CN103786398B

CN103786398B - Decoration hard coat film and decoration are coated with bonding film firmly

Info

Publication number: CN103786398B
Application number: CN201310515896.2A
Authority: CN
Inventors: 渡边大亮; 山川大辅; 高桥佑辅; 须田春奈; 西泽茂年; 高石诗织
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2012-10-31
Filing date: 2013-10-28
Publication date: 2016-08-17
Anticipated expiration: 2033-10-28
Also published as: TWI537137B; JP6075009B2; KR20140056072A; JP2014088010A; TW201433460A; CN103786398A

Abstract

The present invention provides a kind of decoration hard coat film, and it be the composition in slim aspect excellence, is not likely to produce the decline of case hardness simultaneously, and has good punch press process, re-workability.A kind of decoration hard coat film, it has: at least one side at base material has the hard coat film of hard conating, is arranged at the decorative layer of the part on described hard coat film surface and is arranged at the resin bed comprising active energy ray-curable resin composition on the surface with decorative layer of hard coat film, described in comprise active energy ray-curable resin composition the store elastic elastic modelling quantity (E ') of measured under frequency 3.5Hz 60 DEG C of resin bed be 2.0 × 10⁸～9.0 × 10⁸Pa.By described decoration hard coat film, thus become in the excellent composition of slim aspect, the suitable re-workability after being capable of suitable case hardness, punch press process simultaneously and being fixed on other components.

Description

Decoration hard coat film and decoration are coated with bonding film firmly

Technical field

The present invention relates to the dress that such as can use in constituting the manufacture of image display panel etc. of image display device Decorations hard coat film.

Background technology

As the liquid crystal indicator in the miniature electric terminals such as mobile PC, electronic memo, mobile phone Deng image display device, commonly known have the dress being provided with transparent image display panel on the top of image display Put.

Above-mentioned image display panel in most cases utilizes transparent adhesion band etc. and is fixed on above-mentioned image display Deng.

But, above-mentioned image display panel is provided with decorative layer for the purpose of decoration, shading etc. mostly, sometimes exists There is surface and the interface of transparent adhesion band of above-mentioned image display panel by the step discrepancy in elevation part caused by this decorative layer Place, can remain bubble.

As solution to the problems described above, it is known to following method, i.e. such as by being provided with the image of decorative layer Ultraviolet curable resin is filled on the surface of the above-mentioned decorative layer side of display floater, thus utilizes above-mentioned ultraviolet curing resin to make The step discrepancy in elevation part produced owing to arranging decorative layer carries out the method (referring for example to patent documentation 1 and 2) smoothed.

But, during being pushed further into the slimming of above-mentioned image display device, miniaturization, existing using In the case of ultraviolet curing resin, cause the decline of the case hardness of image display panel sometimes or image is being shown Show panel to carry out during punch press process and cause rupturing of image display panel.It addition, with adhesive tape by above-mentioned image display panel After Gu Ding, when being peeled off (reprocessing), sometimes still can cause rupturing of image display panel.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2012-022210 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2013-148618 publication

Summary of the invention

Invent problem to be solved

Problem to be solved by this invention is to provide a kind of decoration hard coat film, and it is slim at image display device etc. The composition that aspect is excellent, will not produce the problem caused by the step discrepancy in elevation part caused by above-mentioned decorative layer simultaneously, and have There is the case hardness of excellence, and there is punch press process and the re-workability of excellence.

For solving the means of problem

The present inventor etc. are studied to solve above-mentioned problem, found that by having the hard painting of decorative layer The resin bed that the surface configuration of film specifies, such that it is able to solve above-mentioned problem.

That is, the present invention relates to a kind of decoration hard coat film, it is characterised in that have: at least one side at base material has hard painting The hard coat film of layer, be arranged at the decorative layer of the part on described hard coat film surface and be arranged at described hard coat film there is decoration The resin bed on the surface of layer, described resin bed uses active energy ray-curable resin composition to be formed, described tree The store elastic elastic modelling quantity of measured under frequency 3.5Hz 60 DEG C of lipid layer (E ') it is 2.0 × 10⁸～9.0 × 10⁸Pa。

The effect of invention

The decoration hard coat film of the present invention is the composition directly arranging decorative layer on hard coat film, therefore at image display device Slimming aspect excellent.It addition, by comprising actinic energy ray curable resion composition by be arranged at decorative layer side Resin bed be set to specific resin bed, thus be not likely to produce the decline of case hardness, and be difficult to firmly when punch press process Coating, resin bed crack, therefore there is suitable punch press process.It addition, consolidated by adhesive phase, adhesive tape In the case of on other components, it is not easy to when reprocessing produce hard conating, the rupturing of resin bed, decorates hard coat film The most broken, therefore, it is possible to realize suitable punch press process.Therefore, the decoration hard coat film of the present invention can be suitable for well and be The device used for image display way of electronic equipment, mobile PC that particularly requirement of slimming or miniaturization is high, electronics The image display panel of the image display device of the miniature electric terminal such as notebook, mobile phone.

Accompanying drawing explanation

Fig. 1 is the figure of an example of the configuration example of the decoration hard coat film representing the present invention.

Fig. 2 is the figure of an example of the configuration example of the decoration hard coat film representing the present invention.

Symbol description

1, hard coat film

2, hard conating (1)

3, hard conating (2)

4, base material

5, decorative layer

6, resin bed

Detailed description of the invention

The decoration hard coat film of the present invention, it is characterised in that have: at least one side at base material has the hard painting of hard conating Film, it is arranged at the decorative layer of the part on hard coat film surface and is arranged at the resin bed on the surface with decorative layer of hard coat film, In above-mentioned decoration hard coat film, have use active energy ray-curable resin composition and the resin bed that formed as above-mentioned Resin bed, the store elastic elastic modelling quantity of measured under frequency 3.5Hz 60 DEG C of this above-mentioned resin bed (E ') is 2.0 × 10⁸～9.0 × 10⁸Pa。

As above-mentioned decoration hard coat film, decoration hard coat film that its gross thickness be 100～170 μm is preferably used.

[base material]

As the base material used in the manufacture of the decoration hard coat film of the present invention, it is possible to use be suitable to the base material of slimming, excellent The base material that choosing uses its thickness to be 50～160 μm, the base material more preferably using its thickness to be 50～130 μm, further preferably make With the base material that thickness is 60～110 μm.By using the base material of above-mentioned thickness such that it is able to suppression makes decoration hard coat film slim The curling that can produce during change.It addition, cut off processing or during punch press process above-mentioned decoration hard coat film is carried out, it is easy to suppress due to The extruding of its cutter and the elongation of base material that causes, and can suitably suppress rupturing of hard conating.

As above-mentioned base material, the film base material of elastic modelling quantity 3～7GPa is preferably used, particularly preferably use elastic modelling quantity 3～ The film base material of 5GPa.Be there is the film base material of the elastic modelling quantity of above-mentioned scope by use, thus when forming decoration hard coat film not It is easily generated the deformation of film base material, it is possible to suppress rupturing of hard conating well, it is possible to the surface suppressing above-mentioned decoration hard coat film is hard The decline of degree.Further, since be able to ensure that the flexibility of above-mentioned film base material, even if therefore decoration hard coat film being attached to composition In the case of the curved face part of the mitigation of adherend etc., it is also easy to follow above-mentioned curved face part.

As above-mentioned film base material, it is possible to use the various resin molding base materials used generally as the base material of hard coat film, can To use such as polyethylene terephthalate, polybutylene terephthalate (PBT), PEN, poly-second Alkene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, cellulose acetate-butyrate, polrvinyl chloride, poly-inclined two chloroethenes Alkene, polyvinyl alcohol, vinyl-vinyl acetate copolymer, polystyrene, Merlon, polymethylpentene, polysulfones, polyether-ether-ketone, The resin molding of polyether sulfone, Polyetherimide, polyimides, fluororesin, nylon, acrylic resin etc..

As above-mentioned film base material, it is possible to use the base material being only made up of above-mentioned resin molding, but in order to improve and hard conating Adaptation, it is possible to use there is the base material of thin priming coat on the surface of above-mentioned resin molding.It addition, it is close in order to improve with hard conating Conjunction property, it is possible to use implement the concave-convex surfaceization by sand-blast or solvent treatment method etc. and process or at corona discharge Reason, chromic acid process, fire scorching processes, hot blast processes, ozone processes or ultraviolet treatment with irradiation, the surface such as oxidation processes on surface Base material after reason.

[hard conating]

As the hard conating of at least one side being arranged at above-mentioned base material, the various hard varnishs of use can be listed and formed Hard conating.

As above-mentioned hard varnish, the hard painting containing active energy ray-curable resin composition can be used well Agent, is preferably used the hard varnish containing carbamate (methyl) acrylate.

As above-mentioned carbamate (methyl) acrylate, it is possible to use the various amino first used as hard varnish Acid esters (methyl) acrylate, wherein, being preferably used must containing polyfunctional carbamate (methyl) acrylate (A) conduct Wanting carbamate (methyl) acrylate of composition, described polyfunctional carbamate (methyl) acrylate (A) is logical (methyl) acrylate (a1) and the polyisocyanate (a2) of crossing (methyl) acryloyl group making to have hydroxyl and more than 2 are anti- Answer and obtain.

