JP5608852B2 - UV curable composition - Google Patents

Description

  The present invention relates to an ultraviolet curable composition.

  Conventionally, as an ultraviolet curable composition used as a protective layer for a molding plastic film, a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule and two (meth) acryloyl in the molecule What contains urethane (meth) acrylate and / or epoxy (meth) acrylate having a group and colloidal silica having a primary particle size of 1 nm or more and 200 nm or less is known (Patent Document 1).

JP 2009-24168 A

In conventional UV curable compositions, it is difficult to achieve both scratch resistance and formability (elongation of the cured film) of the cured film, and in applications where priority is given to scratch resistance, the moldability is poor and the moldability is prioritized. In use, there is a problem that the scratch resistance is inferior.
That is, an object of the present invention is to provide an ultraviolet curable composition excellent in scratch resistance and moldability (elongation of a cured film).

The ultraviolet curable composition of the present invention is characterized by 1 mol of tri- to hexa-isocyanate (A), di (meth) acrylate having a hydroxyl group and / or tri (meth) acrylate (B) 1 to 6 having a hydroxyl group. (Meth) acryloyl group-containing urethane oligomer (C) obtained by reaction with 5 mol ;
Containing the polyoxyalkylene compound (H) represented by the general formula (1) and / or the reaction product (K) of the polyoxyalkylene compound (H) and the diisocyanate (J) ,
The gist is that the di (meth) acrylate having a hydroxyl group and / or the tri (meth) acrylate (B) having a hydroxyl group is a mixture of dihydroxydi (meth) acrylate and monohydroxytri (meth) acrylate .

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

Q is a reaction residue obtained by removing a hydrogen atom from m hydroxyl groups of a non-reducing di- or trisaccharide, OX is an oxyalkylene group, R is an alkyl group, a copolymerizable double bond-containing group and / or a hydrogen atom, ni represents an integer of 0 to 100, m represents an integer of 2 to 4, 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 20 to It is an integer of 100.

  Another feature of the plastic film for molding of the present invention is that it is obtained by coating the ultraviolet curable composition on a plastic base film.

The ultraviolet curable composition of the present invention is remarkably excellent in scratch resistance and moldability (elongation of a cured film).
Therefore, when the ultraviolet curable composition of the present invention is used, a plastic film for molding excellent in scratch resistance and moldability can be obtained.

<Tri- to hexa-isocyanate (A)>
The tri- to hexa-isocyanate (A) includes a modified diisocyanate (J) {nurate, burette, adduct, etc.} (A1), a reaction product (A2) of this modified product with a diol, and a polyol and diisocyanate. A reaction product (A3) with (J) is included.

  Examples of the diisocyanate (J) include aliphatic diisocyanate (J1), aromatic diisocyanate (J2), alicyclic diisocyanate (J3), and diisocyanate prepolymer (J4) obtained by reacting these diisocyanates with diols.

  As aliphatic diisocyanate (J1), C6-C8 alkylene diisocyanate etc. are used, 1, 4- diisocyanato butane, hexamethylene diisocyanate (HDI), etc. are mentioned.

  As the aromatic diisocyanate (J2), arylene diisocyanate having 8 to 15 carbon atoms is used, and paraphenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene, and the like. Examples include range isocyanate and 1,5-naphthalene diisocyanate.

  As the alicyclic diisocyanate (J3), cycloalkylene diisocyanate having 12 to 15 carbon atoms is used, and isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), trans 1,4-cyclohexane. Examples include diisocyanate, hydrogenated TDI, and hydrogenated 1,5-naphthalene diisocyanate.

  The diisocyanate prepolymer (J4) obtained by the reaction of diisocyanate and diol includes a diisocyanate prepolymer obtained by reacting (y + 1) mol of diisocyanate with respect to diol (y) mol. For this reaction, usual methods (reaction ratio, reaction conditions, etc.) can be applied.

  As the diol, any compound having two hydroxy groups can be used without limitation, and a diol 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) (addition number 1 to 80) (carbon number 2 to 2) of alkylene oxide (2 to 3 carbon atoms) to hexanediol, cyclohexanediol, cyclohexanedimethylol and the like and active hydrogen compound (the above diol and bisphenol A etc.) 10 diol alkylene oxide adduct and bisphenol A alkylene oxide adduct). In addition to these, a linear polyester having a hydroxyl group at the terminal produced from a diol and a dicarboxylic acid 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.

  Of these diisocyanates (J), aliphatic diisocyanates (J1) and alicyclic diisocyanates (J3) are preferable, HDI and hydrogenated MDI are more preferable, and HDI is particularly preferable.

  As a reaction product (A2) of a modified diisocyanate (J) and a diol, a reaction obtained by reacting (y) to (y + 1) moles of the modified diisocyanate (J) with respect to the diol (y) mole. Things are included. For this reaction, usual methods (reaction ratio, reaction conditions, etc.) can be applied.

  The reactant (A3) of the polyol and diisocyanate (J) includes a reactant obtained by reacting (y + 1) to (6y) moles of diisocyanate (J) with respect to moles of polyol (y). For this reaction, usual methods (reaction ratio, reaction conditions, etc.) can be applied.

  Examples of the polyol include polyols having 3 to 15 carbon atoms (such as glycerin, trimethylolpropane, dimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol), and alkylene oxide (2 to 3 carbon atoms) adducts of polyol ( 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, 3 to 100 mol adduct of propylene oxide of trimethylolpropane, and ditrimethylolpropane Ethylene oxide 4 to 100 mol adduct, dimethylolpropane propylene oxide 4 to 100 mol adduct, pentaerythritol ethylene oxide 4 to 100 mol adduct, pentaerythr Toluene propylene oxide 4-16 mol adduct, dipentaerythritol ethylene oxide 6-100 mol adduct, dipentaerythritol propylene oxide 4-100 mol adduct, tripentaerythritol ethylene oxide 8-100 mol adduct, tripenta Erythritol propylene oxide 8 to 100 mol adduct, isocyanuric acid ethylene oxide 3 to 100 mol adduct, and isocyanuric acid propylene oxide 3 to 100 mol adduct).

