TWI586767B - Cyclic olefin resin film - Google Patents

Description

Cyclic olefin resin film

The present invention relates to an ultraviolet curable composition for a cyclic olefin resin and a cyclic olefin resin film using the same, and the ultraviolet curable composition for a cyclic olefin resin can be applied to the surface of a cyclic olefin resin. After hardening, a hard coat layer containing a cured coating film having high scratch resistance, excellent adhesion to a substrate, and little coloration is formed.

The cyclic olefin resin film is excellent in transparency, low birefringence, low moisture absorption, heat resistance, electrical insulation, chemical resistance, etc., and is widely used for optical members, medical, packaging films, automobiles, semiconductors, and the like. . In particular, in the case of optical components, we are considering the diversification of units for use in liquid crystal displays and touch panels, and using a cyclic olefin resin film having high transparency and low moisture absorption to replace the polyphenylene terephthalate used in the past. Plastic film such as ethylene glycol formate (PET) or triethylene terephthalate (TAC).

In addition, since the surface hardness of the cyclic olefin resin film is insufficient, and there is damage during processing, in order to improve abrasion resistance and scratch resistance, it is considered to provide a hard coating film containing an ultraviolet curable composition on the surface thereof. A protective layer such as a hard coat layer. However, since the cyclic olefin resin film has a main structure of an alicyclic structure, the surface of the film has a low polarity, and the water contact angle is as high as about 90°, and the ultraviolet curable composition is coated. In the case where the coating material is not easily diffused and coated, there is a problem that the adhesion between the surface of the cyclic olefin resin film and the hard coat layer is low.

As a method of improving the adhesion between the surface of the cyclic olefin resin film and the hard coat layer, it is proposed to provide a primer layer having a polar group-modified olefin resin as a main component on the surface of the cyclic olefin resin film. A method of applying an ionizing radiation-curable resin and hardening it (for example, refer to Patent Document 1). This method can improve the adhesion between the surface of the cyclic olefin resin film and the hard coat layer, but also increases the steps of coating and drying the undercoat layer, thereby causing a problem of reduced yield and increased cost.

Further, as a method of adhering the hard coat layer to the surface of the cyclic olefin resin film without providing the undercoat layer, it is proposed to use a hard coat film containing a curable composition of a (meth) acrylate having an alicyclic structure as a method. Hard coat layer (for example, refer to Patent Document 2). In the case of using the curable composition, in order to obtain sufficient adhesion to the surface of the cyclic olefin resin film, it is necessary to increase the ratio of the (meth) acrylate having an alicyclic structure. However, when the ratio of the (meth) acrylate having an alicyclic structure is increased, the crosslinking density of the cured coating film is lowered, and the scratch resistance of the surface of the cured coating film is insufficient.

Further, as a method of improving the adhesion to the cyclic olefin resin molded article of the ultraviolet curable composition, it is proposed to use a benzophenone structure in the photopolymerization initiator added to the ultraviolet curable composition. 4-benzylidene-4-methyl disulfide (for example, refer to Patent Document 3). However, this ultraviolet curable composition has a problem that the cured coating film is colored yellow.

Then, a hardened coating film having a high abrasion resistance on the surface of the cyclic olefin resin film, an excellent adhesion between the surface of the cyclic olefin resin film and the surface of the cyclic olefin resin film, and a hardened coating film can be formed. An ultraviolet curable composition that does not stain.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-284158

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-89458

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2002-275392

The object of the present invention is to provide an ultraviolet curable composition for a cyclic olefin resin and a cyclic olefin resin film using the same, which can be applied to a cyclic olefin by using an ultraviolet curable composition. The surface of the resin is hardened to form a hard coat layer containing a cured coating film having high scratch resistance, excellent adhesion to a cyclic olefin resin, and little coloration.

In order to solve the above problems, the inventors of the present invention have found that a compound having two or more specific structures in one molecule is used in a photopolymerization initiator for an ultraviolet curable composition. The cured coating film having excellent adhesion to the surface of the cyclic olefin resin molded article such as the cyclic olefin resin film can be formed, and the surface of the cured coating film has high scratch resistance and less coloration, and thus the present invention has been completed.

In other words, the present invention relates to an ultraviolet curable composition for a cyclic olefin resin and a cyclic olefin resin film using the same, and the ultraviolet curable composition for a cyclic olefin resin is characterized by containing an ultraviolet curable compound (A). And a compound which has two or more groups represented by the formula (1) in one molecule as a photopolymerization initiator (B), and is an essential component.