As (methyl) acrylate (a1) of above-mentioned (methyl) acryloyl group with hydroxyl and more than 2, can make With such as trimethylolpropane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) Poly-(methyl) esters of acrylic acids such as acrylate, dipentaerythritol five (methyl) acrylate.It addition, as above-mentioned (methyl) third Olefin(e) acid ester (a1), it is possible to use above-mentioned poly-(methyl) esters of acrylic acid and the addition product of 6-caprolactone, above-mentioned poly-(methyl) propylene The addition product of esters of gallic acid and alkylene oxide and there is epoxy (methyl) acrylate etc. of epoxy radicals.

As above-mentioned (methyl) acrylate (a1), it is preferably used and there are 1 hydroxyl and 3～5 (methyl) acryloyl groups (methyl) acrylate, specifically, from obtaining the aspect of the excellent decoration hard coat film of case hardness, season is preferably used Penta tetrol three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc..

As the above-mentioned polyisocyanate (a2) can reacted with above-mentioned (methyl) acrylate (a1), such as can be independent Use or be applied in combination two or more following substances etc., i.e. 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI), 1, 3-XDI, 4,4 '-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4 '-diphenyl methane The aromatic isocyanates such as diisocyanate；Dicyclohexyl methyl hydride diisocyanate, isophorone diisocyanate, norbornane Diisocyanate, hydrogenation of benzene dimethylene diisocyanate, hydrogenated diphenyl methane diisocyanate, Isosorbide-5-Nitrae-hexamethylene two Carbimide. Esters etc. have the ester ring type isocyanates of 2 NCOs being bonded with ester ring type hydrocarbon；Trimethylene diisocyanate, six Asias The aliphatic diisocyanates etc. such as methyl diisocyanate.

As above-mentioned polyisocyanate (a2), possess, from obtaining, decoration hard coat film that high tenacity and being not likely to produce ruptures etc. Aspect is set out, and aliphatic diisocyanate or ester ring type diisocyanate is preferably used, wherein, more preferably uses isophorone two Isocyanates, norbornene alkyl diisocyanate, hydrogenation of benzene dimethylene diisocyanate, hydrogenated diphenyl methane diisocyanate and Hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, dicyclohexyl methyl hydride-4,4 '-diisocyanate.

For in above-mentioned hard conating, constitute the hard conating on top layer of image display device, sometimes require that higher firmly Balance between the reduction of shrinkage factor when degree and solidification.Described hard conating preferably has the hard painting of two or more circulus Layer, wherein a kind is hetero ring type structure.

As the hard varnish of the above-mentioned hard conating with circulus can be formed, such as, can use and there is circulus Carbamate (methyl) acrylate (A-1) as above-mentioned carbamate (methyl) acrylate (A), wherein, preferably Use and there is carbamate (methyl) acrylate of two or more circulus comprising hetero ring type structure, this be because of For the case hardness of decoration hard coat film can be improved further, and its generation crimped can be suppressed.

For above-mentioned carbamate (methyl) acrylate (A-1) with circulus, it is possible to use such as make With there is (methyl) acrylate of circulus as above-mentioned (methyl) acrylate (a1), and make itself and above-mentioned polyisocyanate Carbamate (methyl) acrylate that ester (a2) reacts and obtains；Use and there is the polyisocyanate of circulus as upper State polyisocyanate (a2), and make it react with above-mentioned (methyl) acrylate (a1) and the carbamate (methyl) third that obtains Olefin(e) acid ester etc..

It addition, as above-mentioned carbamate (methyl) acrylate (A-1) with circulus, example can be listed The amino obtained as made the above-mentioned polyisocyanate (a2) with circulus or its trimer and above-mentioned (a1) carry out addition Formic acid esters (methyl) acrylate.

(methyl) acrylate with circulus that can use as above-mentioned (methyl) acrylate (a1), can To use such as two (acryloyl-oxyethyl) hydroxyethyl isocyanuric acid ester (Aronix M-215), two (acryloxy second Base) hydroxyethyl isocyanuric acid ester (Aronix M-215), three (2-hydroxyethyl) isocyanurate triacrylate (Aronix M-315), caprolactone modification three (acryloyl-oxyethyl) isocyanuric acid ester (Aronix M-325), modified three hydroxyls of neopentyl glycol Diacrylate (Kayarad R-604) etc. has (methyl) acrylate etc. of miscellaneous circulus.

Above-mentioned carbamate (methyl) acrylate (A) can be by making above-mentioned polyisocyanate (a2) and above-mentioned (first Base) acrylate (a1) both compositions reaction manufacture.The equivalent of the hydroxyl that above-mentioned (methyl) acrylate (a1) is had, Isocyanates 1 equivalent being had relative to above-mentioned polyisocyanate (a2), the scope of preferably 0.1～50, more preferably 0.1 ～the scope of 10, the more preferably scope of 0.9～1.3, the scope of particularly preferably 1.01～1.24.

It addition, the reaction temperature of above-mentioned polyisocyanate (a2) and above-mentioned (methyl) acrylate (a1) be preferably 30～ The scope of 150 DEG C, the scope of more preferably 50～100 DEG C.It should be noted that the terminal of above-mentioned reaction can be by the most such as Under method confirm: represent NCO 2250cm^-1Infrared absorption spectrum disappearance, utilize JIS K7301- Method described in 1995 obtains NCO containing ratio.

Carbamate (methyl) acrylate (A) utilizing said method to obtain is preferably averagely has more than 5 (first Base) carbamate (methyl) acrylate of acryloyl group, more preferably there is the ammonia of 5～10 (methyl) acryloyl groups Carbamate (methyl) acrylate.

As above-mentioned carbamate (methyl) acrylate (A), it is preferably used and has 500～1, dividing of the scope of 500 Carbamate (methyl) acrylate of son amount, this is because case hardness height can be obtained and owing to can suppress solid Contraction during change and be not likely to produce the decoration hard coat film of curling.

Above-mentioned carbamate (methyl) acrylate (A-1), relative to the resinous principle 100 contained in above-mentioned hard varnish Mass parts, preferably comprises 5～90 mass parts, more preferably contains 10～70 mass parts, further preferably containing 10～60 mass parts. By using the hard varnish of carbamate (methyl) acrylate (A-1) containing above-mentioned scope, such that it is able to obtain surface Hardness is high and is not likely to produce the decoration hard coat film of curling, the most preferably due to contraction when can suppress solidification.

Above-mentioned hard varnish can use in addition to above-mentioned carbamate (methyl) acrylate (A-1), as required also Containing other compositions as the hard varnish of above-mentioned carbamate (methyl) acrylate (A).

As other compositions above-mentioned, it is possible to use such as in addition to above-mentioned carbamate (methyl) acrylate (A-1) Other carbamates (methyl) acrylate (A-2).

As above-mentioned other carbamates (methyl) acrylate (A-2), can list and not there is circulus Carbamate (methyl) acrylate.

Above-mentioned carbamate (methyl) acrylate (A-2), relative to above-mentioned carbamate (methyl) acrylate (A-1) 100 mass parts, preferably uses, in the range of 10～150 mass parts more preferably in the range of 50～130 mass parts Use.

It addition, as hard varnish, it is possible to use possibly together with other, there is (first as required in addition to above-mentioned composition Base) the hard varnish of polymer (B) of acryloyl group.

As above-mentioned polymer (B), can list such as: make there are hydroxyl, carboxyl, epoxy radicals etc. as anti-at side chain (methyl) acrylate polymer (b1) of Ying Xing functional group, and has NCO, carboxyl, acid halide group, hydroxyl, epoxy radicals In the α of functional group, the polymer etc. with (methyl) acryloyl group that β-unsaturated compound (b2) reacts and obtains.

As above-mentioned polymer (B), it is possible to use such as trimethylolpropane trimethacrylate, two (trimethylolpropanes) The ethylene-oxide-modified triacrylate of tetraacrylate, glycerol triacrylate, isocyanuric acid, tetramethylolmethane three acrylic acid Ester, tetramethylol methane tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate etc., be preferably used season Penta tetrol triacrylate, tetramethylol methane tetraacrylate, 6-caprolactone modification dipentaerythritol acrylate.

Relative to the solid constituent contained in above-mentioned hard varnish, preferably contain above-mentioned polymerization with the scope of 5～40 mass % Thing (B).

As above-mentioned hard varnish, it is possible to use containing the hard varnish of Photoepolymerizationinitiater initiater.As above-mentioned Photoepolymerizationinitiater initiater, Such as benzophenone, benzil, michaelis ketone, thiaxanthone, anthraquinone etc. can be used by dehydrogenation to be produced the type of free radical Compound etc..Above-mentioned Photoepolymerizationinitiater initiater general with as the methyl amine of dehydrogenating agent, diethanolamine, N methyldiethanol amine, three The tertiary amine combinations such as butylamine use.

As Photoepolymerizationinitiater initiater, in addition to above-mentioned Photoepolymerizationinitiater initiater, it is also possible to list divided by intramolecular and Produce the compound of the type of free radical.Specifically, it is possible to use such as benzoin, Dialkoxy acetophenones, acyl oxime ester, benzene Even acyl ketal, hydroxyalkylphenones, halogenated ketone etc..

Relative to quality 100 mass parts of the active energy ray-curable resin composition as above-mentioned hard varnish, on State Photoepolymerizationinitiater initiater preferably to use in the range of 1～10 mass parts, more preferably use in the range of 4～9 mass parts.

As above-mentioned hard varnish, it is possible to use following hard varnish, i.e. containing as required with above-mentioned Photoepolymerizationinitiater initiater Hydroquinone, benzoquinone, methylnaphthohydroquinone, the hard varnish of the polymerization inhibitor such as p-tert-Butylcatechol.