  Of tri- to hexa-isocyanate (A), a reaction product (A2) of a modified product (A1) of a diisocyanate (J) and a diol, and a reaction product (A3) of a polyol and a diisocyanate (J) are more preferable. Is a reaction product of a modified aliphatic or alicyclic diisocyanate (preferably a nurate and a burette) and an aliphatic diol or an alkylene oxide adduct of an aliphatic diol, and an aliphatic or alicyclic diisocyanate and an aliphatic. Reaction product of polyol or aliphatic polyol with alkylene oxide adduct, particularly preferably HDI or hydrogenated MDI modified product and aliphatic diol or reaction product of alkylene oxide adduct, and HDI or hydrogenated MDI and aliphatic polyol Or a reaction product with this alkylene oxide adduct, most preferably Which is a reaction product of an alkylene oxide adduct of the reaction product and hydrogenated MDI and aliphatic polyols with alkylene oxide adducts of the biuret and aliphatic diol isocyanurate, or hydrogenated MDI and hydrogenated MDI.

The di (meth) acrylate having a hydroxyl group and / or the tri (meth) acrylate (B) having a hydroxyl group is at least from a polyol having 3 to 4 hydroxyl groups or an alkylene oxide (carbon number 2 to 3) adduct of this polyol. If one hydroxyl group is left and the other hydroxyl group is blocked with a (meth) acryloyl group, it can be used without limitation, monohydroxy di (meth) acrylate {glycerin di (meth) acrylate, trimethylolpropane di (meth) Di (meth) acrylates of acrylate and isocyanuric acid ethylene oxide adducts}, dihydroxy di (meth) acrylate {diglycerin di (meth) acrylate, ditrimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, etc.} and monohydroxy Tri (meth) acrylate {pentaerythritol tri (meth) acrylate and diglycerol tri (meth) acrylate} and mixtures thereof and the like are used.
Here, (meth) acrylate means acrylate and / or methacrylate, and (meth) acryloyl group means acryloyl group and / or methacryloyl group.

  Of the di (meth) acrylate having a hydroxyl group and / or the tri (meth) acrylate (B) having a hydroxyl group, dihydroxy di (meth) acrylate, monohydroxytri (meth) acrylate and a mixture thereof are preferable, and more preferably mono Hydroxytri (meth) acrylate and mixtures of monohydroxytri (meth) acrylate and dihydroxydi (meth) acrylate, particularly preferably pentaerythritol tri (meth) acrylate and pentaerythritol tri (meth) acrylate and pentaerythritol di (meth) A mixture with acrylate {When using a mixture with dihydroxydi (meth) acrylate, the content (mol%) of dihydroxydi (meth) acrylate is monohydroxytri (meth) acrylate Based on the number of moles of a mixture of dihydroxy di (meth) acrylate and preferably from 1 to 30, more preferably 3 to 20, particularly preferably 5 to 15. }.

  The reaction of tri- to hexa-isocyanate (A) with di (meth) acrylate having a hydroxyl group and / or tri (meth) acrylate (B) having a hydroxyl group is carried out by a known method {for example, JP-A-2007-204567}. Etc. are applicable.

  In the reaction of tri- to hexa-isocyanate (A) with di (meth) acrylate having a hydroxyl group and / or tri (meth) acrylate (B) having a hydroxyl group, di (meth) acrylate and / or hydroxyl group having a hydroxyl group As for the usage-amount (mol) of the tri (meth) acrylate (B) to have, 1-6.5 are preferable with respect to 1 mol of tri- to hexa-isocyanate (A), More preferably, it is 1.5-6.

The number average molecular weight of the (meth) acryloyl group-containing urethane oligomer (C) is preferably 1000 to 10,000, more preferably 1300 to 9000, and particularly preferably 1500 to 8000. When the number average molecular weight is in this range, the scratch resistance and moldability are excellent.
The number average molecular weight is measured by gel permeation chromatography using polystyrene having a known molecular weight as a standard substance.

<(Meth) acryloyl group-containing urethane oligomer (D)>
The ultraviolet curable composition of the present invention preferably contains a (meth) acryloyl group-containing urethane oligomer (D) containing 2 to 3 (meth) acryloyl groups in one molecule. When the (meth) acryloyl group-containing urethane oligomer (D) is contained, the moldability is further improved.

  The (meth) acryloyl group-containing urethane oligomer (D) is obtained by reacting a urethane prepolymer obtained by reacting diisocyanate (J) with a diol or triol, or a diisocyanate nurate and a mono (meth) acrylate having a hydroxyl group. The urethane prepolymer obtained is included.

  The weight average molecular weight of the (meth) acryloyl group-containing urethane oligomer (D) is preferably 800 to 30000, more preferably 1000 to 20000, and particularly preferably 1500 to 10,000. Within this range, the moldability is further improved.

  The weight average molecular weight is measured by gel permeation chromatography using polystyrene having a known molecular weight as a standard substance.

  (Meth) acryloyl group-containing urethane oligomer (D) containing 2 to 3 (meth) acryloyl groups in one molecule can be easily obtained from the market, UV-2000B, UV-3000B manufactured by Nippon Synthetic Chemical Industry Co., Ltd. , UV-3200B, UV-3500BA, UV-3520TL, UV-6100B, UV-6300 or UV-7000B; CN962, CN963, CN964, CN965, CN980, CN981, CN981, CN982, CN983, CN996, manufactured by Sartomer Japan, Inc. CN9001, CN9002, CN9788, CN9873, CN978, CN9782 or CN9783; M-1100, M-1200, M-1210, M-1310 or M-1600 manufactured by Toagosei Co., Ltd .; UN-9000P manufactured by Negami Industrial Co., Ltd. P, UN-9200A, UN-7600, UN-333, UN-1255, UN-6060PTM, UN-6060P or SH-500B; manufactured Photomer 6008 such Cognis Japan Ltd. and the like.

  When the (meth) acryloyl group-containing urethane oligomer (D) is contained, the preferred range varies depending on the use and purpose, but the content (% by weight) of the (meth) acryloyl group-containing urethane oligomer (D) is (meth) acryloyl. Based on the weight of the group-containing urethane oligomer (C) and the (meth) acryloyl group-containing urethane oligomer (D), 3 to 90 is preferable, more preferably 5 to 85, and particularly preferably 10 to 80. The content (% by weight) of the (meth) acryloyl group-containing urethane oligomer (C) is based on the weight of the (meth) acryloyl group-containing urethane oligomer (C) and the (meth) acryloyl group-containing urethane oligomer (D). 10 to 97, more preferably 15 to 95, and particularly preferably 20 to 90.

