 3 to 100 mol adduct of isocyanuric acid and propylene oxide 3 to 100 mol adduct of isocyanuric acid) and the like.

  As the diol, any compound having two hydroxy groups can be used without limitation, and a glycol having 2 to 10 carbon atoms (ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, neopentyl glycol, Diol (addition number 1 to 80) obtained by adding alkylene oxide (2 to 3 carbon atoms) to hexanediol, cyclohexanediol and cyclohexanedimethylol) and an active hydrogen compound (such as glycol having 2 to 10 carbon atoms and bisphenol A) ( An alkylene oxide adduct of a diol having 2 to 10 carbon atoms and an alkylene oxide adduct of bisphenol A). In addition to these, a linear polyester produced from a diol and a dicarboxylic acid and having a hydroxy group at the terminal can also be used as the diol. As dicarboxylic acid, if it is a compound which has two carboxy groups, it can be used without limitation, C2-C10 dicarboxylic acid etc. are used, and oxalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid , Glutaric acid and azelaic acid.

  As the monoalcohol, any compound having one hydroxy group can be used without limitation. The monoalcohol has 1 to 4 monoalcohols (methanol, ethanol, isopropanol, butanol, etc.) and 1 to 4 alcohols with 2 carbon atoms. -4 alkylene oxides (ethylene oxide, propylene oxide, butane oxide, etc.) added to the product (addition number 1 to 10) and the like.

  Reaction of hydrogenated MDI or hydrogenated XDI with diol and / or trivalent or higher polyol; Reaction of hydrogenated MDI, hydrogenated XDI, their nurate body, burette body or adduct body with monoalcohol and / or polyol The usual methods (reaction ratio, reaction conditions, etc.) can be applied.

  Of these, hydrogenated MDI, hydrogenated XDI, and hydrogenated MDI or hydrogenated XDI and urethane prepolymers obtained from the reaction of diols and / or trivalent or higher polyols are preferred, and hydrogenated MDI, water are more preferred. It is a urethane prepolymer containing propylene glycol as the diol as well as XDI.

  As the hydroxy group-containing (meth) acrylate, any (meth) acrylate containing at least one hydroxy group in one molecule can be used, and the hydroxy group-containing (described in JP-A No. 2004-352781 ( A (meth) acrylate etc. can be used.

  The number of (meth) acryloyl groups contained in one molecule of the (meth) acryloyl group-containing urethane oligomer (A1) is preferably 1 to 15, more preferably 2 to 12. The number of (meth) acryloyl groups is preferably 3 to 12 when the radiation curable composition of the present invention is used for applications in which scratch resistance is important, and in applications in which molding / workability is important. When using, 2-6 are preferable.

These (meth) acryloyl group-containing urethane oligomers (A1) may be used alone or in combination of two or more.
When the curable resin (A) contains (meth) acrylate (A2) and / or photopolymerization initiator (A3), the content (% by weight) of the (meth) acryloyl group-containing urethane oligomer (A1) is: Based on the weight of curable resin (A), 3-95 are preferable, More preferably, it is 5-90, Most preferably, it is 10-85. When it is in this range, the fingerprint wiping property and durability of the ultraviolet curable composition of the present invention are further improved.

  As (meth) acrylate (A2), the (meth) acrylate etc. which were described in Unexamined-Japanese-Patent No. 2004-352781 can be used. The (meth) acrylate (A2) includes a (meth) acryloyl group-containing urethane oligomer that does not contain hydrogenated MDI and / or hydrogenated XDI as a structural unit.

  As a (meth) acryloyl group-containing urethane oligomer not containing hydrogenated MDI and / or hydrogenated XDI as a structural unit, an aliphatic diisocyanate {isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), etc.} is used as a structural unit (meta ) An acryloyl group-containing aliphatic urethane oligomer and an aromatic diisocyanate {toluene diisocyanate (TDI) and 4,4′-diphenylmethane diisocyanate (MDI), etc.} are included as structural units. Among these, from the viewpoint of fingerprint wiping properties, (meth) acryloyl group-containing aliphatic urethane oligomers are preferable, and (meth) acryloyl group-containing aliphatic urethane oligomers having IPDI as a structural unit are more preferable.

  The number of (meth) acryloyl groups contained in one molecule of (meth) acrylate (A2) is appropriately determined depending on the number and / or content of (meth) acryloyl groups of (meth) acryloyl group-containing urethane oligomer (A1). Although adjusted, 1-10 are preferable, More preferably, it is 2-8, Most preferably, it is 4-6. Within this range, the curability of the radiation curable composition of the present invention is further improved.

  When (meth) acrylate (A2) is included, from the viewpoint of scratch resistance, it is preferable to contain (poly) pentaerythritol poly (meth) acrylate as (meth) acrylate (A2), more preferably pentaerythritol tris. Containing (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, particularly preferably dipentaerythritol penta (meth) acrylate and dipentaerythritol It contains hexa (meth) acrylate.

These (meth) acrylates (A2) may be used alone or in combination of two or more.
When (meth) acrylate (A2) is contained, the content (% by weight) of (meth) acrylate (A2) is preferably 2 to 95, more preferably 5 based on the weight of curable resin (A). ~ 90, particularly preferably 10-85. When it is in this range, the fingerprint wiping property and durability of the ultraviolet curable composition of the present invention are further improved.

  As a photoinitiator (A3), if it is a compound which can start superposition | polymerization of curable resin (A) by receiving light {preferably ultraviolet-ray (wavelength of about 200-400 nm)}, it can be used without a restriction | limiting, A compound that generates a radical by receiving light is preferable, and a benzoyl group-containing radical initiator, a morpholinyl group-containing radical initiator, a phosphorus atom-containing radical initiator, and a sulfur atom-containing radical initiator are more preferable.

  Examples of the benzoyl group-containing radical initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Examples include 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) benzyl] phenyl] -2-methylpropan-1-one and benzophenone.

  Examples of morpholyl group-containing radical initiators include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). ) Butan-1-one and the like.

  Phosphorus atom-containing radical initiators include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and 2,4 , 6-trimethylbenzoyldiphenylphosphine oxide and the like.

  Examples of the sulfur atom-containing radical initiator include 2,4-diethylthioxanthone and isopropylthioxanthone.

  These photopolymerization initiators (A3) may be used alone or in combination of two or more. Of these photopolymerization initiators (A3), a photoradical initiator is preferred, more preferably a benzoyl group-containing radical initiator, a morpholinyl group-containing radical initiator, and a phosphorus atom-containing radical initiator, particularly preferably a benzoyl group-containing radical. It is an initiator and a morphol group-containing radical initiator.

  When the photopolymerization initiator (A3) is contained, the content (% by weight) of the photopolymerization initiator (A3) is preferably from 1 to 15, more preferably 2 based on the weight of the curable resin (A). -12, particularly preferably 3-10. Within this range, the curability of the radiation curable composition is further improved.