The ultraviolet curable composition of the present invention can impart high scratch resistance to the surface of the cyclic olefin resin molded article, and can obtain a cured coating film which is excellent in adhesion to the cyclic olefin resin molded article and has little coloration. Therefore, the ultraviolet curable composition of the present invention can be used as a material for forming a hard coat layer having high scratch resistance on the surface of various cyclic olefin resin molded articles, particularly on the surface of a cyclic olefin resin film. Further, the cyclic olefin resin film having a hard coat layer containing the cured coating film of the ultraviolet curable composition of the present invention can be used as an optical film used for a liquid crystal display or a touch panel.

[Formation of the Invention]

The ultraviolet curable composition of the present invention contains ultraviolet rays The linear curable compound (A) and a compound having two or more groups represented by the formula (1) in one molecule as the photopolymerization initiator (B).

The ultraviolet curable compound (A) may, for example, be a polyfunctional (meth) acrylate (A1) or a urethane (meth) acrylate (A2). These may be used alone or in combination of two or more.

Further, in the present invention, "(meth)acrylate" means either or both of an acrylate and a methacrylate, and "(propyl)acryloyl group" means a propylene group and a methacryl group. One or both.

The polyfunctional (meth) acrylate (A1) is a compound having two or more (propyl) acryl fluorenyl groups in one molecule. Specific examples of the polyfunctional (meth) acrylate (a1) include 1,4-butanediol di(meth)acrylate and 3-methyl-1,5-pentanediol di(a). Acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylic acid Ester, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, etc. Methyl acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, di(meth) acrylate of bis(2-hydroxyethyl) trimer isocyanate, in new Pentylene glycol 1 molar addition to 4 moles a di(meth)acrylate of a diol derived from ethylene oxide or propylene oxide, a diol derived from a bisphenol A 1 molar addition of 2 moles of ethylene oxide or propylene oxide (Meth) acrylate, trimethylolpropane tri(meth) acrylate, ethylene oxide modified trimethylolpropane tri(meth) acrylate, propylene oxide modified trimethylolpropane (Meth) acrylate, di-trimethylolpropane tri(meth) acrylate, di-trimethylolpropane tetra(meth) acrylate, gin(2-(methyl) propylene decyloxy Ethyl)trimeric isocyanate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol IV (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These polyfunctional (meth) acrylates (A1) may be used alone or in combination of two or more. Further, among these polyfunctional (meth) acrylates (A1), dinopentaerythritol is preferred from the scratch resistance of the cured coating film which can improve the ultraviolet curable composition of the present invention. Methyl) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, neopentyl alcohol tri (meth) acrylate.

The urethane (meth) acrylate (A2) is obtained by reacting a polyisocyanate (a2-1) with a (meth) acrylate (a2-2) having a hydroxyl group.

Examples of the polyisocyanate (a2-1) include an aliphatic polyisocyanate and an aromatic polyisocyanate. However, the color of the cured coating film which can further reduce the ultraviolet curable composition of the present invention is preferably aliphatic. Polyisocyanate.

The aliphatic polyisocyanate is a compound composed of an aliphatic hydrocarbon other than the isocyanate group. As this aliphatic Specific examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, isocyanate diisocyanate, and isocyanuric acid triisocyanate; norbornane diisocyanate, isophorone diisocyanate, and methylene bis ( 4-cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5 An alicyclic polyisocyanate such as diisocyanylcyclohexane. Further, a terpolymer obtained by polymerizing the aliphatic polyisocyanate or the alicyclic polyisocyanate 3 may be used as the aliphatic polyisocyanate. Further, these aliphatic polyisocyanates may be used singly or in combination of two or more.

Among the aliphatic polyisocyanates, in order to improve the scratch resistance of the coating film, among the aliphatic polyisocyanates, hexamethylene diisocyanate or alicyclic diisocyanate of a diisocyanate of a linear aliphatic hydrocarbon is preferred. Decane diisocyanate, isophorone diisocyanate.