<Polymer (E)>
The ultraviolet curable composition of the present invention may contain a polymer (E). When the polymer (E) is contained, the moldability is 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), polyurethane (E3), etc. are contained.

  Among the polymers (E), vinyl polymer (E1), polyurethane (E3) and a mixture thereof are preferable, more preferably a mixture of vinyl polymer (E1) and polyurethane (E3) and polyurethane (E3), particularly preferably polyurethane. (E3).

  The weight average molecular weight of the polymer (E) is preferably 10,000 to 2,000,000, more preferably 30,000 to 1,500,000, and particularly preferably 50,000 to 1,000,000. Within this range, the moldability of the ultraviolet curable composition is further improved.

  When the polymer contains (E), the content (% by weight) is 1 on the basis of the weight of the ultraviolet curable composition of the present invention (excluding the solvent (T) when the solvent (T) is included). -40 is preferable, More preferably, it is 3-30, Most preferably, it is 5-20. Within this range, the moldability of the ultraviolet curable composition is further improved.

<Filler (F)>
The ultraviolet curable composition of this invention can contain a filler (F). When the filler (F) is contained, the scratch resistance is further improved.

  As a filler (F), an inorganic filler (F1), an organic filler (F2), etc. are contained.

  As inorganic filler (F1), 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 (F1) 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 (F2) include an acrylic resin filler, a styrene resin filler, an acrylic / styrene resin filler, a urethane resin filler, and a silicone resin filler.

  The organic filler (F2) may be in the form of a dispersion liquid dispersed in a dispersion medium. Such a dispersion can be prepared by a known method {for example, JP 2007-99897 A}. The organic filler (F2) can be used after removing the dispersion medium from such a dispersion by drying or the like.

  Among these fillers (F), inorganic fillers, acrylic resin fillers, acrylic / styrene resin fillers and mixtures thereof are preferred, more preferred are inorganic fillers, acrylic resin fillers and mixtures thereof, and particularly preferred are inorganic fillers. Of the inorganic fillers (F1), silica, alumina and metal oxides are preferable, silica and metal oxides are more preferable, and silica, tin oxide and zinc oxide are particularly preferable.

The volume average particle diameter of the filler (F) is preferably 1 nm to 5 μm, more preferably 3 nm to 1 μm, and particularly preferably 5 nm to 500 nm. Within this range, the scratch resistance 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-ST150 manufactured by Nikkiso Co., Ltd.) Etc., “Microtrack” is a registered trademark of Leeds, And, Northlap, Company).

  When the ultraviolet curable composition of the present invention is applied to an application requiring transparency, the volume average particle diameter (nm) of the filler (F) is preferably 1 to 400, more preferably 3 to 200, and particularly preferably. Is 5-100. Within this range, the transparency of the molded article is further improved.

  When the filler (F) is contained, the content (% by weight) of the filler (F) is based on the weight of the ultraviolet curable composition of the present invention {when the solvent (T) is included, excluding the solvent (T)}. 1 to 40 is preferable, 3 to 30 is more preferable, and 5 to 25 is particularly preferable. Within this range, the scratch resistance is further improved.

<Mono (meth) acrylate and / or di (meth) acrylate (G)>
The ultraviolet curable composition of the present invention may contain mono (meth) acrylate and / or di (meth) acrylate (G). When mono (meth) acrylate and / or di (meth) acrylate (G) is contained, the scratch resistance is further improved.
As mono (meth) acrylate and / or di (meth) acrylate (G), mono (meth) acrylate and / or di (meth) acrylate described in JP-A No. 2004-352781 can be used.

  Of the mono (meth) acrylates and / or di (meth) acrylates (G), mono (meth) acrylates and / or di (meth) acrylates having a cyclic structure are preferred, more preferably mono (meth) having a cyclic structure. Acrylate or tricyclodecane dimethylol di (meth) acrylate, particularly preferably (meth) acryloylmorpholine or tricyclodecane dimethylol di (meth) acrylate.

  When mono (meth) acrylate and / or di (meth) acrylate (G) is contained, the content (% by weight) of mono (meth) acrylate and / or di (meth) acrylate (G) is the ultraviolet ray of the present invention. 1-60 are preferable based on the weight of the curable composition {excluding the solvent (T) when the solvent (T) is included}, more preferably 3-40, and particularly preferably 5-25. Within this range, scratch resistance and moldability are further improved.

<Polyalkylene oxide compound (H), reaction product thereof with diisocyanate (K)>
In the ultraviolet curable composition of the present invention, the polyoxyalkylene compound (H) represented by the general formula (1) and / or the reaction product (K) of the polyoxyalkylene compound (H) and the diisocyanate (J) are contained. Can be contained. When these are contained, fingerprint wiping properties and the like can be imparted.

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

  Q is a reaction residue obtained by removing a hydrogen atom from m hydroxyl groups of a non-reducing di- or trisaccharide, OX is an oxyalkylene group, R is an alkyl group, a copolymerizable double bond-containing group and / or a hydrogen atom , Ni is an integer of 0 to 100, m is an integer of 2 to 4, i is an integer of 1 to m, m ni may be the same or different, but at least one is 1 or more, and OX The total number (Σni × m) is an integer of 20 to 100.

  Examples of di- or trisaccharides that can constitute a reaction residue (Q) obtained by removing a hydrogen atom from m hydroxyl groups of a non-reducing di- or trisaccharide include sucrose, trehalose, isotrehalose, and isosaccharose. , Gentianose, raffinose, meretitol and planteose. 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. These may be used alone or in combination.

  Examples of the oxyalkylene group having 2 to 4 carbon atoms (OX) 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. When a plurality of types of oxyalkylene groups are contained in OX, there is no limitation on the bonding order (block shape, random shape and combinations thereof) and content ratio of these oxyalkylene groups.

  Among R, the alkyl group includes an alkyl group having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, iso-propyl, n-butyl and iso-butyl. The copolymerizable double bond-containing group includes a (meth) acryloyl-containing group and an alkenyl group having 2 to 3 carbon atoms.