<Polyoxyalkylene compound (B1) and / or reactant (B2) represented by general formula (1)>
When the polyoxyalkylene compound (B1) represented by the general formula (1) and / or the polyoxyalkylene compound (B1) and a reaction product (B2) of diisocyanate are contained, excellent fingerprint wiping properties and the like are imparted. Can do.

  In the general formula (1), the di- or trisaccharide that can constitute the reaction residue (Q) obtained by removing a hydrogen atom from m hydroxyl groups of a non-reducing di- or trisaccharide includes sucrose, Trehalose, isotrehalose, isosaccharose, gentianose, raffinose, meletitose and planteose are included. Of these, sucrose, trehalose, gentianose, raffinose and planteose are preferable from the viewpoint of fingerprint wiping properties, more preferably trehalose and sucrose, and sucrose is particularly preferable from the viewpoints of supplyability and cost.

  The oxyalkylene group (OX) includes an oxyalkylene group having 2 to 4 carbon atoms, and examples thereof include oxyethylene, oxypropylene, oxybutylene, and a mixture thereof. Of these, oxypropylene and oxyethylene are preferable from the viewpoint of fingerprint wiping properties, and oxypropylene is more preferable.

  The ni OXs may be the same or different, and the m (OX) ni may be the same or different. In the case where (OX) ni includes a plurality of types of oxyalkylene groups, there is no limitation on the bonding order (block shape, random shape and combinations thereof) and the content ratio of these oxyalkylene groups.

  ni is preferably an integer of 0 to 100, more preferably an integer of 2 to 98, particularly preferably an integer of 5 to 95, and most preferably an integer of 7 to 90. Within this range, the fingerprint wiping property is further improved.

  m is preferably an integer of 2 to 4, more preferably 3 or 4, and particularly preferably 3. Within this range, the fingerprint wiping property is further improved. This m corresponds to the number of primary hydroxyl groups of the non-reducing di- or trisaccharide.

  i represents an integer of 1 to m, and m ni may be the same value or different values, but at least one ni is 1 or more. That is, for example, when m = 4, ni means n1, n2, n3, and n4.

  The total number of OX (Σni × m) is preferably an integer of 20 to 100, more preferably an integer of 20 to 90, particularly preferably an integer of 25 to 85, and most preferably an integer of 35 to 75. Within this range, the fingerprint wiping property is further improved.

  Preferred examples of the polyoxyalkylene compound (B1) include those described in International Patent Application Pamphlet WO2004 / 101103 (Republished 2004-101103).

  Examples of the diisocyanate include compounds having 6 to 13 carbon atoms having two isocyanato groups, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate, hydrogenated MDI. And hydrogenated XDI. As the diisocyanate, diisocyanate prepolymers obtained by reaction of these compounds with diols can also be used. Of these, HDI, IPDI, hydrogenated MDI, hydrogenated XDI, and diisocyanate prepolymers obtained by reacting these compounds with diols are preferred. Of the diols, from the viewpoint of fingerprint wiping properties, a diol having 2 to 10 carbon atoms and an alkylene oxide (2 to 3 carbon atoms) adduct of a diol having 2 to 10 carbon atoms (addition number 1 to 50) are preferable. More preferred is a diol having 2 to 10 carbon atoms.

  In the reaction product (B2) of the polyoxyalkylene compound (B1) and the diisocyanate, the content (mole part) of the diisocyanate unit is 0.1 to 0.0.1 with respect to 1 mol part of the polyoxyalkylene compound (B1) unit. 8, more preferably 0.15 to 0.75, particularly preferably 0.2 to 0.7, and most preferably 0.25 to 0.65.

  The polyoxyalkylene compound (B1) and the reactant (B2) are prepared by a known method {International Patent Application Pamphlet WO 2004/101103 (Republished 2004-101103), JP 2007-92040 A, JP 2004-224945 A. Gazettes etc.} can be easily obtained.

  The total content (% by weight) of the polyoxyalkylene compound (B1) and the reactant (B2) is preferably from 0.01 to 10, more preferably from 0.1 to 10, based on the weight of the curable resin (A). 5, particularly preferably 0.5 to 3. Within this range, the fingerprint wiping property can be further improved without deteriorating the performance (curing performance, scratch resistance, etc.) of the radiation curable composition.

  As the polyoxyalkylene compound (B1) and the reactant (B2), in addition to the above, a compound in which a (meth) acryloyl group is introduced into the polyoxyalkylene compound (B1) and the reactant (B2) {polyoxyalkylene compound (B1 ') And reactant (B2')} can also be used. When the polyoxyalkylene compound (B1 ′) and the reactant (B2 ′) are used, the durability of the radiation curable composition of the present invention can be further improved.

  As a method for introducing a (meth) acryloyl group into the polyoxyalkylene compound (B1) and the reaction product (B2), a known method can be applied. The polyoxyalkylene compound (B1) or the reaction product (B2) and a hydroxy group-containing Reaction of (meth) acrylate with dicarboxylic acid (maleic acid, phthalic acid, etc.) or diisocyanate {esterification reaction or urethanization reaction}, polyoxyalkylene compound (B1) or reactant (B2), (meth) A method by a reaction with glycidyl acrylate, 2-acryloylethyl isocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, or the like can be applied.

  The number of (meth) acryloyl groups contained in the polyoxyalkylene compound (B1 ′) and the reactant (B2 ′) is preferably 1 to 3 per molecule.

<Filler (C)>
The radiation curable composition of the present invention may contain a filler (C). When the filler (C) is contained, the scratch resistance can be further improved.

  As a filler (C), an inorganic filler (C1) and an organic filler (C2) are contained.

  As the inorganic filler (C1), silica, titanium oxide, talc, clay, calcium carbonate, calcium silicate, barium sulfate, mica, diatomaceous earth silica, aluminum hydroxide, alumina, zirconium oxide, zirconium hydroxide, tin oxide, zinc oxide , Antimony pentoxide, indium oxide, and zinc antimonate. Moreover, what doped these metal oxides with tin, antimony, phosphorus, gallium, etc. can also be used.

  The inorganic filler (C1) may be in the form of an inorganic filler sol dispersion dispersed in a solvent or the like. Such inorganic filler sol dispersions can be easily obtained from the market, and examples thereof include organosilica sol series and Celnax series (manufactured by Nissan Chemical Industries, Ltd., “Cellnax” is a registered trademark of the company). .

  Examples of the organic filler (C2) include an acrylic resin filler, a styrene resin filler, an acrylic / styrene resin filler, a urethane resin filler, a polyethylene filler, and a silicone resin filler.