In order to improve the surfaces characteristic such as the surface smoothness of above-mentioned hard conating, stain resistance, resistance and fingerprint resistance tack, as shape Become in above-mentioned hard conating, constitute the hard varnish of the hard conating on the top layer of image display device, it is possible to use containing having fluorine Carbochain, dimethyl siloxane chain, the hard varnish of compound of hydrocarbon chain of carbon number more than 12.

Wherein, go out in terms of improving the surfaces characteristic such as stain resistance, resistance and fingerprint resistance tack, oiliness ink liquid scrubbability further Send out, compound containing above-mentioned fluorocarbon chain is preferably used, more preferably use heterocycle and poly-(perfluor Asia by bivalence linking base group Alkyl ether) single end of chain or two ends bonding and this heterocycle rolled into a ball by bivalence linking base and be bonded with (methyl) of more than 2 Compound obtained by acryloyl group.

Relative to the total amount of the active energy ray-curable resin composition as above-mentioned hard varnish, above-mentioned have fluorine carbon Chain, dimethyl siloxane chain, the compound of hydrocarbon chain of carbon number more than 12 preferably make in the range of 0.05～5 mass % With, more preferably use in the range of 0.1～2 mass %.

[hard coat film]

As the hard coat film used in the present invention, it is possible to use at least one side at base material has the hard coat film of hard conating. Wherein, from being prone to as slim and be easily achieved suitable case hardness, anti-scratch, it may be preferred to use at the two of base material Mask has the two-sided hard coat film of hard conating.

Be more than H as the case hardness of above-mentioned hard coat film, preferably pencil hardness, further preferred pencil hardness be 2H with On.By being set as this case hardness, such that it is able to improve the scratch resistance of decoration hard coat film further.

In the two sides of above-mentioned base material has the two-sided hard coat film of hard conating, the hard conating of the side of decorative layer to be arranged The pencil hardness of (the hereinafter referred to as first hard conating) is preferably more than H, more preferably more than 2H.It addition, with above-mentioned The pencil hardness of the hard conating (the hereinafter referred to as second hard conating) of the side that one hard conating is contrary is preferably more than 2H, further It is preferably more than 3H.Be there is by use the hard coat film of the pencil hardness of above-mentioned scope, suitably prevent such that it is able to obtain possessing The decoration hard coat film of scratch resistant, punch press process etc..

The thickness of above-mentioned hard conating suitably selects according to the purposes applied, and being applied to, slim requirement is high In the case of miniature electric terminal etc., the scope of preferably 1～15 μm.It addition, constitute the above-mentioned two sides at base material there is hard painting The thickness of the first hard conating of the two-sided hard coat film of layer is preferably the scope of 1～6 μm, constitutes the above-mentioned two sides at base material and has firmly The thickness of the second hard conating of the two-sided hard coat film of coating is preferably the scope of 7～15 μm.By being set as the thickness of above-mentioned scope Degree, such that it is able to accomplished surface characteristic and the decoration hard coat films of slimming such as suitable case hardness, scratch resistance.

There is the two-sided hard coat film of hard conating as the above-mentioned two sides at base material, by being set by the thickness of the first hard conating It is less than the 3/5 of thickness of the second hard conating, preferably 1/10～3/5, more preferably 1/5～3/5, such that it is able to the curling that is inhibited And keep suitable hardness, suppress processing cutter the first hard conating being answered when the second hard conating side entrance when punch press process Power, it is not likely to produce the decoration hard coat film of the crackle of the first hard conating, the most preferably.The hard of above-mentioned specific thickness is possessed by use The two-sided hard coat film of coating, can obtain being not likely to produce curling, keeping high surface hardness, the most resistance to anti-thread breakage i.e. punch press process Excellent decoration hard coat film.Described decoration hard coat film is suitably applied the screen panel of the portable electronic piece terminal requiring microfabrication Purposes etc..

Above-mentioned hard coat film can be by being coated with above-mentioned hard varnish at least one side of above-mentioned base material and making it be solidified to form Hard conating manufactures.

As the method that hard varnish is coated base material, such as gravure coating process, rolling method, comma coating can be enumerated Method, air knife coating method, kiss coating, spraying process, fusion rubbing method, dip coating, spin-coating method, Wheeler rubbing method (Wheeler Coat), spread coating, utilize the coating processes such as the full coat method (ベタ U one ト) of silk screen, bar rubbing method, flow coat method；Graph The printing processes such as brush, typographic printing.Wherein, as above-mentioned coating process, gravure coating process, rolling method, funny spot printing are preferably used Cloth method, air knife coating method, kiss coating, bar rubbing method, the coating process of flow coat method, this is because can be formed have smoother The hard conating on surface.

The coated face formed as making to be coated with hard varnish by said method carries out the method solidified, and can list photograph The method penetrating active energy beam.

As above-mentioned active energy beam, light, ultraviolet, electron ray, lonizing radiation etc. can be listed.

As above-mentioned active energy beam, it is preferred to use ultraviolet.

As the device of the above-mentioned ultraviolet of irradiation, low pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal can be listed Halide lamp, Non-polarized lamp (fusion lamp, Fusion Lamp), chemical lamp, black light lamp, hydrargyrum-xenon lamp, short-arc lamp, helium cadmium laser, Argon laser, sunlight, LED etc..It addition, as above-mentioned irradiation unit, xenon-flash of light that flash-mode be irradiated is preferably used Lamp, this is because can make the heat affecting to base material little.

From suppression curing reaction obstruction aspect, preferably under the inactive gas atmosphere such as nitrogen, carry out above-mentioned ultraviolet The irradiation of isoreactivity energy-ray.It addition, after irradiating above-mentioned active energy beam, heat cure reaction can be carried out by heating.

When producing above-mentioned hard coat film continuously in the way of so-called volume to volume, above-mentioned hard coat film is wound for drum, because of This first hard conating contacts with the another side (the second hard conating etc.) in the face with this hard conating.

Comprise in the case of there is the compound of above-mentioned fluorocarbon chain, dimethyl siloxane chain etc. at above-mentioned first hard conating, Sometimes mentioned component can in above-mentioned second hard conating, be intended to implement the part transfer of decoration, thus under the adaptation of decorative layer Fall.

From preventing the aspect of above-mentioned transfer, in the case of above-mentioned hard coat film is wound as drum, preferably upper State the surface configuration protective layer (protecting film) of hard conating.

[decorative layer]

The decorative layer of the decoration hard coat film constituting the present invention can give various appearance design to hard coat film.As above-mentioned dress Decorations layer, can list such as image display panel to use time visible word or figure around image displaying part Shape or be arranged at the laciniform decorative layer etc. of black of image displaying part with frame-shaped.Wherein, it is arranged at frame-shaped in use In the case of the decorative layer of image displaying part, it is especially susceptible to embody the effect of the present invention.

As the method that decorative layer is arranged at hard coat film, preferably by the method for printing, this is because simply.As Printing process, can be to enumerate such as screen printing mode, screen painting mode, intaglio printing mode, thermal transfer printing mode etc.. Wherein, it is preferably able to print the screen printing mode of opacifying property high decorative layer, screen painting mode, thermal transfer printing mode.

The black liquid used in screen printing mode, screen painting mode, it is possible to use each used in the printing to film Plant ink liquid, solvent system, UV can be used to solidify system.Especially, it is suitable for using solvent system ink liquid, this is because only need to be in drying oven Make solvent seasoning, therefore need not the devices such as UV irradiation unit, therefore, it is possible to print at a low price.

As the black liquid used in thermal transfer mode, it is possible to use resin type, wax pattern.Wherein, resin type is preferably used, this It is because it to have excellent weather resistance.

The thickness of decorative layer is preferably below 30 μm, more preferably 1～15 μm, particularly preferred 2～10 μm.By being set as this The decorative layer of thickness, thus be not likely to produce decolouring, print bad, it is easy to obtain the appearance design being suitable for.

[resin bed]

The resin bed of the decoration hard coat film constituting the present invention is to use active energy ray-curable resin composition and shape The layer become, is that the store elastic modulus (E ') of 60 DEG C recorded under frequency 3.5Hz is 2.0 × 10⁸～9.0 × 10⁸Pa, preferably 2.5×10⁸～7.0 × 10⁸Pa, more preferably 3.0 × 10⁸～5.0 × 10⁸The resin bed of Pa.By using above-mentioned resin bed, from And following decoration hard coat film can be obtained, this decoration hard coat film is the structure of the slim aspect excellence at image display device etc. Become, the unfavorable condition caused by the step discrepancy in elevation part caused by above-mentioned decorative layer will not be produced simultaneously, there is the table of excellence Surface hardness, and possess punch press process and the re-workability of excellence.

As above-mentioned resin bed, the martensite hardness recorded with the Vickers indenter at 136 ° of angle between load 1mN press-in rib is 70～100N/mm², this can obtain possessing applicable scratch resistance, the decoration hard coat film of case hardness, the most preferably.

About the thickness of above-mentioned resin bed, by its maximum gauge is set as more than the thickness of decorative layer, such that it is able to Fill and lead up the step discrepancy in elevation of decorative layer well, thus become prone to guarantee the flatness of above-mentioned resin layer surface.

The active energy ray-curable resin composition used in formation as above-mentioned resin bed, it is possible to use example As containing carbamate (methyl) acrylate (C), there are more than 3 (methyl) acryloyl groups trifunctional more than propylene Acid esters (D), there is the simple function of 1 (methyl) acryloyl group or there are two functional acrylates of 2 (methyl) acryloyl groups And the compositions of Photoepolymerizationinitiater initiater (F) (E).