  (Meth) acryloyl-containing groups include (meth) acryloyl groups, 3- (meth) acryloyloxy-2-hydroxypropyl, 2- (meth) acryloyloxy-1-hydroxymethylethyl and (meth) acryloyloxyethylaminocarbonyl Etc. are included.

  Examples of the alkenyl group having 2 to 3 carbon atoms include vinyl, 2-propenyl and 1-propenyl.

  Of these R, an alkyl group and alkenyl are preferred, more preferably methyl, ethyl, iso-propenyl and 2-propenyl, particularly preferably methyl, ethyl and 2-propenyl, most preferably methyl and ethyl. The m Rs may be the same or different.

  In the case where an alkyl group and / or a copolymerizable double bond-containing group is included in m R, the number of hydrogen atoms among all R is preferably 0 to 3, more preferably when m is 4. 0 to 2, particularly preferably 0 or 1, when m is 3, 0 to 3 is preferable, more preferably 0 or 1, and when m is 2, 0 or 1 is preferable.

  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 25 to 95, particularly preferably an integer of 30 to 90, and most preferably an integer of 35 to 85. Within this range, the fingerprint wiping property is further improved.

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

  Among diisocyanates, from the viewpoint of fingerprint wiping properties, HDI, IPDI, MDI, 1,5-naphthalene diisocyanate, hydrogenated MDI and diisocyanate prepolymers obtained by reaction of these diisocyanates and diols are preferred, more preferably HDI, It is a diisocyanate prepolymer obtained by the reaction of IPDI and these diisocyanates and diols. Of the diols, a diol having 2 to 10 carbon atoms and an alkylene oxide (2 to 3 carbon atoms) adduct (addition number 1 to 50) of a diol having 2 to 10 carbon atoms are preferable, and more preferable. Is a diol having 2 to 10 carbon atoms.

  In the reaction product (K), the use amount (mole part) of the diisocyanate (J) is preferably 0.1 to 0.8, more preferably 0.8, per 1 part by mole of the polyoxyalkylene compound (H). It is 15 to 0.75, particularly preferably 0.2 to 0.7, and most preferably 0.25 to 0.65.

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

  When the polyoxyalkylene compound (H) and / or the reactant (K) is contained, the content (% by weight) of the ultraviolet curable composition of the present invention {when the solvent (T) is included, the solvent (T Is preferably 0.01 to 10, more preferably 0.1 to 5, and particularly preferably 0.5 to 3. Within this range, the fingerprint wiping property can be further improved without deteriorating the performance (such as scratch resistance and processability) of the ultraviolet curable composition.

<Photoradical polymerization initiator (P)>
It is preferable to use a photoradical polymerization initiator (P) in the ultraviolet curable composition of the present invention. The radical photopolymerization initiator (P) can be used without limitation as long as it is a compound that generates radicals by receiving ultraviolet rays (wavelength of about 200 to 400 nm), and includes 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 can be used.

  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 photo radical polymerization initiators (P) may be used alone or in combination of two or more. Of these photoradical polymerization initiators (P), benzoyl group-containing radical initiators, morphyl group-containing radical initiators, and phosphorus atom-containing radical initiators are preferred, and benzoyl group-containing radical initiators and morpholinyl group-containing radicals are more preferred. It is an initiator.

  When the radical photopolymerization initiator (P) is contained, the content (% by weight) is determined by the (meth) acryloyl group-containing urethane oligomer (C) and other ultraviolet curable compounds {(meth) contained if necessary. Based on the weight of the acryloyl group-containing urethane oligomer (D) and mono (meth) acrylate and / or di (meth) acrylate (G)}, 1 to 15 is preferable, more preferably 2 to 12, particularly preferably 3 to 3. 10. Within this range, the curability of the ultraviolet curable composition is further improved.

  The ultraviolet curable composition of the present invention may further contain a polyoxyalkylene-modified silicone (S) for the purpose of further improving the leveling property. Examples of the polyoxyalkylene-modified silicone (S) include branched polyoxyalkylene-modified silicone (S1), terminal-modified polyoxyalkylene-modified silicone (S2), and block-type polyoxyalkylene-modified silicone (S3).

  Examples of the branched polyoxyalkylene-modified silicone (S1) include 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 [HLB = 1], FZ-2118 [HLB = 12], FZ-2120 [HLB = 6], FZ-2123 [H B = 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] {above, manufactured by Toray Dow Corning Co., Ltd.}; 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] {above, 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] {above, manufactured by Toshiba Silicone Co., Ltd.}; and TEGOPREN 5000 series [HLB = 3-15] {above, DEGUSSA, etc.}.

  Examples of the terminal-modified polyoxyalkylene-modified silicone (S2) include L-720 [HLB = 7] and FZ-2122 [HLB = 1] {manufactured by Toray Dow Corning Co., Ltd.}.

  As block type polyoxyalkylene-modified silicone (S3), SF8427 [HLB = 10] and BY16-004 [HLB = 0] {or more, manufactured by Toray Dow Corning Co., Ltd.}; KF-6004 [HLB = 5] {or more, Shin-Etsu Chemical Co., Ltd.}; FZ-2203 [HLB = 1], FZ-2207 [HLB = 3] and FZ-2208 [HLB = 7] {above, Nippon Unicar Co., Ltd.}; and TEGOPREN 3000 series [HLB = 1-5] {above, manufactured by DEGUSSA} and the like.

  Of these polyoxyalkylene-modified silicones, branched polyether-modified silicone (S1) is preferred from the viewpoint of fingerprint wiping properties. These polyoxyalkylene-modified silicones (S) can be used as one type or a mixture of two or more types, but when used as a mixture of two or more types, it is preferable to include a branched polyoxyalkylene-modified silicone (S1). .

  The hydrophilic / lipophilic balance (HLP of Griffin) of the polyoxyalkylene-modified silicone (S) 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. The HLB of Griffin can be determined by a method of calculating from the ratio of organic to inorganic surfactants described on pages 127 to 129 of the new surfactant introduction (published by Sanyo Chemical Industries, Ltd.). .

  When the polyoxyalkylene-modified silicone (S) is contained, the content (% by weight) is based on the weight of the ultraviolet curable composition of the present invention {excluding the solvent (T) when the solvent (T) is included}. 0.01-2, more preferably 0.03-1, and particularly preferably 0.05-0.5.