  The organic filler (C2) may be in the form of a dispersion dispersed in a dispersion medium. Such a dispersion can be prepared by a known method {for example, JP 2007-99897 A}. The organic filler (C2) can also be used after removing the dispersion medium from such a dispersion by drying or the like.

  Of these fillers (C), in the case of applications requiring transparency, inorganic fillers, acrylic resin fillers and mixtures thereof are preferable, more preferably inorganic fillers, particularly preferably silica, alumina, tin oxide and zinc oxide. Most preferred are silica, tin oxide and zinc oxide. On the other hand, when transparency is not required, inorganic fillers and acrylic resin fillers, polyethylene fillers and mixtures thereof are preferred, more preferably silica, alumina, acrylic resin fillers, polyethylene fillers and mixtures thereof, particularly preferably silica and acrylic resins. Fillers, polyethylene fillers and mixtures thereof.

  The volume average particle diameter of the filler (C) is preferably 1 nm to 10 μm, more preferably 3 nm to 8 μm, and particularly preferably 5 nm to 6 μm. Within this range, the scratch resistance is further improved.

  When the radiation curable composition of the present invention is applied to a use requiring transparency, the volume average particle diameter (nm) of the filler (C) is preferably 1 to 400, more preferably 5 to 200, and particularly preferably. Is 10-100. Within this range, the transparency of the coating film is further improved.

  When the radiation curable composition of the present invention is applied to uses where transparency is not required, the volume average particle diameter (μm) of the filler (C) is preferably 0.5 to 10, more preferably 1 to 8, particularly. Preferably it is 2-6. Within this range, the scratch resistance of the coating film is further improved.

  The volume average particle size is determined by dispersing the measurement sample in an appropriate dispersion medium (for example, water, methanol and a mixture thereof), and JIS Z8825-1-2001 “Particle Size Analysis—Laser Diffraction Method—Part 1”: Laser diffraction particle size distribution measuring apparatus having the measurement principle described in the measurement principle (for example, SALD-1100 manufactured by Shimadzu Corporation, LA-950 manufactured by Horiba, Ltd., Microtrack particle size distribution measuring apparatus UPA- manufactured by Nikkiso Co., Ltd.) ST150, “Microtrack” is a registered trademark of Leeds, And, Northlap, Company).

  When the filler (C) is contained, the content (% by weight) of the filler (C) is preferably 1 to 150, more preferably 3 to 120, particularly preferably based on the weight of the curable resin (A). 5-100. Within this range, the scratch resistance is further improved.

<Polyoxyalkylene-modified silicone (D)>
The radiation curable composition of the present invention may further contain a polyoxyalkylene-modified silicone (D) for the purpose of further improving the leveling property. Examples of the polyoxyalkylene-modified silicone (D) include branched polyoxyalkylene-modified silicone (D1), terminal-modified polyoxyalkylene-modified silicone (D2), and block-type polyoxyalkylene-modified silicone (D3).

  The branched polyoxyalkylene-modified silicone (D1) is a silicone in which a polyoxyalkylene chain is chemically bonded as a side chain of a dimethylsiloxane chain, and SH3746 [HLB = 10], SH8428 [HLB = 0], SH3771 [ HLB = 14], BY16-036 [HLB = 9], BY16-027 [HLB = 7], SH8400 [HLB = 8], SH3749 [HLB = 7], SH3748 [HLB = 5], SF8410 [HLB = 6] , L-77 [HLB = 10], L-7001 [HLB = 7], L-7002 [HLB = 7], L-7604 [HLB = 13], Y-7006 [HLB = 7], FZ-2101 [ HLB = 9], FZ-2104 [HLB = 14], FZ-2105 [HLB = 11], FZ-2110 [HL = 1], FZ-2118 [HLB = 12], FZ-2120 [HLB = 6], FZ-2123 [HLB = 8], FZ-2130 [HLB = 7], FZ-2161 [HLB = 18], FZ -2162 [HLB = 15], FZ-2163 [HLB = 13], FZ-2164 [HLB = 8], FZ-2166 [HLB = 5] and FZ-2191 [HLB = 5] Made by company}; KF-351 [HLB = 12], KF-352 [HLB = 7], KF-353 [HLB = 10], KF-354L [HLB = 16], KF-355A [HLB = 12], KF -615A [HLB = 10], KF-945 [HLB = 4], KF-618 [HLB = 11], KF-6011 [HLB = 12] and KF-6015 [HLB = 4] Manufactured by Shin-Etsu Chemical Co., Ltd.}; TSF4440 [HLB = 12], TSF4445 [HLB = 7], TSF4446 [HLB = 7], TSF4452 [HLB = 7], TSF4453 [HLB = 6] and TSF4460 [HLB = 1] {Manufactured by Toshiba Silicone Co., Ltd.}; and TEGOPREN 5000 series [HLB = 3-15] {manufactured by DEGUSSA}.

  The terminal-modified polyoxyalkylene-modified silicone (D2) is a silicone in which a polyoxyalkylene chain is chemically bonded to a terminal (one terminal or both terminals) of a dimethylsiloxane chain, and L-720 [HLB = 7] and FZ-2122 [HLB = 1] {manufactured by Toray Dow Corning Co., Ltd.} and the like.

  The block-type polyoxyalkylene-modified silicone (G3) is a silicone in which a dimethylsiloxane chain and a polyoxyalkylene chain are repeatedly chemically bonded in a block shape, and SF8427 [HLB = 10] and BY16-004 [HLB = 0] {above, manufactured by Toray Dow Corning Co., Ltd.}; KF-6004 [HLB = 5] {above, manufactured by Shin-Etsu Chemical Co., Ltd.}; FZ-2203 [HLB = 1], FZ-2207 [HLB = 3] and FZ-2208 [HLB = 7] {above, manufactured by Nihon Unicar Co., Ltd.}; and TEGOPREN 3000 series [HLB = 1-5] {above, manufactured by DEGUSSA}.

  Of these polyoxyalkylene-modified silicones (D), branched polyether-modified silicones (D1) are preferred from the viewpoint of fingerprint wiping properties. These polyoxyalkylene-modified silicones (D) can be used as one kind or a mixture of two or more kinds, but when used as a mixture of two or more kinds, it is preferable to include a branched polyoxyalkylene-modified silicone (D1). .

  The hydrophilic / lipophilic balance (HLP of Griffin) of the polyoxyalkylene-modified silicone (D) is preferably 20 or less, more preferably 15 or less, particularly preferably 10 or less, and most preferably 5 or less. Within these ranges, the fingerprint wiping property is further improved, which is preferable. In addition, the HLB of Griffin is calculated | required by the method of calculating from the organic and inorganic ratio of surfactant described in the 127-129 page of a new surfactant introduction (Sanyo Kasei Kogyo Co., Ltd. issue).