Here, about above-mentioned (C)～the mixing ratio of each composition of (F), preferably with respect to the total of (C)～(E) composition 100 mass parts, carbamate (methyl) acrylate (C) is that the acrylate (D) of more than 30～60 mass parts, trifunctional is 5～30 mass parts, simple function or two functional acrylates (E) add up to 20～60 mass parts, and become relative to (C)～(E) Total 100 mass parts divided, above-mentioned Photoepolymerizationinitiater initiater (F) is 0.1～10 mass parts, has appropriateness concurrently this is because be easily formed Flexibility and the store elastic modulus (E ') of hardness and record under frequency 3.5Hz 60 DEG C be 2.0 × 10⁸～9.0 × 10⁸ Resin bed.

From the viewpoint of coating excellence, the viscosity of above-mentioned active energy ray-curable resin composition preferably 300 ～the scope of 1000mPa.s, it addition, from the viewpoint of the flexibility balancing good with curable, active energy ray-curable The double bond concentration of type resin combination is preferably the scope of 4～6mmol/g.

As above-mentioned carbamate (methyl) acrylate (C), it is possible to use such as contain the amino of NCO The urethane acrylate that urethane prepolymer and (methyl) acrylate (c3) with hydroxyl react and obtain, institute State the carbamate prepolymer containing NCO by making aliphatic polyester polyols (c1) and polyisocyanate (c2) React and obtain.By use above-mentioned carbamate (methyl) acrylate (C), it is possible to formed possess appropriateness flexibility, Possess the resin bed of required store elastic modulus (E '), and the decoration that punch press process, re-workability are excellent can be obtained Hard coat film, the most preferably.

As above-mentioned aliphatic polyester polyols (c1), can enumerate and such as make malonic acid, 1,3-propanedicarboxylic acid, adipic acid, the last of the ten Heavenly stems two The aliphatic polycarboxylic acid such as acid, dodecanedioic acid, with ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, new penta 2 Alcohol, 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexanediol, 1, the fat such as 9-nonanediol, glycerol, trimethylolpropane, tetramethylolmethane Race's polyol reaction and the PEPA that obtains；By the lactone compounds such as gamma-butyrolacton, δ-valerolactone, 6-caprolactone with The ring-opening polymerisation of above-mentioned aliphatic polyol and the PEPA that obtains.In these materials, from obtained carbamate From the viewpoint of (methyl) acrylate (C) can show good flexibility, preferably 6-caprolactone and aliphatic polyol Reactant.

The change that the intermiscibility with other compositions is excellent is become from making obtained carbamate (methyl) acrylate (C) The viewpoint of compound and make obtained carbamate (methyl) acrylate (C) not only have good flexibility but also From the viewpoint of can having the curable of excellence and the hardness of solidfied material concurrently, the number of above-mentioned aliphatic polyester polyols (c1) is divided equally The scope of son amount (Mn) preferably 300～1000, from the viewpoint of becoming significantly from making described effect, particularly preferred 400～600 Scope.Here, number-average molecular weight (Mn) is the value calculated by the hydroxyl value of above-mentioned aliphatic polyester polyols (c1).

Above-mentioned polyisocyanate (c2) can list such as toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, The aromatic diisocyanates such as naphthalene diisocyanate, XDI, tetramethylxylylene diisocyanate Ester；The aliphatic isocyanates such as hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate；Isosorbide-5-Nitrae-hexamethylene two Isocyanates, HMDI, methylcyclohexane diisocyanate, 1,2-bis-(methyl isocyanate Base) the ester ring type diisocyanate such as hexamethylene, norborene diisocyanate.Wherein, from making obtained carbamate third From the viewpoint of olefin(e) acid ester becomes the compound that the intermiscibility with other compositions is excellent, preferably ester ring type diisocyanate, especially Preferably isophorone diisocyanate.

Above-mentioned (methyl) acrylate (c3) with hydroxyl, can list such as (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate etc. have hydroxyl (methyl) acrylic acid of 1 acryloyl group Ester；Glycerol two (methyl) acrylate, isocyanuric acid ethylene-oxide-modified two (methyl) acrylate, tetramethylolmethane three (first Base) acrylate, two (trimethylolpropane) three (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc. have Hydroxyl (methyl) acrylate of more than 2 acryloyl groups.In these materials, from making obtained carbamate (methyl) third From the viewpoint of the compound of the balancing good that olefin(e) acid ester becomes flexibility and curable, preferably there are more than 2 acryloyl groups Hydroxyl (methyl) acrylate, particularly preferred tetramethylolmethane three (methyl) acrylate.

Carbamate (methyl) acrylate (C) obtained about making above-mentioned each composition react, from flexibility with solid From the viewpoint of the balancing good of the property changed, its double bond concentration is preferably the scope of 4～6mmol/g.

(methyl) acrylate (D) more than above-mentioned trifunctional is can be in above-mentioned active energy ray curable resin group The solidfied material of compound keeps good flexibility and shows the curable of excellence and the composition of the hardness of solidfied material.

As (methyl) acrylate (D) more than above-mentioned trifunctional, it is possible to use have more than 3 (methyl) acryloyls (methyl) acrylate of base, can enumerate such as: trimethylolpropane tris (methyl) acrylate, two (trimethylolpropanes) Four (methyl) acrylate, glycerol three (methyl) acrylate, isocyanuric acid ethylene-oxide-modified three (methyl) acrylate, Tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate and by above-mentioned (methyl) acrylate alkyl, oxirane, epoxy third The compound that alkane, 6-caprolactone etc. are in addition modified and obtain.Wherein, as (methyl) acrylate more than above-mentioned trifunctional (D), from the viewpoint of the flexibility balancing good with curable, tetramethylolmethane three (methyl) acrylate, season are preferably used Penta tetrol four (methyl) acrylate, 6-caprolactone modification dipentaerythritol six (methyl) acrylate.

Above-mentioned simple function or two senses (methyl) acrylate (E) are for making above-mentioned active energy ray curable resin The viscosity of compositions reduces and makes the composition that the coating characteristics of said composition improves, it is possible to use have 1 or 2 (methyl) (methyl) acrylate of acryloyl group, can enumerate such as (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) Butyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxyl fourth Ester, (methyl) acryloyl morpholine, tetrahydrofurfuryl (methyl) acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- Octyl Nitrite, (methyl) isobornyl acrylate, (methyl) benzyl acrylate, phenoxy group (methyl) acrylate, methoxyl group are poly- Ethylene glycol (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, (gathering) butanediol two (methyl) propylene Acid esters, neopentyl glycol two (methyl) acrylate, hexanediol two (methyl) acrylate, the oxide-modified two (first of bisphenol-A epoxy Base) acrylate, modified (methyl) acrylate of Bisphenol F diepoxide for example etc..In these materials, close from the first hard conating Conjunction property is excellent and skin irritation more weak from the viewpoint of, preferably tetrahydrofurfuryl carbinol (methyl) acrylic polyester, TEG Two (methyl) acrylate.

As above-mentioned Photoepolymerizationinitiater initiater (F), such as benzophenone, thiaxanthone, michaelis ketone, hydroxyphenylacetic acids can be enumerated Esters (oxyphenylacetic acid esters) etc. produce the light trigger of free radical by dehydrogenation；Benzoin, dialkoxy Benzoylformaldoxime, acyl oxime ester, benzil ketals, hydroxyalkylphenones, amino alkylphenone, acylphosphine oxide etc. are by molecule implosion Solution produces the light trigger of free radical.Wherein, as above-mentioned Photoepolymerizationinitiater initiater (F), particularly preferably use 2-hydroxyl-2-first Base-1-phenyl-propane-1-ketone, this is because it is aqueous, and can easily mix with other compositions.

Resin bed is formed as using the above-mentioned active energy ray-curable resin composition that can form resin bed Method, the decorative layer that has that above-mentioned active energy ray-curable resin composition coated hard coat film can be listed The surface of side, and make its method solidified.

As the method being coated with above-mentioned active energy ray-curable resin composition, such as intaglio plate coating can be listed Method, rolling method, comma rubbing method, air knife coating method, kiss coating, spraying process, fusion rubbing method, dip coating, spin-coating method, Wheeler are coated with Cloth method, spread coating, utilize the coating processes such as the full coat method of silk screen, bar rubbing method, flow coat method；Hectographic printing, typographic printing, silk The printing processes such as wire mark brush, screen painting.

The method being solidified to form resin bed as the coated face making above-mentioned active energy ray-curable resin composition, The method irradiating active energy beam can be listed.As active energy beam and irradiation unit thereof, can use and as energy The active energy beam that goes out illustrated in enough active energy beams used when forming above-mentioned hard conating and irradiation unit thereof and Its irradiation unit is identical.Above-mentioned active energy beam is preferably ultraviolet.

It addition, in order to realize polymerization high efficiency, be preferably irradiated under the inactive gas atmosphere such as nitrogen.It addition, can So that being used in the method being carried out under the state utilizing film, face glass smoothly to extrude solidifying by active energy beam. Furthermore it is possible to be applied in combination hot as the energy as required, can carry out at heat after utilizing active energy beam to solidify Reason.

The maximum gauge of above-mentioned resin bed is preferably 5～30 μm.