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

  As the solvent (T), (meth) acryloyl group-containing urethane oligomer (C) and other components {(meth) acryloyl group-containing urethane oligomer (D), polymer (E), polyoxyalkylene compound (H), if necessary. Reactant (K), mono (meth) acrylate and / or di (meth) acrylate (G), and / or radical photopolymerization initiator (P), etc.} can be uniformly dissolved {filler (F) as other component] If it contains, it may be a solvent that can uniformly disperse the filler (F), such as ketone (acetone, methyl ethyl ketone and methyl isobutyl ketone), glycol ether (methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether and propylene glycol monoethyl). Ether), glycol ester (methyl) B cellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate, etc.), alcohols (methanol, ethanol, propanol and butanol) and aromatic hydrocarbons (toluene and xylene) is. These solvents are used alone or in combination.

  When the solvent (T) is contained, the content (% by weight) of the solvent (T) is appropriately determined depending on the viscosity of the ultraviolet curable composition, the coating method, the film thickness after drying, and the like.

<Photosensitizer (U)>
The ultraviolet curable composition of the present invention may further contain a photosensitizer (U) for the purpose of further improving curability.

  As a photosensitizer (U), a well-known photosensitizer etc. can be used and an alkylamino photosensitizer (U1), a dialkylaminophenyl photosensitizer (U2), etc. are contained.

  Examples of the alkylamino photosensitizer (U1) 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).

  Examples of the dialkylaminophenyl photosensitizer (U2) include 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.
Of these photosensitizers, trialkylamine and dialkylaminophenyl photosensitizer (U2) are preferable, dialkylaminophenyl sensitizers are more preferable, and 4,4′-dialkylaminobenzophenone is particularly preferable.

  When the photosensitizer (U) is contained, the content (% by weight) is preferably 0.1 to 100, more preferably 1 to 50, based on the weight of the radical photopolymerization initiator (P). Especially preferably, it is 5-50. In addition, when not containing radical photopolymerization initiator (P), a photosensitizer (U) is not contained.

<Ultraviolet absorber (V)>
The ultraviolet curable composition of the present invention may contain an ultraviolet absorber (including a light stabilizer) (V) for the purpose of improving the weather resistance. Examples of the ultraviolet absorber (V) include benzotriazole ultraviolet absorber (V1), hindered amine ultraviolet absorber (V2), benzophenone ultraviolet absorber (V3), salicylic acid ultraviolet absorber (V4), and triazine ultraviolet absorber (V5). Is included.

  Examples of the benzotriazole ultraviolet absorber (V1) include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole. .

  As the hindered amine ultraviolet absorber (V2), 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 (V3) 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 (V4) include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.

  As a triazine ultraviolet absorber (V5), 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 may be used alone or in combination of two or more. When two or more types are used in combination, a hindered amine ultraviolet absorber (V2) and a triazine ultraviolet absorber (V5) are used in combination. Is preferred. Of these ultraviolet absorbers (V), benzotriazole ultraviolet absorbers (V1), hindered amine ultraviolet absorbers (V2) and triazine ultraviolet absorbers (V5) are preferred, more preferably hindered amine ultraviolet absorbers (V2) and triazines. It is an ultraviolet absorber (V5).

  When the ultraviolet absorber (V) is contained, the content (% by weight) is based on the weight of the ultraviolet curable composition of the present invention (excluding the solvent (T) when the solvent (T) is included), 0.1-10 are preferable, More preferably, it is 0.3-8, Most preferably, it is 0.5-5.

<Other additives>
The ultraviolet 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 content (% by weight) of the 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. 0.01-50 are preferable based on the weight of the curable composition {when solvent (T) is included, excluding solvent (T)}, more preferably 0.05-30, particularly preferably 0.1-0.1. 10.

  In addition to the (meth) acryloyl group-containing urethane oligomer (C), the (meth) acryloyl group-containing urethane oligomer (D), polymer (E), filler (F) polyoxyalkylene compound ( H), reactant (J), mono (meth) acrylate and / or di (meth) acrylate (G), photoradical polymerization initiator (P), photosensitizer (U), ultraviolet absorber (V) and In the case of containing other additives, the ultraviolet 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 used, the polymer (E) is uniformly dissolved in the solvent (T) to obtain a polymer solution, and then the (meth) acryloyl group-containing urethane oligomer (C) and other components {(meta ) Acrylyl group-containing urethane oligomer (D), filler (F), polyoxyalkylene compound (H), reactant (K), mono (meth) acrylate and / or di (meth) acrylate (G), photoradical polymerization initiation Agent (P), photosensitizer (U), ultraviolet absorber (V) and / or other additives, etc.} and the polymer solution are preferably mixed uniformly.

  When the filler (F) is used, after the filler (F) is uniformly dispersed in the solvent (H) to prepare a dispersion, the (meth) acryloyl group-containing urethane oligomer (C) and other components {( (Meth) acryloyl group-containing urethane oligomer (D), polymer (E), polyoxyalkylene compound (H), reactant (K), mono (meth) acrylate and / or di (meth) acrylate (G), radical photopolymerization It is preferable to mix the initiator (P), photosensitizer (U), ultraviolet absorber (V) and / or other additives, etc.} with the dispersion.

  The disperser for dispersing and mixing the filler (F) is not particularly limited as long as it can be uniformly dispersed. For example, a dissolver, a 2-shaft mixer, a 3-shaft mixer, a planetary mixer, a 3-shaft planetary mixer, a 3-roll, 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 uniform mixing / dispersing temperature (° 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 ultraviolet curable composition of the present invention can be applied to various plastic protective layers, and is particularly suitable as a protective layer for molding plastic films.
The protective layer is formed by coating a plastic base (plastic base film for molding) with the ultraviolet curable composition of the present invention and, if necessary, heating and drying, followed by ultraviolet irradiation.
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.

As an irradiation amount (mJ / cm < ² >) of an ultraviolet-ray, about 100-2,000 are preferable, More preferably, it is 200-1,000.

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

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

  As for the thickness (micrometer) of the plastic base film for shaping | molding, about 10-5000 are preferable, More preferably, it is 50-2000.