  When the polyoxyalkylene-modified silicone (D) is contained, the content (% by weight) of the polyoxyalkylene-modified silicone (D) is preferably 0.01 to 2 based on the weight of the curable resin (A). More preferably, it is 0.03-1, Most preferably, it is 0.05-0.5. Within this range, the leveling property can be further improved without adversely affecting the fingerprint wiping property.

<Polymer (E)>
The radiation curable composition of the present invention may contain a polymer (E). When the polymer (E) is contained, the impact resistance can be further improved.

  As a polymer (E), the polymer etc. which were described in Unexamined-Japanese-Patent No. 2009-114302 can be used, and vinyl polymer (E1), polyester (E2), and polyurethane (E3) are contained.

  When the polymer contains (E), the content (% by weight) of the polymer (E) is preferably 1 to 150, more preferably 3 to 100, particularly preferably based on the weight of the curable resin (A). Is 5-50. Within this range, the moldability / workability of the radiation curable composition is further improved.

<Solvent (F)>
The radiation curable composition of the present invention may further contain a solvent (F) as necessary for the purpose of further improving handling properties (coating properties and the like).

  Examples of the solvent (F) include a curable resin (A), a polyoxyalkylene compound (B1), a reaction product (B2), and other components that can be contained if necessary {polyoxyalkylene-modified silicone (D) and / or polymer ( E)} can be dissolved uniformly {if the filler (C) is included as another component, the filler (C) can be uniformly dispersed} may be a solvent such as ketone (acetone, methyl ethyl ketone and methyl isobutyl ketone), glycol Ethers (such as methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether and propylene glycol monoethyl ether), glycol esters (methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ether acetate and propylene glycol ethyl ether) Ether acetate, etc.), alcohols (methanol, ethanol, propanol and butanol) and aromatic hydrocarbons (toluene and xylene) is. These solvents (F) are used alone or in combination.

  When it contains a solvent (F), content of a solvent (F) is suitably determined by the viscosity of a radiation-curable composition, the coating method, the film thickness after drying, etc.

<Photosensitizer (G)>
The radiation-curable composition of the present invention can further contain a photosensitizer (G) for the purpose of further improving curability.

  As a photosensitizer (G), a well-known photosensitizer etc. can be used and an alkylamino photosensitizer (G1) and a dialkylaminophenyl photosensitizer (G2) are contained.

  Examples of the alkylamino photosensitizer (G1) include monoalkylamines (such as n-butylamine and 2-ethylhexylamine), dialkylamines (such as din-butylamine, diethanolamine, and methyldecylamine), and trialkylamines (trimethylamine, triethylamine). , Triethanolamine, triisopropanolamine, 2-dimethylaminoethylbenzoic acid and the like).

  As the dialkylaminophenyl photosensitizer (G2), 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, ethyl dimethylaminobenzoate, 2- (n-butoxy) ethyl dimethylaminobenzoate and dimethyl An aminobenzoic acid isoacyl etc. are mentioned.

In addition to these, phosphorus compounds such as tri-n-butylphosphine can also be used as the photosensitizer (G).
Of these photosensitizers (G), trialkylamine and dialkylaminophenyl photosensitizer (G2) are preferable, more preferably dialkylaminophenyl photosensitizer (G2), and particularly preferably 4,4 ′. -Dialkylaminobenzophenone.

  When the photosensitizer (G) is contained, the content (% by weight) of the photosensitizer (G) is preferably 0.1 to 100 based on the weight of the photopolymerization initiator (A3). Preferably, it is 1-50, Most preferably, it is 5-50. In addition, when not containing a photoinitiator (A3), a photosensitizer (G) is also not contained.

<Ultraviolet absorber (H)>
The radiation curable composition of the present invention may contain an ultraviolet absorber (including a light stabilizer) (H) for the purpose of improving the weather resistance. Examples of the ultraviolet absorber (H) include benzotriazole ultraviolet absorber (H1), hindered amine ultraviolet absorber (H2), benzophenone ultraviolet absorber (H3), salicylic acid ultraviolet absorber (H4) and triazine ultraviolet absorber (H5). included.

  Examples of the benzotriazole ultraviolet absorber (H1) include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole. .

  As the hindered amine ultraviolet absorber (H2), bis (1,2,2,6,6-pentamethyl-4-piperidyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl) ] Butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl sebacate and bis (2,2,6) , 6-tetramethyl-4-piperidyl) sebacate and the like.

  Examples of the benzophenone ultraviolet absorber (H3) include 2,4-dihydrobenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone and 2,2 ′. -Dihydroxy-4-methoxybenzophenone etc. are mentioned.

  Examples of the salicylic acid ultraviolet absorber (H4) include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.

  As a triazine ultraviolet absorber (H5), 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine and 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl-1,3,5-triazine).

  These ultraviolet absorbers (H) may be used alone or in combination of two or more, and when used in combination of two or more, hindered amine ultraviolet absorber (H2) and triazine ultraviolet absorber (H5). Is preferably used together. Of these ultraviolet absorbers (H), benzotriazole ultraviolet absorbers (H1), hindered amine ultraviolet absorbers (H2) and triazine ultraviolet absorbers (H5) are preferred, more preferably hindered amine ultraviolet absorbers (H2) and triazines. It is an ultraviolet absorber (H5).

  When the ultraviolet absorber (H) is contained, the content (% by weight) of the ultraviolet absorber (H) is preferably 0.1 to 10, more preferably 0, based on the weight of the curable resin (A). .3 to 8, particularly preferably 0.5 to 5.

<Other additives>
The radiation curable composition of the present invention may contain other additives (for example, dyes, pigments, heat stabilizers, adhesion promoters, antifoaming agents, anti-sagging agents, and / or flame retardants) as necessary. Can be added.
When other additives are contained, the total content (% by weight) of other additives can exhibit the characteristics of each additive and can be added within a range that does not impair the effects of the present invention. Based on the weight of (A), 0.01-50 are preferable, More preferably, it is 0.05-30, Most preferably, it is 0.1-10.

  The radiation-curable composition of the present invention can be easily obtained by uniformly mixing and dispersing the respective constituent components, and the production method is not limited.

  When the polymer (E) is contained, the polymer (E) is uniformly dissolved in the solvent (F) to obtain a polymer solution, and then the curable resin (A), the polyoxyalkylene compound (B1), and the reaction product (B2). If necessary, other components {filler (C), polyoxyalkylene-modified silicone (D), photosensitizer (G), ultraviolet absorber (H) and / or other additives} and the polymer solution are uniformly mixed. It is preferable to do.

  When the filler (C) is contained, the filler (C) is uniformly dispersed in the solvent (F) to prepare a filler dispersion, and then the curable resin (A), the polyoxyalkylene compound (B1), the reactant ( B2) and other components {polyoxyalkylene-modified silicone (D), polymer (E), photosensitizer (G), ultraviolet absorber (H) and / or other additives} if necessary, and filler dispersion Are preferably mixed uniformly.