The aforementioned (meth) acrylate (a2-2) is a compound having a hydroxyl group and a (propyl) acrylonitrile group. Specific examples of the (meth) acrylate (a2-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxy butyl ( Methyl) acrylate, 4-hydroxybutyl (meth) acrylate, 1,5-pentanediol mono(meth) acrylate, 1,6-hexanediol mono(meth) acrylate, neopentyl Mono(meth)acrylate of divalent alcohol such as diol mono(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol mono(meth)acrylate; trimethylolpropane di(meth)acrylic acid Ester, ethylene oxide (EO) modified trimethylolpropane (meth) acrylate, propylene oxide (PO) modified trimethylolpropane di(meth) acrylate, glycerol di(methyl) a mono- or di-(meth) acrylate of a trihydric alcohol such as acrylate or bis(2-(methyl) propylene decyloxyethyl) hydroxyethyl tripolyisocyanate, or Mono- and di(meth)acrylates having a hydroxyl group in which a part of the alcoholic hydroxyl group is modified with ε-caprolactone; neopentyl alcohol tri(meth)acrylate, di-trimethylolpropane a compound having a monofunctional hydroxyl group and a trifunctional or higher (propyl) acrylonitrile group such as tris(meth)acrylate or dipentaerythritol penta(meth)acrylate, or having the compound further ε-hexyl Polyfunctional (meth) acrylate of lactone-modified hydroxyl group; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene a (meth) acrylate having an alkylene chain such as a diol mono(meth)acrylate; a polyethylene glycol-polypropylene glycol mono(meth)acrylate, a polyoxybutylene-polyoxypropyl propyl group (meth) acrylate having a block structure of an alkylene chain such as mono(meth)acrylate; poly(ethylene glycol-butanediol) mono(meth)acrylate, poly(propylene glycol-extension) (Meth) acrylate having a random structure of an alkylene chain such as a mono(meth)acrylate such as a mono(meth)acrylate. These (meth) acrylates (a2-2) may be used alone or in combination of two or more.

Among the urethane (meth) acrylates (A2), it is preferable to have four or more in one molecule because the scratch resistance of the cured coating film of the ultraviolet curable composition of the present invention can be improved ( Propyl) acrylonitrile. In order to make the urethane (meth) acrylate (A2) have four or more (propyl) acrylonitrile groups in one molecule, as the (meth) acrylate (a2-2), It is preferred to have two or more (propyl) acrylonitrile groups. Examples of such a (meth) acrylate (a2-2) include trimethylolpropane di(meth)acrylate and ethylene oxide-modified trimethylolpropane di(meth)acrylic acid. Ester, propylene oxide modified trimethylolpropane di(meth) acrylate, glycerol di(meth) acrylate, bis(2-(methyl) propylene fluorenyl Oxyethyl)hydroxyethyltrimeric isocyanate, pentaerythritol tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylic acid Ester and the like. One type of these (meth) acrylates (a2-2) may be used alone or two or more types may be used in combination with one type of the above-mentioned aliphatic polyisocyanate (a1). Further, among these (meth) acrylates (a2-2), pentaerythritol tri(meth) acrylate and dipentaerythritol penta (meth) acrylate are improved in abrasion resistance. good.

The reaction of the above polyisocyanate (a2-1) with the above (meth) acrylate (a2-2) can be carried out by a conventional urethanation reaction. Further, in order to promote the progress of the urethanization reaction, it is preferred to carry out the urethanization reaction in the presence of a urethanization catalyst. Examples of the urethane-based catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; and phosphorus compounds such as triphenylphosphine and triethylphosphine. An organotin compound such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate or tin octylate, or an organic zinc compound such as zinc octylate.

Further, if necessary, an epoxy group (A) can be used as the ultraviolet curable compound (A) other than the polyfunctional (meth)acrylate (A1) or the urethane (meth)acrylate (A2). Higher molecular weight (meth) acrylate (A3) such as acrylate, polyester (meth) acrylate, or polyether (meth) acrylate. Examples of the epoxy group (meth) acrylate include (meth)acrylic acid by a bisphenol epoxy resin, a novolac epoxy resin, a polyepoxypropyl methacrylate, or the like. Reacted and esterified. Further, the polyester (meth) acrylate may, for example, be obtained by polycondensation of a polyvalent carboxylic acid and a polyhydric alcohol. a polyester having a hydroxyl group at the end, which is obtained by reacting and esterifying (meth)acrylic acid; or by reacting and esterifying (meth)acrylic acid by adding an alkylene oxide to a polycarboxylic acid; By. In addition, as the polyether (meth) acrylate, for example, a (meth)acrylic acid is reacted and esterified with a polyether polyol. Further, the (meth) acrylate (A3) may be used singly or in combination of two or more.

Further, in the ultraviolet curable composition of the present invention, in addition to (A1) to (A3) exemplified as the ultraviolet curable compound (A), a (meth) acrylate having a phosphate group (A4) is blended. Therefore, it is preferable because the adhesion to the substrate can be further improved. The (meth) acrylate (A4) having a phosphoric acid group is a (meth) acrylate having at least one phosphate group in one molecule. Examples of the (meth) acrylate (A4) having a phosphoric acid group include, for example, (meth) acryloyloxyethyl phosphate, di(methyl) propylene decyloxyethyl phosphate, and phosphoric acid (Methyl) propylene decyloxyethyl ester, caprolactone-modified phosphoric acid (meth) propylene decyloxyethyl ester, etc., and it is also possible to use two or more (propyl) acryl fluorenyl groups in one molecule. Compound. Further, these (meth) acrylates (A4) having a phosphoric acid group may be used singly or in combination of two or more kinds.