  As the molding method, in-mold molding (transfer molding), insert molding, and the like, which are simultaneous molding methods, can be applied. Specific methods for in-mold molding (transfer molding) and insert molding are described in JP-A-10-58895 and JP-A-2007-291380.

  When the molding plastic film of the present invention is molded by in-mold molding or insert molding, it is subjected to a decoration treatment or adhesion improving treatment by printing or the like on a cured film of an ultraviolet curable resin or on the opposite surface through a plastic base film. Can do.

  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 isocyanate group content was measured in accordance with method A (potentiometric titration method) of JIS K1603-1: 2007.

  The hydroxyl value was measured according to JIS K1557-1: 2007 Method A (potentiometric titration).

  The heating residue was measured under the conditions of 105 ° C. for 1 hour in accordance with JIS K5601-1-2: 1999 (dish: diameter 70 mm, edge height 15 mm, circulating air dryer).

  When the (meth) acryloyl group-containing urethane oligomer was synthesized, the molecular weight of the isocyanate was calculated from the isocyanate content as in the following formula, and the molecular weight of the diol or polyol was calculated from the hydroxyl value as in the following formula.

(Molecular weight of isocyanate) = 42 ÷ (isocyanate content ÷ 100) × number of functional groups (molecular weight of diol or polyol) = 56100 × number of functional groups ÷ (hydroxyl value)

<Production Example 1>
Isocyanurate of 1,6-hexane diisocyanate (trade name: Duranate TPA-100, manufactured by Asahi Kasei Co., Ltd., “Duranate” is a registered trademark of Asahi Kasei Chemicals Corporation. 545 parts (1 mol), polyethylene glycol (trade name: PEG-600, Sanyo Chemical Industries, Ltd.) 295 parts (0.5 mol), dibutyltin dilaurate (reaction catalyst) 0.05 parts and methyl ethyl ketone 210 parts (heating) The remaining 80% of the theoretical value was refluxed for 30 minutes with stirring, then cooled to 30 ° C. or lower, and acrylate (trade name: Light acrylate PE-3A, Kyoeisha Chemical Co., Ltd.) containing pentaerythritol triacrylate as a main component. Company-made pentaerythritol tetra-, tri-, di- 826 parts (1.7 mol of triacrylate, 0.2 mol of diacrylate, 2.0 mol of hydroxy group) and hydroquinone monomethyl ether (polymerization inhibitor) 0.5 A solution in which 207 parts of methyl ethyl ketone was dissolved in 207 parts of methyl ethyl ketone (theoretical value with a heating residue of 80%) was added dropwise over 30 minutes with stirring, and the reflux was continued until the isocyanate group content was 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 (c1). A solution was obtained. The number average molecular weight of the acryloyl group-containing urethane oligomer (c1) was 2900.

<Production Example 2>
“545 parts of 1,6 hexane diisocyanate isocyanurate body” was changed to “536 parts (1 mol) of 1,6 hexane diisocyanate burette body (trade name: Duranate 24A-100, manufactured by Asahi Kasei Corporation)”, “polyethylene Glycol 498 parts ”was changed to“ polypropylene glycol (trade name: New Pole PP-1000, manufactured by Sanyo Chemical Industries, “New Pole” is a registered trademark of the company) 505 parts (0.5 mol) ”. The methyl ethyl ketone solution of the acryloyl group-containing urethane oligomer (c2) was obtained in the same manner as in Production Example 1 (methyl ethyl ketone was the theoretical amount that the heating residue was 80%). The number average molecular weight of the acryloyl group-containing urethane oligomer (c2) was 3,500.

<Production Example 3>
“545 parts of isocyanurate of 1,6 hexane diisocyanate” is replaced with “1,6 hexane diisocyanate (trade name: Takenate 700, manufactured by Mitsui Takeda Chemical Co., Ltd.,“ Takenate ”is a registered trademark of Mitsui Chemicals, Inc.) 504 Changed to "parts (3 mol)", "polyethylene glycol 498 parts" changed to "propylene oxide modified glycerin (trade name: Newpol GP-600, manufactured by Sanyo Chemical Industries, Ltd.) 602 parts (1 mol)", Same as Production Example 1 except that “826 parts of acrylate based on pentaerythritol triacrylate” was changed to “1239 parts (2.5 mol of triacrylate, 0.3 mol of diacrylate, 3.0 mol as hydroxy group)” (Methyl ethyl ketone is 8 % To become the theoretical amount), to obtain a methyl ethyl ketone solution of acryloyl group-containing urethane oligomer (c3). The number average molecular weight of the acryloyl group-containing urethane oligomer (c3) was 2100.

<Production Example 4>
“545 parts of isocyanurate of 1,6 hexane diisocyanate” was changed to “504 parts (3 mol) of 1,6 hexane diisocyanate (trade name: Takenate 700, manufactured by Mitsui Takeda Chemical Co., Ltd.)”, “498 parts of polyethylene glycol "Propylene oxide modified glycerin (trade name: Newpol GP-4000, manufactured by Sanyo Chemical Industries, Ltd.) 3990 parts (1 mol)" and "826 parts acrylate mainly composed of pentaerythritol triacrylate" Except for changing to "1239 parts (2.5 mol of triacrylate, 0.3 mol of diacrylate, 3.0 mol as hydroxy group)", the same as in Production Example 1 (methylethylketone is the theoretical amount of 80% in the heating residue) ), Urethane resin containing acryloyl group To obtain a methyl ethyl ketone solution of Goma (c4). The number average molecular weight of the acryloyl group-containing urethane oligomer (c4) was 5600.

<Production Example 5>
In a reaction vessel capable of heating, stirring, cooling, dropping, pressurizing and depressurizing, sucrose {trade name; sucrose, manufactured by Wako Pure Chemical Industries, Ltd., first grade} 342 parts (1 mol) and dimethylformamide (DMF) {Mitsubishi Gas Chemical Co., Ltd.} After uniformly mixing 1000 parts, using nitrogen gas, pressurize until the pressure reaches 0.4 MPa with gauge pressure and exhaust until 0.02 MPa (pressurized nitrogen substitution) 3 times It was. Thereafter, the temperature was raised to 100 ° C. with stirring, 4350 parts (75 mol) 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 react with the remaining PO. I let you. Next, the mixture was heated to 120 ° C., and 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 700 {Synthetic inorganic adsorbent, "Kyoward" manufactured by Kyowa Chemical Industry Co., Ltd. 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. Filtered with 2 filter paper {manufactured by Toyo Filter Paper Co., Ltd.} to remove Kyoward 700, and further dehydrated at 120 ° C. under reduced pressure of 0.01 to 0.02 MPa for 1 hour to obtain a polyoxyalkylene compound (h1) ( Sucrose / PO 75 mol) was obtained.