  The disperser for dispersing and mixing the filler (C) is not particularly limited as long as it can be uniformly dispersed. For example, a dissolver, a twin screw mixer, a three screw mixer, a planetary mixer, a three screw planetary mixer, three rolls, Examples thereof include a ball mill and a bead mill. Among these, a dissolver, a 2-axis mixer, a 3-axis mixer, and a 3-axis planetary mixer are preferable, a dissolver, a 3-axis mixer, and a 3-axis planetary mixer are more preferable, and a dissolver and a 3-axis planetary mixer are particularly preferable.

  The temperature (° C.) of the dispersion and mixing is not particularly limited as long as it can be uniformly dispersed, but is preferably 10 to 60, more preferably 15 to 50, and particularly preferably 20 to 40.

  Although there will be no restriction | limiting in particular if it can disperse | distribute uniformly as time (minutes) of dispersion | distribution mixing, 10-600 are preferable, More preferably, it is 20-300, Most preferably, it is 30-180.

  The temperature for uniform mixing (° C.) is not particularly limited as long as uniform mixing can be performed, but is preferably 25 to 60, more preferably 30 to 50, and particularly preferably 35 to 45.

The radiation-curable composition of the present invention can be applied to various plastic protective layers, and is particularly suitable as a protective layer for plastic base films to which fingerprints adhere, such as touch panels.
The protective layer can be obtained by coating the plastic base film with the radiation curable composition of the present invention, heating and drying it if necessary, and then irradiating it with radiation.
As a coating method, a roll coating method, a dip method, a spray method, a flow coating method, a screen printing method, or the like can be applied.

In the case of heat drying, the heat drying temperature (° C.) is preferably about 30 to 120, more preferably 40 to 110, and particularly preferably 50 to 100. The heating temperature may be changed stepwise (for example, temperature increase) within this range.
The heat drying time (minutes) is preferably about 0.5 to 30, and more preferably 1 to 20.

The radiation dose (mJ / cm ² ) is preferably about 100 to 2,000, and more preferably 200 to 1,000.

  When the radiation curable composition of the present invention is applied to a plastic base film, the thickness (μm) of the coating layer of the radiation curable composition is preferably about 0.1 to 100, more preferably 1 to 30. .

  Examples of the material for the plastic base film include polyethylene terephthalate, polycarbonate, triacetyl cellulose, and polymethyl methacrylate. Of these, polyethylene terephthalate, polycarbonate and polymethyl methacrylate are preferred.

  The thickness (μm) of the plastic base film is preferably about 10 to 5000, and more preferably 50 to 2000.

  The plastic film obtained by coating and curing the radiation curable composition of the present invention on a plastic base film can be applied to a protective film for a touch panel, a film for automobile interior, a molded film for an electronic device casing such as a mobile phone, and the like. .

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.
The heating residue was measured in accordance with JIS K5601-1-2: 2008 under the conditions of 105 ° C. and 1 hour (dish: diameter 70 mm, edge height 15 mm, circulating air dryer).

<Production Example 1>
4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) (trade name: Desmodur W, manufactured by Sumika Bayer Urethane Co., Ltd., "Desmodur" is Bayer 262 parts (1 mole part), hydroxy group-containing (meth) acrylate (hm1) {trade name: Light acrylate PE-3A, manufactured by Kyoeisha Chemical Co., Ltd., pentaerythritol tetra- , A mixture of tri- and di-acrylate (35: 60: 5 by weight ratio)} 826 parts (1.7 mol parts of triacrylate, 0.2 mol parts of diacrylate, 2 mol parts of hydroxy group contained), dibutyltin Dilaurate (reaction catalyst) 0.05 parts, hydroquinone monomethyl ether (polymerization inhibitor) .5 parts of methyl ethyl ketone 273 parts After 30 minutes stirring put (heating residue theoretical value of 80%) was gradually raised to refluxing. Further, the reflux was continued until the isocyanate group content became 0.2%. Thereafter, the mixture is cooled to 30 ° C. or lower, filtered through a stainless steel mesh with a mesh opening of 45 μm, the heating residue of the filtrate is measured, adjusted with methyl ethyl ketone to 80%, and then methyl ethyl ketone of the acryloyl group-containing urethane oligomer (a11). A solution was obtained.
The acryloyl group-containing urethane oligomer (a11) contains 27% (in the heating residue) of (meth) acrylate (a21) (pentaerythritol tetraacrylate) that does not participate in the urethanization reaction.
The isocyanate group content was measured in accordance with JIS K1603-1: 2007 “Method A”.

<Production Example 2>
“Bis (isocyanatomethyl) cyclohexane (hydrogenated XDI)” (trade name: Takenate 600, manufactured by Mitsui Chemicals, Inc., “262 parts (1 mole part) of 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI)” “Takenate” is a registered trademark of the same company.) 188 parts (1 mole part) ”except that it was changed to“ 188 parts (1 mole part) ”, except that methyl ethyl ketone was used in a theoretical amount of 80% in the heating residue. ), A methyl ethyl ketone solution of the acryloyl group-containing urethane oligomer (a12) was obtained.
The acryloyl group-containing urethane oligomer (a12) contains 29% (in the heating residue) of (meth) acrylate (a21) (pentaerythritol tetraacrylate) that does not participate in the urethanization reaction.

<Production Example 3>
The amount of 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) was changed from “262 parts (1 mole part)” to “524 parts (2 mole parts)”, and “polypropylene glycol (trade name: New) Paul PP-400, manufactured by Sanyo Chemical Industries, Ltd., “New Pole” is a registered trademark of the same company.) 395 parts (1 mole part) ”was added in the same manner as in Production Example 1 except that methyl ethyl ketone was used. Used a theoretical amount of 80% in the heating residue.), And a methyl ethyl ketone solution of the acryloyl group-containing urethane oligomer (a13) was obtained.
The acryloyl group-containing urethane oligomer (a13) contains 13% (in the heating residue) of (meth) acrylate (a21) (pentaerythritol tetraacrylate) that does not participate in the urethanization reaction.

<Production Example 4>
The amount of 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) was changed from “262 parts (1 mole part)” to “786 parts (3 mole parts)”, and “glycerin propylene oxide adduct (product) Name: SANNICS GP-3000, manufactured by Sanyo Chemical Industries, Ltd., “SANNICS” is a registered trademark of Sanyo Chemical Industries, Ltd.) 3010 parts (1 mole part) ”,“ hydroxy group-containing ( 826 parts (hydroxy group-containing (meth) acrylate (hm2) {hydroxyethyl acrylate, trade name: HEA, manufactured by Osaka Organic Chemical Industry Co., Ltd.}) (3 parts by mole) "except that it was changed to" 3 parts by mole ", except that methyl ethyl ketone was 80% in the heating residue. The methyl ethyl ketone solution of the acryloyl group-containing urethane oligomer (c14) was obtained.