When the ultraviolet curable composition of the present invention is blended with the (meth) acrylate (A4) having a phosphoric acid group, the blending amount thereof can further enhance the adhesion to the substrate, and the surface of the hardened coating film can be further improved. The scratch resistance is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 20% by mass, based on the ultraviolet curable compound (A).

The ultraviolet curable composition of the present invention contains, as an essential component, the ultraviolet curable compound (A), and contains The compound (B1) having two or more groups represented by the following formula (1) in one molecule, as the photopolymerization initiator (B). Further, the phenyl group in the following formula (1) may be a substituent having a substituent such as an alkyl group, an alkoxy group or a halogen group.

When the compound (B1) is used as a photopolymerization initiator, the cured coating film of the ultraviolet curable composition of the present invention has high scratch resistance, excellent adhesion to a cyclic olefin resin, and less coloration. An excellent hard coat layer can be formed.

The compound (B1), for example, 2-(2-oxo-2-phenylethenyloxyethoxy)ethyl oxyphenylacetate represented by the following formula (2).

The photopolymerization initiator (B) contained in the ultraviolet curable composition of the present invention contains the compound (B1) as an essential component, but a photopolymerization initiator (B2) other than the above may be used. The photopolymerization initiator (B2) may, for example, be diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, or oligomeric {2-hydroxy- 2-methyl-1-[4-(1-methylvinyl)phenyl]acetone}, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2- Methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- Phytyl (4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Acetophenone-based compound such as phenylphenyl)-butanone; benzoin-based compound such as benzoin, benzoin methyl ether, benzoin isopropyl ether; 2,4,6-trimethylbenzene a mercaptophosphine oxide compound such as diphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide; benzyl (diphenylmethylhydrazine), a benzyl compound such as methylphenylacetaldehyde decyl ester or 2-(2-hydroxyethoxy)ethyl oxyphenylacetate; benzophenone, o-benzylidene benzoic acid methyl- 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, propylene deuterated diphenyl Methyl ketone, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2, a benzophenone compound such as 4,6-trimethylbenzophenone or 4-methylbenzophenone; 2-isopropyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 9-oxosulfur Compound; amino benzophenone-based compound such as rice ketone, 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylhydrazine , 9,10-phenanthrenequinone, camphorquinone, 1-[4-(4-benzylidenephenylsulfonyl)phenyl]-2-methyl-2-(4-methylphenylindenyl) Propane-1-one and the like.

The blending amount of the compound (B1) in the ultraviolet curable composition of the present invention is improved from the curable property and the adhesion to the cyclic polyolefin is improved with respect to the ultraviolet curable compound ( A) 100 parts by mass, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10% by mass.

Further, it is contained in the ultraviolet curable composition of the present invention. The ratio of the compound (B1) in the photopolymerization initiator (B) is preferably 50% by mass or more, more preferably 65% by mass or more, and still more preferably 80% by mass or more.

In addition to the ultraviolet curable compound (A) and the photopolymerization initiator (B), the ultraviolet curable composition of the present invention may be blended with a photosensitizer, an organic solvent, or a polymerization inhibitor depending on the intended use and desired characteristics. Surface conditioning agent, antistatic agent, antifoaming agent, viscosity modifier, light stabilizer, weathering stabilizer, heat stabilizer, ultraviolet absorber, antioxidant, leveling agent, organic pigment, inorganic pigment, pigment dispersant, Additives such as organic beads; inorganic fillers such as cerium oxide (vermiculite particles), aluminum oxide, titanium oxide, zirconium oxide, and antimony pentoxide. These other blends may be used singly or in combination of two or more.

Among the inorganic fillers, by blending the vermiculite particles, the scratch resistance of the surface of the cured coating film of the ultraviolet curable composition of the present invention can be further improved, and the adhesion to the substrate can be further improved. The vermiculite particles may be those whose surface is modified with an organic surface or which may not be surface-modified. Further, the vermiculite particles are preferably fine-grained fine particles of a nanometer size from the viewpoint of improving the transparency of the cured coating film of the ultraviolet curable composition of the present invention and the scratch resistance of the surface. It is a colloidal vermiculite. The average particle diameter of the fine particles of the vermiculite is preferably in the range of 5 to 200 nm, more preferably in the range of 5 to 100 nm. Further, the average particle diameter is a value measured by a dynamic light scattering method.