<Production Example 6>
469 parts (0.1 mol) of the polyoxyalkylene compound (h1) 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 to 100 under a reduced pressure of 1.3 to 2.7 Pa. Dehydrated at 1 ° C. for 1 hour. Then, after cooling to 50 ° C., 12 parts (0.07 mol) of 1,6-hexane diisocyanate {trade name: Takenate 700, manufactured by Mitsui Takeda Chemical Co., Ltd.} was added, and nitrogen substitution was performed three times in the same manner as in Production Example 5. Repeated. 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 (k1) was obtained. It was.

<Example 1>
In a mixing tank made of stainless steel with a stirring blade and a motor, 106.3 parts of methyl ethyl ketone solution (85 parts as a heating residue) of the (meth) acryloyl group-containing urethane oligomer (c1) prepared in Production Example 1 and (meth) acryloyl group-containing Urethane oligomer (d1) {Bifunctional urethane oligomer, trade name: CN9783, manufactured by Sartomer Japan, Ltd.} 15 parts, 0.2 parts of polyalkylene oxide compound (h1) obtained in Production Example 5, obtained in Production Example 6 Charged with 1 part of reactant (k1), 5 parts of photo radical initiator (p1) {1-hydroxycyclohexyl phenyl ketone}, and 227 parts of solvent {methyl ethyl ketone} (theoretical value with 30% heating residue) at 40 ° C. Mix for 1 hour, then measure the heating residue and use solvent (t1) {methyl ethyl ketone} so that the heating residue is 30%. The ultraviolet curable composition (1) of this invention was obtained by adjusting and filtering with the filter paper with a reserved particle diameter of 2 micrometers {Toyo Filter Paper Co., Ltd., PF020}.

<Examples 2 to 7>
Table 10 shows "10. 3 parts of methyl ethyl ketone solution of (meth) acryloyl group-containing urethane oligomer (c1)", "15 parts of (meth) acryloyl group-containing urethane oligomer (d1)", and "227 parts of solvent {methyl ethyl ketone}". Except having changed to what was shown and the usage-amount (part), it carried out similarly to Example 1, and obtained the ultraviolet curable composition (2)-(7) of this invention.
In addition, description of Table 1 showed the value as a heating residue.

  In Table 1, c1, c2, c3, c4, c5, d1, d2, d3, g1, e1, h1, k1, s1, f1, f2, and p1 are as follows.

c1: Acrylyl group-containing urethane oligomer prepared in Production Example 1 {reaction product of tetraisocyanate (1 mol), diacrylate (0.2 mol) and triacrylate (1.7 mol), number average molecular weight 2900}
c2: acryloyl group-containing urethane oligomer prepared in Production Example 2 {reaction product of tetraisocyanate (1 mol), diacrylate (0.2 mol) and triacrylate (1.7 mol), number average molecular weight 3500}
c3: Acrylyl group-containing urethane oligomer prepared in Production Example 3 {reaction product of triisocyanate (1 mol), diacrylate (0.3 mol) and triacrylate (2.5 mol), number average molecular weight 2100}
c4: Acrylyl group-containing urethane oligomer prepared in Production Example 4 {reaction product of triisocyanate (1 mol), diacrylate (0.3 mol) and triacrylate (2.5 mol), number average molecular weight 5600}
c5: Acryloyl group-containing urethane oligomer {Negami Kogyo Co., Ltd. Art Resin UN-909, number average molecular weight 3000; 1 mol of triisocyanate (prepolymer), pentaerythritol triacrylate and 1 to 6.5 mol of pentaerythritol diacrylate Acrylyl group-containing urethane oligomer obtained by reaction}

d1: An acryloyl group-containing urethane oligomer containing two acryloyl groups {CN9783 from Sartomer Japan Co., Ltd.}
d2: an acryloyl group-containing urethane oligomer containing three acryloyl groups {PHOTOMER6008 manufactured by Cognis Japan Co., Ltd.}
d3: Acryloyl group-containing urethane oligomer containing two acryloyl groups {Nippon Gosei Kagaku Kogyo Kogyo UV-7000B}

g1: Tricyclodecane dimethylol diacrylate (Light acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.)
g2: Acryloylmorpholine {ACMO manufactured by Kojin Co., Ltd. ("ACMO" is a registered trademark of the same company)}

e1: Polyurethane {Byron 3210 manufactured by Toyobo Co., Ltd., methyl ethyl ketone solution, heating residue 30%, "Byron" is a registered trademark of the company. }

h1: Polyalkylene oxide compound prepared in Production Example 5

k1: Reaction product of polyalkylene oxide compound (h1) prepared in Production Example 6 and 1,6-hexane diisocyanate

s1: Polyoxyalkylene-modified silicone {Fz-2110 manufactured by Toray Dow Corning Co., Ltd.}

f1: Silica {organosilica sol MEK-ST manufactured by Nissan Chemical Industries, Ltd., methyl ethyl dispersion, heating residue 30%, volume average particle size 15 nm}
f2: Phosphorus-doped tin oxide {Sellnax CX-S204IP manufactured by Nissan Chemical Industries, Ltd., isopropyl alcohol solution, volume average particle size 12 nm, "Selnax" is a registered trademark of the same company. }

p1: Photoradical initiator (1-hydroxycyclohexyl phenyl ketone)

<Comparative Example 1 {corresponding to Example 1 described in Japanese Patent Laid-Open No. 2009-24168}, Comparative Example 2>
“100 parts of methyl ethyl ketone solution of (meth) acryloyl group-containing urethane oligomer (c1)”, “20 parts of (meth) acryloyl group-containing urethane oligomer (d1)”, “228 parts of solvent {methyl ethyl ketone}” are shown in Table 2. Comparative UV curable compositions (1) and (2) were obtained in the same manner as in Example 1 except that the amount and the amount (parts) were changed.
In addition, description of Table 2 showed the value as a heating residue.