<Production Example 5>
"262 parts (1 mole part) of 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI)" was changed to "isophorone diisocyanate (IPDI) (trade name: IPDI, manufactured by Perstorp) 222 parts (1 mole part)" Except for this, a methyl ethyl ketone solution of the acryloyl group-containing urethane oligomer (a24) was obtained in the same manner as in Production Example 1 (however, methyl ethyl ketone was used in a theoretical amount of 80% in the heating residue).
The acryloyl group-containing urethane oligomer (a24) contains 28% (in the heating residue) of (meth) acrylate (a21) (pentaerythritol tetraacrylate) that does not participate in the urethanization reaction.

<Production Example 6>
In a reaction vessel capable of heating, stirring, cooling, dripping, pressurizing and depressurizing, sucrose {trade name; sucrose, manufactured by Wako Pure Chemical Industries, Ltd., first grade} 342 parts (1 mol part) and dimethylformamide (DMF) {Mitsubishi Gas Chemical Co., Ltd.} After uniformly mixing 1000 parts, using nitrogen gas, pressurize to 0.4 MPa with gauge pressure and discharge to 0.02 MPa (hereinafter, this nitrogen gas is used) The operation was abbreviated as pressurized nitrogen replacement.) Was repeated three times. Thereafter, the temperature was raised to 100 ° C. while stirring, 4350 parts (75 mole parts) of propylene oxide (PO) was added dropwise at the same temperature over 4 hours, and stirring was continued for 30 minutes at the same temperature to leave the remaining PO. Was reacted. Next, the mixture was heated to 120 ° C., while maintaining the same temperature, DMF was distilled off under reduced pressure of 0.01 to 0.1 MPa, then cooled to 90 ° C., 20 parts of ion-exchanged water was added, and then synthetic inorganic Adsorbent {KYOWARD 700, manufactured by Kyowa Chemical Industry Co., Ltd., "KYOWARD" is a registered trademark of the company. } 100 parts were added and stirred at the same temperature for 1 hour. Next, at the same temperature, no. 2 filter paper {manufactured by Toyo Filter Paper Co., Ltd.} to remove the synthetic inorganic adsorbent, and further dehydrated at 120 ° C. under reduced pressure of 0.01 to 0.02 MPa for 1 hour to obtain a polyoxyalkylene compound (b11) (Sucrose / PO75 mol adduct) was obtained.

<Production Example 7>
In a reaction vessel similar to Production Example 6, 342 parts (1 mole part) of sucrose and 1000 parts of DMF were uniformly mixed, and then nitrogen replacement was repeated three times using nitrogen gas. Thereafter, the temperature was raised to 100 ° C. with stirring, and 1740 parts (30 mole parts) of propylene oxide (PO) was added dropwise at the same temperature over 4 hours, and then stirring was continued for 30 minutes at the same temperature to leave the remaining PO. Was reacted. Subsequently, 360 parts (5 mole parts) of butylene oxide (BO) was added dropwise at the same temperature over 2 hours, and then the remaining BO was reacted by continuing stirring for 4 hours. Next, the mixture was heated to 120 ° C., while maintaining the same temperature, DMF was distilled off under reduced pressure of 0.01 to 0.1 MPa, then cooled to 90 ° C., 20 parts of ion-exchanged water was added, and then synthetic inorganic 100 parts of adsorbent was added and stirred at the same temperature for 1 hour. Next, at the same temperature, no. 2 filter paper {manufactured by Toyo Filter Paper Co., Ltd.} to remove the synthetic inorganic adsorbent, and further dehydrated at 120 ° C. under reduced pressure of 0.01 to 0.02 MPa for 1 hour to obtain a polyoxyalkylene compound (b12) (Sucrose / PO 30 mol · BO 5 mol adduct) was obtained.

<Production Example 8>
469 parts (0.1 mol part) of the polyoxyalkylene compound (b11) obtained in Production Example 5 was charged into a pressure-resistant reaction vessel capable of heating, cooling, stirring and sealing, and the pressure was reduced from 1.3 to 2.7 Pa. Dehydrated at 100 ° C. for 1 hour. Then, after cooling to 50 ° C., 12 parts (0.07 mol part) of diisocyanate (di1) was added, and the pressure nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 120 ° C. over 1 hour while stirring, and after stirring for 12 hours at the same temperature, it was confirmed that the isocyanate group content was 0.2%, and a reaction product (b21) was obtained. It was.

<Production Example 9>
In a reaction vessel similar to Production Example 8, 50 parts (0.05 mole part) of polypropylene glycol (trade name: Sannix PP-1000, manufactured by Sanyo Chemical Industries Ltd.) and 24 parts (0.11 mole part) of IPDI are charged. The pressurized nitrogen substitution was repeated 3 times. Then, it heated up to 110 degreeC in 1 hour, stirring, and also continued stirring for 5 hours, and obtained the diisocyanate prepolymer. Subsequently, the diisocyanate prepolymer was cooled to 80 ° C., and 293 parts (0.12 mol part) of the polyoxyalkylene compound (b12) (sucrose / PO 30 mol · BO 5 mol adduct) obtained in Production Example 7 was added and stirred. Then, the temperature was raised to 120 ° C. over 1 hour, and after further stirring for 12 hours, it was confirmed that the isocyanate group content was 0.2% to obtain a reaction product (b22).

<Example 1>
50 parts of methylethylketone solution of acryloyl group-containing urethane oligomer (a11) prepared in Production Example 1 (40 parts as heating residue), (meth) acrylate (a22) {dipentaerythritol Mixture of hexaacrylate and dipentaerythritol pentaacrylate, trade name: Neomer DA600, manufactured by Sanyo Chemical Industries, Ltd. (“Neomer” is a registered trademark of the same company)} 55 parts, photopolymerization initiator (a31) {1- Hydroxycyclohexyl phenyl ketone, trade name: Irgacure 184, manufactured by BASF (“Irgacure” is a registered trademark of Ciba Holding Inc.)} 5 parts, polyaxoxyalkylene compound (b11) obtained in Production Example 6 2 parts , Reaction product obtained in Production Example 7 (b21 1 part and 143 parts of a solvent (f1) {methyl ethyl ketone} (theoretical value that the heating residue becomes 40%) are mixed and mixed at 40 ° C. for 1 hour, and then the heating residue is measured and the heating residue is 40%. The radiation curable composition (1) of the present invention was obtained by adjusting with a solvent (f1) and filtering with a filter paper having a retention particle diameter of 2 μm {PF020 manufactured by Toyo Roshi Kaisha, Ltd.}.