[decoration hard coat film]

The decoration hard coat film of the present invention has following composition: have on the surface with decorative layer of above-mentioned decoration hard coat film Above-mentioned resin bed.Above-mentioned resin bed can have following any one and constitute: with the part by being arranged at hard coat film surface The mode that decorative layer covers, is arranged at the whole region on the surface with decorative layer of decoration hard coat film so that it is surface planarisation Composition (Fig. 1)；Or, at the decoration hard coat film surface configuration resin being provided with beyond the part of decorative layer of decoration hard coat film Layer, the thickness making resin bed is identical with the thickness of decorative layer, thus makes the composition (Fig. 2) of the surface planarisation of decoration hard coat film.

Composition shown in Fig. 1 is prone to guarantee simply the flatness on surface, the most preferably；Composition shown in Fig. 2 is prone to make The decoration further slimming of hard coat film, the most preferably.

[decoration is coated with bonding film firmly]

The hard bonding film that is coated with of the decoration of the present invention has adhesive phase on the surface of the resin bed constituting above-mentioned decoration hard coat film.

Above-mentioned decoration is firmly coated with bonding film and can be manufactured by following method etc.: be transferred to by previously fabricated adhesive phase The method on the surface of above-mentioned decoration hard coat film or at the surface coating adhesive of above-mentioned decoration hard coat film and make its side being dried Method etc..

As the binding agent that can form above-mentioned adhesive phase, it is possible to use containing known acrylic resin, rubber It it is the binding agent of the binder resin such as resin, silicone-based resin.Wherein, as above-mentioned binding agent, it is preferably used containing acrylic acid series The binding agent of resin.Due to the excellent adhesion with above-mentioned resin bed, therefore it is preferably used containing (methyl) acrylic ester polymerization The binding agent of thing, described (methyl) acrylate polymer by will containing (methyl) alkoxyalkyl acrylate monomer and There is the polymerizing monomer components of (methyl) alkyl acrylate monomer of the alkyl of carbon number 1～4 and obtain.

As (methyl) alkoxyalkyl acrylate that can use in the manufacture of (methyl) acrylate polymer Monomer, specifically, can list acrylic acid 2-methoxy acrylate, acrylic acid 2-ethoxy ethyl ester, acrylic acid 2-methoxyl group Triglycol ester, acrylic acid 3-methoxyl group propyl ester, acrylic acid 3-ethyoxyl propyl ester, acrylic acid 4-methoxybutyl, acrylic acid 4- Ethoxybutyl etc..Wherein, as (methyl) alkoxyalkyl acrylate monomer, possesses excellent cohesiveness from being formed The aspect of adhesive phase is set out, and acrylic acid 2-methoxy acrylate, acrylic acid 2-ethoxy ethyl ester etc. are preferably used.

As (methyl) alkyl acrylate monomer of the above-mentioned alkyl with carbon number 1～4, specifically, permissible List ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, acrylic acid uncle Butyl ester, methyl methacrylate, ethyl methacrylate, n propyl methacrylate, isopropyl methacrylate, metering system Acid N-butyl, the secondary butyl ester of methacrylic acid, Tert-butyl Methacrylate etc..

As (methyl) alkyl acrylate monomer of the above-mentioned alkyl with carbon number 1～4, above-mentioned described In material, the alkyl acrylate monomer with alkyl that carbon number be 1～4 is preferably used, from above-mentioned resin bed being composed The aspect of the cementability giving excellence is set out, and n-butyl acrylate is preferably used.

As the monomer component that can use in the manufacture of above-mentioned (methyl) acrylate polymer, except above-mentioned material In addition, it is also possible to use the monomer with carboxyl as required.

As the above-mentioned monomer with carboxyl, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, bar can be enumerated Bean acid, acrylic acid dimer, ethylene-oxide-modified succinic acid acrylate etc., be preferably used the acrylic acid that versatility is high.

The usage amount of the above-mentioned monomer with carboxyl, uses relative in the manufacture of above-mentioned (methyl) acrylate polymer The total amount of monomer component be preferably below 1 mass %, below more preferably 0.5 mass %, glued attaching to comprise composition In the case of the metallic surface of thing, owing to being possible to prevent the above-mentioned corrosion comprising metallic surface, the most more preferably Below 0.1 mass %.

As the monomer component that can use in the manufacture of above-mentioned (methyl) acrylate polymer, except above-mentioned material In addition, it is also possible to form the purpose of the high adhesive phase of cohesiveness for reacting with cross-linking agent described later, and make as required With the monomer with the functional group reacted with cross-linking agent.As above-mentioned vinyl monomer, it is not particularly limited, third can be listed Olefin(e) acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 4-hydroxybutyl etc. have the vinyl monomer etc. of hydroxyl.

The above-mentioned monomer with functional group, relative to the monomer used in the manufacture of above-mentioned (methyl) acrylate polymer The total amount of composition, preferably uses, in the range of 0.1 mass %～10 mass % more preferably in the range of 0.5～5 mass % Use.

As the weight average molecular weight of (methyl) acrylate polymer, preferably 300,000～1,600,000, more preferably 400,000～ 1300000, owing to above-mentioned resin bed can be given excellent cementability, the most more preferably 500,000～1,000,000.

It addition, the molecular weight distribution (weight-average molecular weight/number-average molecular weight) of (methyl) acrylate polymer is preferably 10 ～50, more preferably 10～30, owing to being difficult in its interface when attaching decoration hard coat film to the surface of image display Containing bubble, the most more preferably 10～20.

It should be noted that in the present invention, the weight average molecular weight of above-mentioned (methyl) acrylate polymer can be passed through Gel permeation chromatography (GPC) is measured.More specifically, it is possible to use TOSOH Co., Ltd's system " SC8020 " is as GPC Determinator, utilizes polystyrene conversion value to be measured under following GPC condition determination and obtain.

(condition determination of GPC)

Sample concentration: 0.5 weight % (tetrahydrofuran solution)

Sample injection rate: 100 μ L

Eluent: oxolane (THF)

Flow velocity: 1.0mL/min

Column temperature (mensuration temperature): 40 DEG C

Post: TOSOH Co., Ltd's system " TSKgel GMHHR-H "

Detector: differential refraction

As above-mentioned binding agent, for the purpose of the cohesiveness improving adhesive phase further, it is preferably used containing crosslinking The binding agent of agent.

As above-mentioned cross-linking agent, isocyanates system cross-linking agent, epoxy cross-linking agent, chelating system crosslinking can be listed Agent, aziridine system cross-linking agent, polyfunctional acrylic ester system cross-linking agent etc., be preferably used isocyanates system cross-linking agent.

Relative to above-mentioned (methyl) acrylate polymer 100 mass parts, above-mentioned cross-linking agent is preferably in 0.05～2 mass parts In the range of use, more preferably in the range of 0.07～1.5 mass parts use, owing to being prone to the gel percentage of adhesive phase Rate adjusts in the range of suitably, therefore further preferably uses in the range of 0.1～1 mass parts.

About above-mentioned adhesive phase, toluene impregnates the 24 little percent gel represented by following formula constantly and is preferably 30～80 mass %, more preferably 30～70 mass %, even if owing to being fixed on image display by decoration hard coat film Be not easy in the case of surface to produce through time stripping, and be difficult to contain bubble, the most more preferably in its interface 40～60 mass %.

Percent gel (%)=[(quality after the toluene dipping of adhesive phase)/(before the toluene dipping of adhesive phase Quality)] × 100

The thickness of above-mentioned adhesive phase is preferably 5～30 μm, more preferably 8～20 μm.By being set as this thickness range, Such that it is able to the surface making decoration firmly be coated with bonding film obtains high pencil hardness, and can be easily obtained good punch press process.

Embodiment

Hereinafter, embodiment and comparative example is utilized to further illustrate the present invention.

(synthesis example 1)

In the flask possessing agitator, gas introduction tube, condensing tube and thermometer, addition butyl acetate 250 mass parts, Norbornene alkyl diisocyanate 206 mass parts, p methoxy phenol 0.5 mass parts, dibutyl tin acetate 0.5 mass parts, Be warming up to 70 DEG C while being blown into air, then with 1 hour dropping pentaerythritol triacrylate (hereinafter referred to as " PE3A ")/ Tetramethylol methane tetraacrylate (hereinafter referred to as " PE4A ") mixture (PE3A/PE4A mass ratio is the mixture of 75/25) 795 Mass parts.

After completion of dropwise addition, react 3 hours at 70 DEG C, then carry out reacting until representing the 2250cm of NCO^-1's Infrared absorption spectrum disappears, obtain having the polyfunctional carbamate acrylate (A1) of ester ring type structure and PE4A and Mixture (mixture of [A1/PE4A and PE3A] (mass ratio)=80/20, the acetic acid of nonvolatile component 80 mass % of PE3A Butyl acetate solution).It should be noted that the molecular weight (value of calculation) of urethane acrylate (A1) is 802.

(synthesis example 2)

In the flask possessing agitator, gas introduction tube, condensing tube and thermometer, addition butyl acetate 254 mass parts, Isophorone diisocyanate 222 mass parts, p methoxy phenol 0.5 mass parts, dibutyl tin acetate 0.5 mass parts, rise After warm to 70 DEG C, by 1 hour dropping PE3A/PE4A mixture (mixture of mass ratio 75/25) 795 mass parts.