In Table 2, d1, f1, and p1 have the same meaning as in Table 1.
g2: Mixture of dipentaerythritol hexaacrylate and pentaacrylate {Neomer DA600, “Neomer” manufactured by Sanyo Chemical Industries, Ltd. is a registered trademark of the same company. }
g3: Bisphenol A type epoxy acrylate {Ebecryl 600 manufactured by Daicel-Cytec Co., Ltd.}
p2: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

  The UV curable compositions obtained in Examples and Comparative Examples were evaluated for processability, processing stability, scratch resistance, scratch resistance, storage shape retention and practicality as follows. The 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 (ultraviolet 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.
After that, for evaluation of scratch resistance and evaluation of fingerprint wiping properties, a 10 cm × 10 cm square was cut out, and for evaluation of workability, it was cut out to 5 mm × 120 mm to prepare a sample for evaluation.

<Abrasion resistance>
About the sample for evaluation, using an apparatus (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.) prepared in accordance with “5.5 light transmittance and total light reflectance, (1) apparatus” of JIS K7105 (1981), 23 ± 2. After measuring haze (%) in an environment of 50 ° C. and a relative humidity of 50 ± 5% (initial value), an apparatus conforming to JIS L0849: 2004 wear tester I type (clock meter) {rubbing manufactured by Imoto Seisakusho Co., Ltd. A sample is attached to the sample stand of tester B1052}, and steel wool {Bonster No. 0000 "Bonster" is a registered trademark of the same company}, and the cured film surface was worn 10 times with a load of 500 g / cm ² . After the worn surface was wiped off dust such as steel wool and scraped cured film with Japanese Pharmacy Type I absorbent cotton, haze was measured again in the same manner as above (after wear). Haze (after wear) −haze (initial value) was defined as scratch resistance. The smaller the value, the better the scratch resistance.

<Moldability>
The sample for evaluation was attached to a tensile tester {Shimadzu small tabletop tester EZ-L, pulling speed 100 mm / min, manufactured by Shimadzu Corporation) with a grip distance of 5 cm, in an environment of 23 ± 2 ° C and relative humidity 50 ± 5%. Then, the film was stretched until a crack occurred in the coating film visually, and (elongation) ÷ 5 × 100 was calculated from the elongation (cm) when the crack occurred, and was defined as moldability. For example, when the distance at which the crack occurs is 6 cm, the elongation is 1 cm (6-5 cm), and is calculated as 20% (1 cm / 5 cm × 100). The larger the value, the better the moldability.

<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 average of 5 times was defined as the fingerprint wiping property (when the wiping property was 30 or more, x was displayed). The smaller the value, the better the fingerprint wiping property.

In applications where scratch resistance is prioritized (scratch resistance of 0.5% or less, Examples 1 and 2 and Comparative Example 1), the ultraviolet curable compositions of the present invention (Examples 1 and 2) are ultraviolet rays for comparison. Compared to the curable composition (Comparative Example 1), the moldability and the fingerprint wiping property were remarkably excellent.
Further, in applications where moldability is prioritized (moldability of 20% or more, Examples 3 to 5 and Comparative Example 2), the ultraviolet curable compositions (Examples 3 to 5) of the present invention are comparative ultraviolet curable. Compared to the composition (Comparative Example 2), the scratch resistance and the fingerprint wiping property were remarkably excellent.
In applications where the scratch resistance is not strongly questioned (scratch resistance of about 4, Examples 6 and 7 and Comparative Example 2), the ultraviolet curable compositions of the present invention (Examples 6 and 7) are for comparison. Compared to the ultraviolet curable composition (Comparative Example 2), the moldability and the fingerprint wiping property were extremely excellent.

  The ultraviolet 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 most suitable as a coating agent for thermoforming films used for in-mold molding (transfer shaping), insert molding, and the like.

  Examples of the plastic molded article include a molded article for home appliances, a molded article for vehicles, a molded article for building materials, and the like. Examples of the molded article for home appliances include a TV, audio or mobile phone exterior material, and a protective plate such as a liquid crystal. Examples of the vehicle molded body include a headlamp lens, a blinker lens, a sunroof, a meter cover, a motorcycle windshield, and a helmet shield. Examples of the molded body for building materials include highway soundproof walls, partition boards, and daylighting windows. In addition to these, the present invention can also be applied to frame plastic plates, display panels, optical lenses, plastic containers, and decorative items.

Claims (6)

(Meth) obtained by reaction of 1 mol of tri- to hexa-isocyanate (A) with 1 to 6.5 mol of di (meth) acrylate having a hydroxyl group and / or tri (meth) acrylate (B) having a hydroxyl group An acryloyl group-containing urethane oligomer (C) ;
Containing the polyoxyalkylene compound (H) represented by the general formula (1) and / or the reaction product (K) of the polyoxyalkylene compound (H) and the diisocyanate (J) ,
The ultraviolet curable composition characterized in that the di (meth) acrylate having a hydroxyl group and / or the tri (meth) acrylate (B) having a hydroxyl group is a mixture of dihydroxydi (meth) acrylate and monohydroxytri (meth) acrylate. object.

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

Q is a reaction residue obtained by removing a hydrogen atom from m hydroxyl groups of a non-reducing di- or trisaccharide, OX is an oxyalkylene group, R is an alkyl group, a copolymerizable double bond-containing group and / or a hydrogen atom, ni represents an integer of 0 to 100, m represents an integer of 2 to 4, 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 20 to It is an integer of 100. The ultraviolet curable composition of Claim 1 which further contains the (meth) acryloyl group containing urethane oligomer (D) which contains 2-3 (meth) acryloyl groups in 1 molecule. Furthermore, the ultraviolet curable composition of Claim 1 or 2 containing a polymer (E). Furthermore, the ultraviolet curable composition in any one of Claims 1-3 containing a filler (F). Furthermore, the ultraviolet curable composition in any one of Claims 1-4 containing a mono (meth) acrylate and / or di (meth) acrylate (G). A plastic film for molding obtained by coating the ultraviolet curable composition according to any one of claims 1 to 5 on a plastic base film.