<Examples 2 to 7>
“Methyl ethyl ketone solution 50 parts of acryloyl group-containing urethane oligomer (a11) (40 parts as heating residue)” “55 parts of (meth) acrylate (a22)”, “5 parts of photopolymerization initiator (a31)”, “Polyoxy Axylene compound (b11) 2 parts "," reactant (b21) 1 part "shown in Table 1 {acryloyl group-containing urethane oligomer (A1), (meth) acrylate (A2), polyoxyalkylene compound ( B1), the reactant (B2)} and the amount used (parts) were changed, respectively, and the dispersion of filler (C) and the amount used (parts) shown in Table 1 in Examples 5 to 7 (the amount used was The radiation-curable compositions (2) to (7) of the present invention were obtained in the same manner as in Example 1 except that (indicated by the heating residue) was used. In addition, regarding the “solvent (f1)”, the amount that the heating residue was 40% was used. In addition, description of Table 1 showed the value as a heating residue.

<Example 8>
In a mixing vessel made of stainless steel with a stirring blade and a motor, 50 parts of methylethylketone solution of acryloyl group-containing urethane oligomer (a11) (40 parts as a heating residue), 55 parts of (meth) acrylate (a22), photopolymerization initiator (a31) 5 parts, 1 part of polyaxoxyalkylene compound (b12), 1 part of reactant (b22), 0.1 part of polyoxyalkylene-modified silicone (d1) and 143 parts of solvent (f1) (theoretical heating residue is 40%) Value), mixed at 40 ° C. for 1 hour, and filtered through a filter paper with a reserved particle diameter of 2 μm (manufactured by Toyo Filter Paper Co., Ltd., PF020) to obtain a mixture. Thereafter, the temperature of the mixture was adjusted to 25 ° C., and 10 parts of filler (c4) {acrylic filler, trade name: GM-1015, volume average particle size 2 μm, manufactured by Aika Industry Co., Ltd.} was added, and 15 minutes in a dissolver. A dispersion was obtained by mixing and dispersing. Thereafter, the heating residue of the dispersion was measured, adjusted with methyl ethyl ketone so that the heating residue was 40%, filtered through a stainless steel mesh with an opening of 45 μm, and the radiation curable composition (8) of the present invention was obtained. Obtained.

<Example 9>
“Acryloyl group-containing urethane oligomer (a11) 40 parts” was changed to “acryloyl group-containing urethane oligomer (a11) 40 parts” and “acryloyl group-containing urethane oligomer (a14) 30 parts”, “polyoxyalkylene compound (b12) ) 1 part "was changed to" 1 part of polyaxoxyalkylene compound (b11) "," Reactant (b22) 1 part "was changed to" Reactant (b21) 1 part "," Filler (c4) A radiation-curable composition (9) of the present invention was obtained in the same manner as in Example 8, except that “10 parts” was changed to “20 parts of filler (c5)”.

  Each component in Table 1 is as follows.

a11: Acrylyl group-containing urethane oligomer prepared in Production Example 1 {contains 27% of (meth) acrylate (a21) (pentaerythritol pentaacrylate)}
a12: Acrylyl group-containing urethane oligomer prepared in Production Example 2 {containing (meth) acrylate (a21) (pentaerythritol pentaacrylate) 29%}
a13: Acrylyl group-containing urethane oligomer prepared in Production Example 3 {containing (meth) acrylate (a21) (pentaerythritol pentaacrylate) 13%}
a14: Acrylyl group-containing urethane oligomer prepared in Production Example 4

a22: (meth) acrylate {mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, Neomer DA600 manufactured by Sanyo Chemical Industries Ltd.}
a23: (meth) acrylate {tricyclodecane dimethylol diacrylate, Kyoeisha Chemical Co., Ltd. light acrylate DCP-A}
a24: (Meth) acrylate prepared in Production Example 5 {acryloyl group-containing urethane oligomer not containing hydrogenated MDI and hydrogenated XDI as a constituent component, containing 28% of (meth) acrylate (a21)}

a31: Photopolymerization initiator {1-hydroxycyclohexyl phenyl ketone, Irgacure 184 manufactured by BASF Corporation}

b11: Polyoxyalkylene compound prepared in Production Example 6 b12: Polyoxyalkylene compound prepared in Production Example 7

b21: Reaction product of polyoxyalkylene compound (b11) prepared in Preparation Example 6 and 1,6-hexane diisocyanate b22: Reaction product of polyoxyalkylene compound (b12) prepared in Preparation Example 7, IPDI and polypropylene glycol

c1: Inorganic filler {silica filler methyl ethyl ketone dispersion (heating residue 30%), Nissan Chemical Industries, Ltd. MEK-ST, volume average particle size 15 nm}
c2: inorganic filler {silica isopropyl alcohol dispersion (heating residue 30%), IPA-ST-Z manufactured by Nissan Chemical Industries, Ltd., volume average particle size 90 nm}
c3: Inorganic filler {Isopropyl alcohol dispersion of phosphorus-doped tin oxide filler (heated residue 20%), Cellulax CX-S204IP, Nissan Chemical Industries, Ltd., volume average particle size 12n}
c4: Organic filler {acrylic filler, GM-1015 manufactured by Aika Industry Co., Ltd., volume average particle diameter 2 μm}
c5: Organic filler {polyethylene filler, Honeywell Acumist B-6, volume average particle diameter 6 μm, “Acmist” is a registered trademark of Honeywell International Inc. }

d1: Branched polyoxyalkylene-modified silicone {Fz-2110 manufactured by Toray Dow Corning Co., Ltd.}

<Comparative Example 1 {an example corresponding to the example described in Japanese Patent Laid-Open No. 2009-104054}>
50 parts of methylethylketone solution of acryloyl group-containing urethane oligomer (a11) prepared in Production Example 1 (40 parts as heating residue), (meth) acrylate (a22) {dipentaerythritol Mixture of hexaacrylate and dipentaerythritol pentaacrylate} 55 parts, photopolymerization initiator (a31) 5 parts of {1-hydroxycyclohexyl phenyl ketone}, acrylate having a fluorinated alkyl group (trade name: Megafax RS-75, DIC) 12.5 parts of heating residue 40% (methyl ethyl ketone / methyl isobutyl ketone = 93/7 (% /%) solution (“MegaFac” is a registered trademark of the company)) manufactured by Co., Ltd. Parts) and solvent (f1) {methyl ethyl ketone} 140 parts (Theoretical value that the heat residue becomes 40%) and mixed at 40 ° C. for 1 hour, and then the heating residue is measured and adjusted with the solvent (f1) so that the heating residue becomes 40%. A comparative radiation-curable composition (H1) was obtained by filtering with filter paper {Toyo Filter Paper Co., Ltd., PF020}.