When the blending amount of the inorganic filler is blended, the scratch resistance of the surface of the cured coating film of the ultraviolet curable composition of the present invention is further improved, and the adhesion to the substrate is further improved. Ultraviolet The linear curable compound (A) is preferably 1 to 150 parts by mass, more preferably 5 to 100 parts by mass, per 100 parts by mass.

Examples of the photosensitizer include a tertiary amine compound such as diethanolamine, N-methyldiethanolamine or tributylamine, a urea compound such as o-tolylsulfuric acid, and sodium diethyldithiophosphate. And a sulfur compound such as s-benzylisothiourea-p-toluenesulfonate. The blending amount of the light sensitizing agent is preferably 0.01 to 20 parts by mass, more preferably 0.5 to 10% by mass, based on 100 parts by mass of the ultraviolet curable compound (A).

The organic solvent is useful for suitably adjusting the solution viscosity of the active energy ray-curable composition of the present invention, and in particular, for film coating, it is easy to adjust the film thickness. Examples of the organic solvent that can be used herein include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and t-butanol; ethyl acetate, butyl acetate, and propylene glycol monomethyl. Esters such as ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used singly or in combination of two or more.

In the ultraviolet curable composition of the present invention, since a cured coating film having excellent adhesion to a cyclic olefin resin is obtained, the substrate to which the ultraviolet curable composition of the present invention is applied is preferably a ring. An olefin resin molded article, particularly a cyclic olefin resin film. In addition, as the cyclic olefin resin, any polymer or copolymer may be used without particular limitation as long as it is a polymerized cyclic olefin. For example, "ZEONOR" and "ZEONEX" manufactured by Japan ZEON Co., Ltd.; "ARTON" manufactured by JSR Co., Ltd.; "TOPAS" manufactured by POLYPLASTICS Co., Ltd., etc., etc. .

The cyclic olefin resin film is one in which a cyclic olefin resin is formed on a film. In addition, the surface of the cyclic olefin resin film is improved in adhesion to the cured coating film of the ultraviolet curable composition of the present invention, and is preferably subjected to surface unevenness treatment by a sand blast method or a solvent treatment method. Electrical treatment (corona discharge treatment, atmospheric piezoelectric slurry treatment), chromic acid treatment, flame treatment, hot air treatment, ozone. Ultraviolet light. The processor such as the electron beam irradiation treatment or the oxidation treatment is more preferably an electric processor such as a corona discharge treatment or an atmospheric piezoelectric slurry treatment.

Further, the thickness of the cyclic olefin resin film is preferably in the range of 50 to 200 μm, more preferably in the range of 80 to 150 μm, still more preferably in the range of 90 to 130 μm. When the thickness of the film substrate is within this range, when a hard coat layer is provided on the single surface of the cyclic olefin resin film by the ultraviolet curable composition of the present invention, curling can be easily suppressed.

The cyclic olefin resin film of the present invention is obtained by coating the ultraviolet curable composition of the present invention on at least one side of the film and then irradiating ultraviolet rays as a cured coating film. The method of applying the ultraviolet curable composition of the present invention to the cyclic olefin resin film may, for example, die coating, micro gravure coating, gravure coating, roll coating, doctor blade coating, air knife coating, and conformal coating. Spray coating, pass coating, dip coating, spin coating, Wheeler coating, brush coating, full-plate coating by screen printing, wire bar coating, flow coating, and the like.

Moreover, in order to cure the ultraviolet curable composition, as a means for irradiating ultraviolet rays, for example, a low pressure mercury lamp and high pressure water are mentioned. Silver lamp, ultra-high pressure mercury lamp, metal halide lamp, electrodeless lamp (Fusion lamp), chemical lamp, black light, mercury-xenon lamp, short arc lamp, 氦. Cadmium laser, argon laser, sunlight, LED, etc.

The cyclic olefin resin film having the cured coating film of the ultraviolet curable composition of the present invention is excellent in surface scratch resistance due to excellent optical properties, dimensional stability, heat resistance and transparency of the substrate. It can be applied to various applications, but is particularly useful as an optical film used in an image display unit of an image display device such as a liquid crystal display (LCD) or an organic EL display (OLED). In particular, since it has excellent scratch resistance even in a thin shape, it can be preferably used in combination as a miniaturization or thinning requirement such as an electronic notebook, a mobile phone, a smart phone, a portable audio player, a mobile personal computer, and a portable terminal. A high optical film of an image display portion of an image display device that carries an electronic terminal. Further, when used as an optical film, it can be used as a protective film for the outermost surface of the image display portion of the image display device or a substrate of the touch panel. Further, when used as a protective film, for example, an image display device having a structure for protecting a transparent panel of the image display module on an upper portion of an image display module such as an LCD module or an OLED module is attached thereto. It is used on the surface or the back surface of the transparent panel, and is effective in preventing scattering damage or scattering of the transparent panel.