After completion of dropwise addition, react 3 hours at 70 DEG C, then carry out reacting until representing the 2250cm of NCO^-1's Infrared absorption spectrum disappears, obtain having the polyfunctional carbamate acrylate (A1) of ester ring type structure and PE4A and Mixture (mixture of [A2/PE4A and PE3A] (mass ratio)=80/20, the acetic acid of nonvolatile component 80 mass % of PE3A Butyl acetate solution).It should be noted that the molecular weight (value of calculation) of urethane acrylate (A2) is 818.

(synthesis example 3)

In the flask possessing agitator, gas introduction tube, condensing tube and thermometer, addition butyl acetate 254 mass parts, Isophorone diisocyanate 222 mass parts, p methoxy phenol 0.5 mass parts, dibutyl tin acetate 0.5 mass parts, rise Temperature dripped two (acryloyl-oxyethyl) hydroxyethyl isocyanuric acid ester 369 mass parts and PE3A/PE4A with 1 hour after 70 DEG C Mixture (PE3A/PE4A mass ratio is the mixture of 75/25) 398 mass parts.

After completion of dropwise addition, react 3 hours at 70 DEG C, then carry out reacting until representing the 2250cm of NCO^-1's Infrared absorption spectrum disappears, and obtains the polyfunctional carbamate acrylate with the ring structures containing hetero ring type structure (A3) with mixture (mixture of [A3/PE4A and PE3A] (mass ratio)=91/9, nonvolatile component 80 matter of PE4A and PE3A The butyl acetate solution of amount %).It should be noted that the molecular weight (value of calculation) of urethane acrylate (A3) is 889.

(synthesis example 4)

In the flask possessing agitator, gas introduction tube, condenser and thermometer, add Aronix M-305 [East Asia Synthesis (strain) society pentaerythritol triacrylate/tetramethylol methane tetraacrylate=60/40 (mass ratio) mixture, hydroxyl value 116mgKOH/g] 549.1 mass parts, dibutyl tin acetate 0.1 mass parts, Smilizer BHT [Sumitomo Chemical (strain) Antioxidant processed] 0.6 mass parts, Methoquinone [Seiko chemical industry (strain) polymerization inhibitor processed] 0.1 mass parts and acetic acid fourth Ester 160 mass parts, heats up mixed uniformly while lentamente.Desmodur H [Sumimoto is added when reaching 60 DEG C Bayer Urethane Co., Ltd. preparing hexamethylene radical diisocyanate, NCO%=50 mass %) 90.9 mass parts, then exist React 5 hours at 80 DEG C, obtain urethane acrylate (A4) 800 mass parts.

(synthesis example 5)

In the flask possessing agitator, gas introduction tube, condensing tube and thermometer, add methyl propenoic acid glycidyl Ester 250 mass parts, lauryl mercaptan 1.3 mass parts, methyl iso-butyl ketone (MIBK) 1000 mass parts and 2,2 '-azodiisobutyronitrile 7.5 matter Amount part, while being stirred under nitrogen flowing, was warming up to 90 DEG C with 1 hour, and reacted 1 hour at 90 DEG C.

Then, while being stirred at 90 DEG C, glycidyl methacrylate 750 matter is comprised with dropping in 2 hours Amount part, lauryl mercaptan 3.7 mass parts, 2, after the mixed liquor of 2 '-azodiisobutyronitrile 22.5 mass parts, react 3 little at 100 DEG C Time.

Then, addition 2,2 '-azodiisobutyronitrile 10 mass parts, then react 1 hour at 100 DEG C, then heat to 120 Near DEG C, react 2 hours.

It is cooled to 60 DEG C, nitrogen ingress pipe is replaced by air leading-in conduit, add acrylic acid 507 mass parts, to methoxyl group After phenol 2 mass parts, triphenylphosphine 5.4 mass parts mixing, with air, reactant liquor is carried out bubbling, is warming up to 110 DEG C simultaneously, And react 8 hours.

Then, add p methoxy phenol 1.4 mass parts, and be cooled to room temperature, then so that nonvolatile component reaches 50 The mode of quality % adds methyl iso-butyl ketone (MIBK), thus obtains the methyl isobutyl ketone solution (nonvolatile component of polymer (B1) 50 mass %).It should be noted that the weight average molecular weight of obtained polymer (B1) (poly-based on by GPC that be 31,000 Styrene converts and obtains), (methyl) acryloyl group equivalent is 300g/eq.

(preparation example 1)

By ethyl acetate 23.01 mass parts, have the polyfunctional carbamate acrylate (A1) of ester ring type structure with Mixture (mixture of [A1/PE4A and PE3A] (mass ratio)=80/20, nonvolatile component 80 mass % of PE4A and PE3A Butyl acetate solution) 19.64 mass parts, the polyfunctional carbamate acrylate (A2) with ester ring type structure and PE4A Mixture (mixture of [A2/PE4A and PE3A] (mass ratio)=80/20, the second of nonvolatile component 80 mass % with PE3A Acid butyl ester solution) 19.64 mass parts, there is the polyfunctional carbamate acrylic acid of ester ring type structure containing hetero ring type structure Ester (A3) and mixture (mixture of [A3/PE4A and PE3A] (mass ratio)=91/9, the nonvolatile component 80 of PE4A and PE3A The butyl acetate solution of quality %) 15.71 mass parts, dipentaerythritol acrylate 18.86 mass parts, draw as photopolymerization Send out 1-hydroxycyclohexylphenylketone 2.51 mass parts of agent, as (2,4, the 6-trimethylbenzoyl) two of Photoepolymerizationinitiater initiater After phenyl phosphine oxide 0.63 mass parts mixes equably, by propylene glycol list first in the way of making nonvolatile component reach 40 mass % Ether is diluted, and thus prepares hard varnish (1).

(preparation example 2)

By ethyl acetate 23.01 mass parts, have the polyfunctional carbamate acrylate (A1) of ester ring type structure with Mixture (mixture of [A1/PE4A and PE3A] (mass ratio)=80/20, nonvolatile component 80 mass % of PE4A and PE3A Butyl acetate solution) 19.64 mass parts, there is the polyfunctional carbamate acrylate (A2) of ester ring type structure) with Mixture (mixture of [A2/PE4A and PE3A] (mass ratio)=80/20, nonvolatile component 80 mass % of PE4A and PE3A Butyl acetate solution) 19.64 mass parts, there is the polyfunctional carbamate third of ester ring type structure containing hetero ring type structure Olefin(e) acid ester (A3) and the mixture of PE4A and PE3A (mixture of [A3/PE4A and PE3A] (mass ratio)=91/9, non-volatile become The butyl acetate solution of point 80 mass %) 15.71 mass parts, dipentaerythritol acrylate 18.86 mass parts, gather as light Close 1-hydroxycyclohexylphenylketone 2.51 mass parts of initiator, as (2,4, the 6-trimethylbenzoyl of Photoepolymerizationinitiater initiater Base) diphenyl phosphine oxide 0.63 mass parts, reactive F anti-fouling agent (OPTOOL DAC-HP；Daikin Ind Ltd's system, no Volatile ingredient 20 mass %) after 2.0 mass parts mix equably, with the third two in the way of making nonvolatile component reach 40 mass % Alcohol monomethyl ether is diluted, and thus prepares hard varnish (2).

(preparation example 3)

By ethyl acetate 13.74 mass parts, have the polyfunctional carbamate acrylate (A2) of ester ring type structure with Mixture (mixture of [A2/PE4A and PE3A] (mass ratio)=80/20, nonvolatile component 80 mass % of PE4A and PE3A Butyl acetate solution) 47.08 mass parts, the methyl isobutyl ketone solution (nonvolatile component 50 mass %) of polymer (B1) 20.92 mass parts, dipentaerythritol acrylate 12.74 mass parts, 1-hydroxy-cyclohexyl benzene as Photoepolymerizationinitiater initiater Base ketone 1.30 mass parts, (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide 0.92 mass as Photoepolymerizationinitiater initiater Part, reactive F anti-fouling agent (OPTOOL DAC-HP；Daikin Ind Ltd's system, nonvolatile component 20 mass %) 2.0 mass After part mixing equably, it is diluted with propylene glycol monomethyl ether in the way of making nonvolatile component reach 40 mass %, thus makes For going out hard varnish (3).

(preparation example 4)

Add butyl acetate in the urethane acrylate (A4) and be diluted so that nonvolatile component concentration Reach 35%, then coordinate Irgacure#184 [Ciba (strain) Photoepolymerizationinitiater initiater processed, 1-hydroxy-cyciohexyl phenyl ketone] 3.2 parts, prepare hard varnish (4).

(synthesis example 7)

In the flask possessing agitator, gas introduction tube, condenser and thermometer, [(strain) is big to add PLACCEL205U Match fine jade aliphatic poly caprolactone diol, hydroxyl value 212mgKOH/g, number-average molecular weight (Mn) 529] 133 mass parts, dibutyl Oxalic acid stannum 0.1 mass parts, Smilizer BHT [Sumitomo Chemical (strain) antioxidant processed] 2.3 mass parts, Methoquinone [Seiko chemical industry (strain) polymerization inhibitor processed] 0.2 mass parts, uniformly mixes.

Add Desmodur I [Sumimoto Bayer Urethane Co., Ltd. preparing isophorone diisocyanate, NCO%=47 mass %] 111 mass parts, and after being to slowly warm up to 85 DEG C, react 1 hour.

Add Aronix M-305 [East Asia synthesis (strain) pentaerythritol triacrylate/tetramethylol methane tetraacrylate processed =60/40 (mass ratio) mixture, hydroxyl value 116mgKOH/g] 247 mass parts, react 3 hours at 85 DEG C, thus obtain double Urethane acrylate (A5) 493.6 mass parts of key concentration 5.39mmol/g.