<Comparative Examples 2 and 3>
“50 parts of methyl ethyl ketone solution of acryloyl group-containing urethane oligomer (a11)”, “55 parts of (meth) acrylate (a22)”, “5 parts of photopolymerization initiator (a31)”, “2 parts of reactant (b21)” Comparative radiation curable compositions (2) and (3) were obtained in the same manner as in Example 1 except that the amounts shown in Table 2 and the amounts used (parts) were changed.
With respect to the solvent (f1), an amount such that the heating residue was 40% was used.
In addition, description of Table 2 showed the value as a heating residue.

  The radiation curable compositions obtained in Examples and Comparative Examples were evaluated for fingerprint wiping property, recoatability and durability as follows, and the evaluation results are shown in Table 3.

<Preparation of sample for evaluation>
Easy-adhesion-treated polyester film {manufactured by Toyobo Co., Ltd., product number A4100, thickness 100 μm} is cut into 30 cm (length) x 15 cm (width) corners, the coated surface is wiped with isopropyl alcohol, isopropyl alcohol is dried, and coating is performed. A plastic base film was prepared. Next, a bar coater equivalent to JIS K5101-4: 2004 “Pigment test method—Part 4: Hiding power—Hiding rate test paper method—4. Apparatus and instrument, (d) Bar coater” (No. 12: Stainless steel Using an automatic coating apparatus PI-1210 manufactured by Tester Sangyo Co., Ltd., an evaluation sample (radiation curable composition) is applied to a plastic base film for coating using a diameter 0.30 mm). After coating in the longitudinal direction of the plastic base film at a high speed, the coated film is heated and dried at 80 ° C. for 1 minute in a circulating drier so that the coated surface is horizontal, and ultraviolet light (high pressure) is applied to the coated surface. A mercury lamp, 300 mJ / cm ² ) was irradiated perpendicularly to the coated surface.
Then, for evaluation of fingerprint wiping property, recoating property and durability, a 10 cm × 10 cm square was cut out to prepare an evaluation sample.

<Fingerprint wiping>
Randomly press the thumbs of five testers against the coated surface of the sample for evaluation (5 sheets each) to attach a fingerprint to the coated surface (1 person / sheet), then sample the sample with the fingerprint. Attached to the table, the attached fingerprint is attached to a weighted arm of a rubbing tester B1052 manufactured by Imoto Seisakusho Co., Ltd. A Japanese pharmacy type I absorbent cotton is attached, and the sample stage is moved while applying a load of 500 g / cm ² and wiped off. The number of reciprocations of the sample stage was measured until no longer visible, and the arithmetic average of the five samples for evaluation was defined as the fingerprint wiping property (when the wiping property was 30 or more, “−” was displayed in the number column). The smaller the value, the better the fingerprint wiping property.

The fingerprint wiping property was evaluated as follows, and the evaluation was indicated by ◎, ○, Δ, and ×.
◎: 10 times or less (very good fingerprint wiping performance)
○: 11-15 times (Excellent fingerprint wiping)
Δ: 16-30 times (fingerprint wiping property is slightly inferior)
×: More than 30 times (inferior to fingerprint wiping)

<Recoatability>
Using Zebra Co., Ltd. Himacky (oil-based marker, 6 mm wide, 4 colors; black, red, blue and yellow), a straight line is 5 cm long and approximately 1.5 cm apart on the coated surface of the sample for evaluation. Each line was drawn, and this straight line was evaluated according to the following criteria.

A: No repelling (excellent recoatability)
○: Repelling could be confirmed at one or two places (excellent recoatability)
Δ: Flick or part of line end was missing at 3 or more locations (recoatability is slightly inferior)
▲: All ends of the line were missing (inferior in recoatability)
×: Not remained as a line (remarkably inferior in recoatability)

<Durability>
Samples for evaluation (5 sheets each) were stored for 96 hours in an environment of 60 ° C. × 95 RH%, and the above-described fingerprint wiping test was performed (“−” was displayed when the wiping property was 60 or more).
Compared with the fingerprint wiping property test, the number of times of reciprocation (arithmetic mean) was increased.

The durability was evaluated as follows, and the evaluation was indicated by ◎, ○, Δ, ▲ and ×.
A: Increased number of times is 2 or less (excellent durability)
○: Increased 3 to 5 times (excellent durability)
Δ: Increased 6 to 10 times (durability is slightly inferior)
▲: Increased 11 to 20 times (durability is inferior)
X: Increase number exceeds 20 times (durability is poor)

The following evaluation was performed as a comprehensive evaluation.
All evaluations are ◎ and ○,
◎ is very good with 2 or 3 (◎)
Excellent ◎ is 1 to 0 (○)
Those with ▲ and × in the evaluation were considered inferior (×).

  The radiation curable compositions of the present invention (Examples 1 to 9) are superior in recoatability compared to the radiation curable composition of Comparative Example 1, and superior in durability to the radiation curable compositions of Comparative Examples 2 and 3. The fingerprint wiping property was superior to the radiation curable composition of Comparative Example 3.

The radiation curable composition of the present invention can be used as a coating agent for wood, stone, glass, concrete, metal, plastic, metal-deposited plastic and the like. Furthermore, it can also be set as a molded object as a three-dimensional modeling curable coating composition. Among these, it is suitable as a coating agent for plastics and metal-deposited plastics, and is particularly suitable as a coating agent for plastics. Among plastic coating agents, it is optimal as a coating agent for plastic films with excellent fingerprint wiping properties.

Claims (4)

A curable resin containing a (meth) acryloyl group-containing urethane oligomer (A1) comprising 4,4′-dicyclohexylmethane diisocyanate and / or bis (isocyanatomethyl) cyclohexane and a hydroxy group-containing (meth) acrylate as structural units ( A) and
A radiation curable product comprising the polyoxyalkylene compound (B1) represented by the general formula (1) and / or a reaction product (B2) of the polyoxyalkylene compound (B1) and diisocyanate. Composition.

{H- (OX) ni-} mQ (1)

Q is a reaction residue obtained by removing a hydrogen atom from m primary hydroxyl groups of a non-reducing di- or trisaccharide, OX is an oxyalkylene group, H is a hydrogen atom, ni is an integer of 0 to 100, m is 2 to 2 An integer of 4, i represents an integer of 1 to m, and m ni may be the same or different, but at least one is 1 or more, and the total number of OX (Σni × m) is an integer of 20 to 100 is there. Furthermore, the radiation curable composition of Claim 1 containing a filler (C). Furthermore, the radiation curable composition of Claim 1 or 2 containing polyoxyalkylene modified silicone (D). A plastic film obtained by coating the radiation curable composition according to claim 1 on a plastic base film and curing the composition.