[Examples]

The invention will be more specifically described below by way of examples.

(Synthesis Example 1: Synthesis of urethane acrylate (A2-1))

245 parts by mass of butyl acetate, 222 parts by mass of isophorone diisocyanate, 0.5 parts by mass of p-methoxyphenol, and 0.5 parts by mass of dibutyltin diacetate were placed in a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer. After raising the temperature to 70 ° C while blowing air, a mixture of pentaerythritol triacrylate (hereinafter referred to as "PE3A") and pentaerythritol tetraacrylate (hereinafter referred to as "PE4A") was added dropwise for 1 hour. (PE3A/PE4A=75/25 (mass ratio)) 400 parts by mass and 497 parts by mass of isomeric cyanuric acid-modified diacrylate. After the completion of the dropwise addition, the reaction was carried out at 70 ° C for 3 hours, and the reaction was further carried out until the infrared absorption spectrum of 2250 cm ^-1 showing the isocyanate group disappeared, and a urethane acrylate having 6 propylene groups in one molecule was obtained. A solution of (A2-1) having a nonvolatile content of 80% by mass. Further, in this solution, the nonvolatile matter contained 19.5% by mass of PE4A in addition to the urethane acrylate (A2-1).

(Example 1)

A mixture of dipentaerythritol hexaacrylate (hereinafter abbreviated as "DPHA") and dipentaerythritol pentaacrylate (hereinafter referred to as "DPPA") was uniformly stirred (DPHA/DPPA = 65/35 (mass ratio) 35 parts by mass, polyester acrylate (4-functional, molecular weight 1,800), 65 parts by mass, vermiculite fine particles ("MEK-ST" manufactured by Nissan Chemical Industries, Ltd., average particle diameter 10-20 nm, organic vermiculite sol 30 Mass % methyl ethyl ketone dispersion; hereinafter referred to as "fine stone fine particle dispersion (1)") 25 parts by mass (7.5 parts by mass of vermiculite particles), and 2-(2- side of oxyphenylacetic acid) 3 parts by mass of oxy-2-phenylethenyloxyethoxy)ethyl ester (hereinafter referred to as "photopolymerization initiator (B1-1)"), diluted with methyl ethyl ketone, and not prepared An ultraviolet curable composition (1) having 25% by mass of volatile matter.

[Production of evaluation film]

The ultraviolet curable composition (1) obtained above was applied to a cyclic olefin resin film (manufactured by Japan ZEON Co., Ltd.) by electroplating (corona discharge treatment; output of 100 W, speed: 1.0 m/min) in advance. After heating at 60 ° C for 90 seconds on a ZeonorFilm ZF16-100" and a thickness of 100 μm), an ultraviolet irradiation device ("MIDN-042-C1" manufactured by iGrafx Co., Ltd., lamp: 120 W/cm, high-pressure mercury lamp) was used in an air atmosphere. The ultraviolet light was irradiated with an irradiation light amount of 0.3 J/cm ² to obtain a film for evaluation having a cured coating film having a thickness of 4 μm.

[Evaluation of scratch resistance]

The surface of the cured coating film of the evaluation film obtained above was tested by a Crock Meter type friction tester (diameter 1.0 cm circular friction, stainless steel cotton #0000, weight 300 g, back and forth 10 times) to visually observe the test. The surface of the coating film was hardened, and the scratch resistance was evaluated in accordance with the following criteria.

A: The number of injuries is 9 or less.

B: The number of injuries is more than 10.

[Evaluation of adhesion]

On the evaluation film obtained above, 11 slits of vertical and horizontal were cut at intervals of 1 mm on the surface of the cured film of the film to prepare 100 lattices. Next, the operation of peeling off the commercially available celluloid tape on the surface thereof was repeated twice. The number of unremoved lattices was counted, and the adhesion was evaluated according to the following criteria.

A: The number of remaining grids is 100.

B: The number of remaining lattices is 80 or more and 99 or less.

C: The number of remaining lattices is 60 or more and 80 or less.

D: The number of remaining lattices is 59 or less.

[Evaluation of Thick Film Adhesion]

In the same manner as the production of the evaluation film described above, a film for evaluating a thick film adhesion having a cured coating film having a thickness of 6 μm was obtained, except that the coating amount of the ultraviolet curable composition (1) was changed. The obtained film was evaluated in the same manner as the above evaluation of the adhesion, and the thick film adhesion was evaluated.