(synthesis example 6)

In the flask possessing agitator, gas introduction tube, condenser and thermometer, add PLACCELL205AL [(strain) Daicel aliphatic poly esterdiol, hydroxyl value 224mgKOH/g, number-average molecular weight (Mn) 501] 125 mass parts, dibutyl two Tin acetate 0.1 mass parts, Smilizer BHT [Sumitomo Chemical (strain) antioxidant processed] 2.3 mass parts, Methoquinone [Seiko chemical industry (strain) polymerization inhibitor processed] 0.2 mass parts, uniformly mixes.

Add DesmodurI [Sumimoto Bayer Urethane Co., Ltd. preparing isophorone diisocyanate, NCO%=47 mass %] 111 mass parts, and after being to slowly warm up to 85 DEG C, react 1 hour.

Add Aronix M-305 [East Asia synthesis (strain) pentaerythritol triacrylate/tetramethylol methane tetraacrylate processed =60/40 (mass ratio) mixture, hydroxyl value 116mgKOH/g] 247 mass parts, react 3 hours at 85 DEG C, thus obtain double Urethane acrylate (A6) 485.6 mass parts of key concentration 5.31mmol/g.

(preparation example 5)

The ratio recorded with table 1 below, by urethane acrylate (A5) or urethane acrylate (A6), Multi-functional monomer 1 (East Asia synthesis (strain) system " Aronix M-305 ", pentaerythritol triacrylate and tetramethylolmethane tetrapropylene The mixture of acid esters), multi-functional monomer 2 (Japan's chemical medicine (strain) system " Kayarad DPCA-60 ", 6-caprolactone modified two seasons Penta tetrol six acrylate), mono-functional's monomer 1 (Osaka Organic Chemical Industry (strain) system " Viscoat150D " oxolane first Alcohol acrylic polyester), mono-functional's monomer 2 (East Asia synthesis (strain) system " Aronix M-240 " tetraethylene glycol diacrylate), Photoepolymerizationinitiater initiater (BASF (strain) Darocur1173 processed) mixes, and thus prepares active energy ray curable resin combination Thing (1)～(8).

Table 1

<(methyl) acrylate polymer (1)>

In the reaction vessel possessing agitator, reflux condenser, thermometer, Dropping funnel and nitrogen inlet, by third Olefin(e) acid N-butyl 80 mass parts, acrylic acid 4 mass parts, methyl methacrylate 15 mass parts and as the 2 of polymerization initiator, 2 '-azodiisobutyronitrile 0.2 mass parts is dissolved in ethyl acetate 100 mass parts, after carrying out nitrogen displacement, is polymerized at 80 DEG C 8 hours, then use ethyl acetate that solid constituent is adjusted to 30 mass %, thus obtain comprising the third of weight average molecular weight 700,000 The binding agent (1) of olefin(e) acid analog copolymer (1) solution.

<(methyl) acrylate polymer (2)>

In the reaction vessel possessing agitator, reflux condenser, thermometer, Dropping funnel and nitrogen inlet, by third Olefin(e) acid 2-methoxy acrylate 75 mass parts, n-butyl acrylate 24 mass parts, Hydroxyethyl Acrylate 1 mass parts and conduct are poly- Closing the 2 of initiator, 2 '-azodiisobutyronitrile 0.2 mass parts is dissolved in ethyl acetate 100 mass parts, after carrying out nitrogen displacement, It is polymerized at 80 DEG C 8 hours, then uses ethyl acetate that solid constituent is adjusted to 30 mass %, thus obtain comprising weight average and divide The binding agent (2) of acrylic copolymer (2) solution of son amount 700,000.

By above-mentioned binding agent (1) 100 mass parts and isocyanates system cross-linking agent (Nippon Polyurethane Industry (Ltd.) Coronate L-45, solid constituent 45 mass %) 0.1 mass parts is mixed and stirred for 15 minutes, so that dried thickness is 10 Gains are coated the polyester film (letter below of one side thickness 50 μm after silicone compounds in addition lift-off processing by the mode of μm Surface referred to as " #50 stripping film "), and be dried 5 minutes at 75 DEG C, it is consequently formed adhesive phase.

Then, in the surface of above-mentioned adhesive phase laminating one side thickness 38 μm after silicone compounds in addition lift-off processing Polyester film (hereinafter referred to as " #38 stripping film "), and ripening 7 days in the environment of 23 DEG C, thus obtain thickness 10 μm, solidifying The bonding sheet (1) of glue percentage rate 70 mass %.

By above-mentioned binding agent (2) 100 mass parts and isocyanates system cross-linking agent (Nippon Polyurethane Industry (Ltd.) Coronate HX, solid constituent 75 mass %) 0.1 mass parts is mixed and stirred for 15 minutes, so that dried thickness is 10 μm Mode gains are coated the surface of #50 stripping film, and be dried 5 minutes at 75 DEG C, be consequently formed adhesive phase.

Then, #38 stripping film of fitting on the surface of above-mentioned adhesive phase, and ripening 7 days in the environment of 23 DEG C, thus To thickness 10 μm, percent gel 50 mass % bonding sheet (2).

(embodiment 1)

Use the polyethylene terephthalate masking ((strain) Cosmo processed Shine A4300 spins in Japan) of thickness 75 μm As film base material, the above-mentioned hard varnish of coated on one side (1) at this film base material is also dried 90 seconds, then at air atmosphere at 60 DEG C Under, use ultraviolet lamp (Japan Fusion UV system (strain) system " F450 ", lamp: 120W/cm, H bulb), with 0.2J/ cm²Irradiation light quantity irradiation ultraviolet radiation, be consequently formed the hard conating (1) of thickness 3 μm.

Then, the another side (not having the face of hard conating (1)) at above-mentioned film base material is coated with above-mentioned hard varnish (2) and 60 It is dried at DEG C 90 seconds, the most in air atmosphere, uses ultraviolet lamp (Japan Fusion UV system (strain) system " F450 ", lamp: 120W/cm, H bulb) with 0.2J/cm²Irradiation light quantity irradiation ultraviolet radiation, be consequently formed the hard painting of thickness 12 μm Layer (2).

By via above-mentioned operation, the mask being formed in above-mentioned film base material has hard conating (1) and at another mask There is the hard coat film (1) of hard conating (2).

Then, on the surface of hard conating (1) constituting above-mentioned hard coat film (1), with the shape of frame-shaped (profile 45mm × 45mm, live width 10mm (region of no decoration layer: 25mm × 25mm)) so that the thickness of the decorative layer formed after drying is 5 μm Mode, the black liquid SG740 that silk screen printing SeikoAdvance (strain) makes, and at 85 DEG C be dried 30 minutes, be consequently formed dress Decorations layer.

Then, solid at the active energy beam described in the surface coating table 1 of the hard coat film (1) being provided with above-mentioned decorative layer Change type resin combination (1).Now, it is coated in the way of the thickness apart from the surface of above-mentioned hard conating (1) is 25 μm.

Then, in air atmosphere, use ultraviolet lamp (Japan Fusion UV system (strain) system " F450 ", Lamp: 120W/cm, H bulb), with 0.2J/cm²Irradiation light quantity to above-mentioned coated face irradiation ultraviolet radiation, be consequently formed thickness 25 μm Resin bed.

By via above operation, obtaining the decoration hard coat film (1) of gross thickness 115 μm.

It addition, on the surface of the resin bed constituting above-mentioned decoration hard coat film (1), attach and constitute removing of above-mentioned bonding sheet (1) Removing the sheet material after #38 mold release film, the decoration thus obtaining having gross thickness 125 μm of adhesive phase is coated with bonding film (1) firmly.

(embodiment 2)

Use bonding sheet (2) to replace above-mentioned bonding sheet (1), in addition, obtain total thickness with method similarly to Example 1 The decoration of 125 μm is coated with bonding film (2) firmly.

(embodiment 3)

Active energy ray-curable resin composition (2) is used to replace active energy ray-curable resin composition (1), in addition, obtain decorating hard coat film (3) with method similarly to Example 2 and decoration is coated with bonding film (3) firmly.

(embodiment 4)

Active energy ray-curable resin composition (3) is used to replace active energy ray-curable resin composition (1), in addition, obtain decorating hard coat film (4) with method similarly to Example 2 and decoration is coated with bonding film (4) firmly.

(embodiment 5)

Active energy ray-curable resin composition (4) is used to replace active energy ray-curable resin composition (1), in addition, obtain decorating hard coat film (5) with method similarly to Example 2 and decoration is coated with bonding film (5) firmly.

(embodiment 6)

The thickness of resin bed is changed to 20 μm from 25 μm, in addition, obtains total thickness with method similarly to Example 2 The decoration of the decoration hard coat film (6) and gross thickness 120 μm of spending 110 μm is coated with bonding film (6) firmly.

(embodiment 7)

The thickness of resin bed is changed to 10 μm from 25 μm, in addition, obtains total thickness with method similarly to Example 2 The decoration of the decoration hard coat film (7) and gross thickness 110 μm of spending 100 μm is coated with bonding film (7) firmly.

(embodiment 8)

The thickness of hard conating (2) is changed to 7 μm from 12 μm, in addition, obtains always with method similarly to Example 1 The decoration hard coat film (8) of thickness 110 μm and the decoration of gross thickness 120 μm are coated with bonding film (8) firmly.

(embodiment 9)

The thickness of hard conating (1) is changed to 5 μm from 3 μm, in addition, obtains always with method similarly to Example 1 The decoration hard coat film (9) of thickness 117 μm and the decoration of gross thickness 127 μm are coated with bonding film (9) firmly.

(embodiment 10)

The hard varnish (4) is used to replace hard varnish (1) to form hard conating (4), in addition, with similarly to Example 2 The decoration of decoration hard coat film (10) and gross thickness 125 μm that method obtains gross thickness 115 μm is coated with bonding film (10) firmly.

(embodiment 11)

The hard varnish (3) is used to replace hard varnish (2) to form hard conating (3), in addition, with similarly to Example 2 The decoration of decoration hard coat film (11) and gross thickness 125 μm that method obtains gross thickness 115 μm is coated with bonding film (11) firmly.

(embodiment 12)

It is not provided with hard conating (1), in addition, obtains decorating hard coat film (12) with method similarly to Example 2.

Attach above-mentioned bonding sheet (2) on the surface of the resin bed constituting above-mentioned decoration hard coat film (12), thus decorated Firmly it is coated with bonding film (12).

(embodiment 13)

((strain) Cosmo processed Shine spins to the polyethylene terephthalate masking of use thickness 125 μm in Japan A4300) the polyethylene terephthalate masking ((strain) Cosmo processed Shine A4300 spins in Japan) of thickness 75 μm is replaced, In addition, the decoration hard coat film (13) of gross thickness 165 μm and gross thickness 175 μm are obtained with method similarly to Example 2 Decoration is coated with bonding film (13) firmly.

(comparative example 1)

Active energy ray-curable resin composition (5) is used to replace active energy ray-curable resin composition (1) decoration hard coat film (14) and gross thickness 125 μ of gross thickness 115 μm, in addition, is obtained with method similarly to Example 2 The decoration of m is coated with bonding film (14) firmly.

(comparative example 2)

Active energy ray-curable resin composition (6) is used to replace active energy ray-curable resin composition (1) decoration hard coat film (15) and gross thickness 125 μ of gross thickness 115 μm, in addition, is obtained with method similarly to Example 2 The decoration of m is coated with bonding film (15) firmly.

(comparative example 3)

Active energy ray-curable resin composition (7) is used to replace active energy ray-curable resin composition (1) decoration hard coat film (16) and gross thickness 125 μ of gross thickness 115 μm, in addition, is obtained with method similarly to Example 2 The decoration of m is coated with bonding film (16) firmly.

(comparative example 4)

Active energy ray-curable resin composition (8) is used to replace active energy ray-curable resin composition (1) decoration hard coat film (17) and gross thickness 125 μ of gross thickness 115 μm, in addition, is obtained with method similarly to Example 2 The decoration of m is coated with bonding film (17) firmly.

(comparative example 5)

Use bonding sheet (1) to replace bonding sheet (2), in addition, obtain total thickness 125 μ with the method as comparative example 3 The decoration of m is coated with bonding film (19) firmly.

(comparative example 6)

Use bonding sheet (1) to replace bonding sheet (2), in addition, obtain total thickness 125 μ with the method as comparative example 4 The decoration of m is coated with bonding film (20) firmly.

Above-mentioned active energy ray-curable resin composition (1)～(8) are respectively coated on glass plate, at air gas Ultraviolet lamp (Japan Fusion UV system (strain) system " F450 ", lamp: 120W/cm, H bulb) is used under atmosphere, with 0.2J/cm²Irradiation light quantity irradiation ultraviolet radiation, be consequently formed the film of thickness 25 μm.

Use Fisher scope HM2000Xyp (Fischer Instruments company), with between load 1mN press-in rib The Vickers indenter that angle is 136 ° measures the martensite hardness on the surface of above-mentioned film.

For the surface of above-mentioned film, dumbbell cutter is used to carry out the shape of the test film type 5 that stamping-out is JIS K7127, will Gains are as test film.

Use obtained test film, utilize the Measurement of Dynamic Viscoelasticity device RSA-II of Rheometrics company (frequently Rate 3.5Hz, programming rate 3 DEG C/min) it is measured, obtain the store elastic modulus at 60 DEG C.

Regulation based on JIS K5600-5-4 (version in 1999), uses well unit of Co., Ltd. to make made film lead Stroke trace testing machine (manual type), measures and obtains in the pencil hardness on the surface of above-mentioned film and embodiment and comparative example The pencil hardness on the surface of the hard hard conating (2) being coated with bonding film of decoration.

The unilateral #38 stripping film of the bonding sheet (1) obtained in above-mentioned and (2) is peeled off, poly-to benzene with thickness 25 μm Naphthalate base material is fitted, and thus makes the adhesive tape of width 25mm, length 10cm.

In the environment of temperature 23 DEG C, relative humidity 50%RH, above-mentioned adhesive tape is attached to glass plate and constitutes decoration The resin face of hard coat film, uses 2kg roller, crimps with the crimping number of times once come and gone, and at temperature 23 DEG C, relative humidity 1 hour is stood in the environment of 50%RH.

For the above-mentioned adhesive tape attached, measure the peeling rate with 300mm/min, gluing when peeling off along 180 ° of directions Relay (180 ° of peeling adhesion forces).

<re-workability evaluation methodology>

Use roller to be coated with bonding film fit to the surface of glass plate respectively by hard for the decoration obtained in above-mentioned, 50 DEG C, 5 big Air pressure, carry out heating pressurization deaeration under conditions of 20 minutes and process, then 23 DEG C, place 24 hours under 50% environmental condition.

Then, according to following metewand, the peeling rate with 300mm/min is peeled off the hard painting of decoration along 90 ° of directions During bonding film, decoration hard painting bonding film is evaluated with the state of glass.

The hard bonding film that is coated with of ◎: decoration does not crush, and does not has residual adhesive on the surface of glass plate.

Zero: although the hard bonding film that is coated with of decoration does not crush, but there is a little binding agent at the remained on surface of glass plate.

×: the hard bonding film that is coated with of decoration crushes, and also remains binding agent on the surface of glass plate or decoration is coated with bonding film firmly A part.

Use Vickers cutter (nose angle 42 degree), with the circle of diameter 3mm, from the table of the hard hard conating (2) being coated with bonding film of decoration Face side blow cuts out the face to the mold release film constituting opposing face.

Then, remaining hard conating bonding film after the test film of above-mentioned circle and above-mentioned stamping-out is attached at glass respectively Plate, uses microscope (50 times) to observe hard conating (1) and (2) and splitting with or without resin bed from the face side of hard conating (2) Stricture of vagina, and be evaluated according to following metewand.

Crackle is not had on ◎: hard conating and resin bed.

Zero: the very small percentage at hard conating or resin bed observes crackle, but does not has obvious crackle.

×: observe obvious crackle at hard conating or resin bed.

[table 2]

[table 3]

[table 4]

From above-mentioned table, the decoration of the present invention is firmly coated with bonding film and has high pencil hardness, and re-workability, stamping-out add Work is excellent.On the other hand, the decoration of comparative example 1,2 is hard, and to be coated with the pencil hardness of bonding film not enough, comparative example 3～6 reprocessing, Broken, crackle is easily produced during punch press process.

Claims

1. a decoration hard coat film, it is characterised in that

Have: at least one side at base material has the hard coat film of hard conating, is arranged at the dress of the part on described hard coat film surface Decorations layer and be arranged at the resin bed on the surface with decorative layer of described hard coat film,

Described resin bed use active energy ray-curable resin composition and formed, described resin bed in frequency Store elastic modulus E of measured under 3.5Hz 60 DEG C ' it is 3.0 × 10⁸～5.0 × 10⁸Pa, and described resin bed with carry The Vickers indenter at 136 ° of angle between lotus 1mN press-in rib and the martensite hardness that records is 70～100N/mm²。

Decoration hard coat film the most according to claim 1, its gross thickness is 100～170 μm, the maximum gauge of described resin bed It is 5～30 μm.

Decoration hard coat film the most according to claim 1, wherein, described hard coat film is to have hard conating on the two sides of base material Hard coat film.

Decoration hard coat film the most according to claim 3, wherein, forms the side contrary with the face arranging described decorative layer The pencil hardness of the hard conating in face is more than 3H.

Decoration hard coat film the most according to claim 1, wherein, described active energy ray-curable resin composition contains Carbamate (methyl) acrylate.

Decoration hard coat film the most according to claim 1, wherein, described resin bed will be arranged at described hard coat film surface The resin bed that the decorative layer of a part covers, and be the resin bed after its surface is planarized.

Decoration hard coat film the most according to claim 1, wherein, described resin bed is arranged at the setting on described hard coat film surface There is the hard coat film surface beyond the part of decorative layer, and the thickness of described resin bed is identical with the thickness of described decorative layer.

8., according to the decoration hard coat film according to any one of claim 1～7, it is for the image display dress of miniature electric terminal In the image display panel put.

9. a decoration is coated with bonding film firmly, it is characterised in that be firmly coated with constituting the decoration according to any one of claim 1～8 The surface of the described resin bed of film, is provided with adhesive phase.

Decoration the most according to claim 9 is coated with bonding film firmly, and wherein, described adhesive phase is to use containing acrylic acid series The acrylic adhesive composition of polymer and formed, described acrylic acid series polymeric compounds is to make containing alkyl acrylate epoxide alkane The monomer component of base ester carries out being polymerized and obtaining.