[Evaluation of film coloring]

The evaluation film obtained above was cut into a size of 50 mm × 80 mm, and the film was wound around a rod having an outer diameter of 8 mm and fixed with a cellophane tape. Next, after the rod was pulled out, the color tone of the film for evaluation of the roll shape was visually observed, and the coloring of the coating film was evaluated in accordance with the following criteria.

A: No color.

B: There is a yellow color.

(Example 2)

The ultraviolet curable composition (2) was prepared in the same manner as in Example 1 except that the blending amount of the photopolymerization initiator (B1-1) was changed from 3 parts by mass to 6 parts by mass.

(Example 3)

An ultraviolet curable composition having a nonvolatile content of 25% by mass was prepared in the same manner as in Example 1 except that the blending amount of the photopolymerization initiator (B1-1) was changed from 3 parts by mass to 9 parts by mass. 3).

(Example 4)

The polyfunctional urethane acrylate (A2-1) (nonvolatile matter 80% by mass) obtained in Synthesis Example 1 was uniformly stirred in an amount of 125 parts by mass. 100 parts by mass of the acrylate, and 25 parts by mass of the vermiculite fine particle dispersion (1) (7.5 parts by mass of the vermiculite particles) and 3 parts by mass of the photopolymerization initiator (B1-1), The ethyl ethyl ketone was diluted to prepare an ultraviolet curable composition (4) having a nonvolatile content of 25% by mass.

(Example 5)

An ultraviolet curable composition having a nonvolatile content of 25% by mass was prepared in the same manner as in Example 4 except that the blending amount of the photopolymerization initiator (B1-1) was changed from 3 parts by mass to 6 parts by mass. 5).

(Example 6)

An ultraviolet curable composition having a nonvolatile content of 25% by mass was prepared in the same manner as in Example 4 except that the blending amount of the photopolymerization initiator (B1-1) was changed from 3 parts by mass to 9 parts by mass. 6).

(Example 7)

125 parts by mass of the polyfunctional urethane acrylate (A2-1) (nonvolatile content: 80% by mass) obtained in Synthesis Example 1 (100 parts by mass based on the polyfunctional acrylate), vermiculite Microparticles (MEK-ST40, manufactured by Nissan Chemical Industries, Ltd.), 40% by mass of methyl ethyl ketone dispersion with an average particle diameter of 10 to 20 nm and an organic vermiculite sol; hereinafter referred to as "fine particles of fine particles (2) ”62.5 parts by mass (25 parts by mass of vermiculite particles) and 6 parts by mass of photopolymerization initiator (B1-1), and then diluted with methyl ethyl ketone to prepare a nonvolatile content of 25% by mass. Ultraviolet curable composition (7).

(Example 8)

Uniformly stirring the polyfunctional urethane acrylate (A2-1) (nonvolatile matter 80% by mass) 123.75 parts by mass (based on the polyfunctional acrylate) 99 parts by mass), methacrylate having a phosphate group ("MIRAMER SC1400" manufactured by MIWON Co., Ltd.; hereinafter referred to as "phosphoric acid methacrylate (1)"), 1 part by mass, vermiculite fine particle dispersion (2) 62.5 mass A part (25 parts by mass of vermiculite particles) and 6 parts by mass of a photopolymerization initiator (B1-1) were diluted with methyl ethyl ketone to prepare a UV curable composition having a nonvolatile content of 25% by mass. (8).

(Example 9)

The polyfunctional urethane acrylate (A2-1) (nonvolatile matter 80% by mass) was uniformly stirred, 118.75 parts by mass (95 parts by mass based on the polyfunctional acrylate), and phosphoric acid methacrylate (1) 5 The mass fraction, the vermiculite fine particle dispersion (2), 62.5 parts by mass (25 parts by mass in terms of vermiculite particles), and 6 parts by mass of the photopolymerization initiator (B1-1) are diluted with methyl ethyl ketone. Further, an ultraviolet curable composition (9) having a nonvolatile content of 25% by mass was prepared.

(Embodiment 10)

The polyfunctional urethane acrylate (A2-1) (nonvolatile matter 80% by mass) was uniformly stirred, 113.75 parts by mass (91 parts by mass based on the polyfunctional acrylate), and phosphoric acid methacrylate (1) 9 The mass fraction, the vermiculite fine particle dispersion (2), 62.5 parts by mass (25 parts by mass in terms of vermiculite particles), and 6 parts by mass of the photopolymerization initiator (B1-1) are diluted with methyl ethyl ketone. Further, an ultraviolet curable composition (10) having a nonvolatile content of 25% by mass was prepared.

(Example 11)

The ultraviolet curable composition (11) having a nonvolatile content of 25% by mass was prepared in the same manner as in Example 7 except that the vermiculite fine particle dispersion (2) was not blended.

(Embodiment 12)

An ultraviolet curable composition (12) having a nonvolatile content of 25% by mass was prepared in the same manner as in Example 9 except that the vermiculite fine particle dispersion (2) was not blended.

(Comparative Example 1)

In addition to 4-(4-methylphenylthio)benzophenone (hereinafter referred to as "photopolymerization initiator (R1)"), instead of the photopolymerization initiator (B1-1) used in Example 1, The ultraviolet curable composition (R1) was prepared in the same manner as in Example 1.

(Comparative Example 2)

An ultraviolet curable composition was prepared in the same manner as in Example 1 except that 9 parts by mass of the photopolymerization initiator (R1) was used in place of 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1. R2).

(Comparative Example 3)

Except that 6 parts by mass of 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as "photopolymerization initiator (R2)") was used instead of 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1, The ultraviolet curable composition (R3) was prepared in the same manner as in Example 1.

(Comparative Example 4)

In addition to 2-benzyl-2-dimethylamino-1-(4- 6 parts by mass of the morphylphenyl)-1-butanone (hereinafter referred to as "photopolymerization initiator (R3)"), in place of 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1, The ultraviolet curable composition (R4) was prepared in the same manner as in Example 1.

(Comparative Example 5)

In addition to 2-methyl-1-(4-methylthiophenyl)-2- 6 parts by mass of the morphyl propan-1-one (hereinafter referred to as "photopolymerization initiator (R4)"), in place of 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1, 1 was carried out in the same manner to prepare an ultraviolet curable composition (R5).

(Comparative Example 6)

In addition to 2-hydroxy-1-[4-(2-hydroxyethoxy)-phenyl]-2-methyl-1-propan-1-one (hereinafter referred to as "photopolymerization initiator (R5)" In the same manner as in Example 1, except that 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1 was used, the ultraviolet curable composition (R6) was prepared.

(Comparative Example 7)

In place of 6 parts by mass of diphenyl(2,4,6-trimethylbenzylidene)phosphine oxide (hereinafter referred to as "photopolymerization initiator (R6)"), instead of the photopolymerization used in Example 1, The ultraviolet curable composition (R7) was prepared in the same manner as in Example 1 except that the starting agent (B1-1) was used in an amount of 3 parts by mass.

(Comparative Example 8)

In place of 6 parts by mass of 2-hydroxy-2-methyl-1-phenyl-1-propanone (hereinafter referred to as "photopolymerization initiator (R7)"), the photopolymerization initiator (B1) used in Example 1 was replaced. In the same manner as in Example 1, except that the amount of -1) was 3 parts by mass, the ultraviolet curable composition (R8) was prepared.

(Comparative Example 9)

In addition to 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-1-propanone (hereinafter referred to as "light" In the same manner as in Example 1, except that 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1 was used, the ultraviolet curable composition (R9) was prepared. ).

(Comparative Example 10)

In addition to 2,4-diethyl 9-oxosulfur In the same manner as in Example 1, except that 6 parts by mass of the photopolymerization initiator (B1-1) used in Example 1 was used instead of 3 parts by mass of the photopolymerization initiator (R9), ultraviolet rays were prepared. Hardenable composition (R10).

The ultraviolet curable compositions (2) to (12) and (R1) to (R10) obtained in the above Examples 2 to 12 and Comparative Examples 1 to 10 were evaluated for scratch resistance and adhesion in the same manner as in Example 1. Sex, thick film adhesion, and film coloring.

The compositions and evaluation results of the ultraviolet curable compositions used in the above Examples 1 to 12 and Comparative Examples 1 to 10 are shown in Tables 1 to 4. Further, the compositions in Tables 1 to 4 are described as non-volatile components.

As a result of the evaluation shown in Table 1, it is understood that the materials of Examples 1 to 12 of the ultraviolet curable composition of the present invention have excellent scratch resistance on the surface of the cured coating film and are adhered to the cyclic polyolefin resin film of the substrate. The sex was also high, and the color of the film was not observed. In particular, the ultraviolet curable compositions (8) to (10) of Examples 8 to 10 in which a phosphoric acid group-containing acrylate and vermiculite fine particles are blended have excellent adhesion even with a thick film.

On the other hand, the ultraviolet curable composition of Comparative Examples 1 to 10 is an example of a photopolymerization initiator which does not contain a compound which is an essential component in the present invention. These ultraviolet curable compositions do not fully satisfy the sufficient scratch resistance of the surface of the cured coating film, sufficient adhesion to the cyclic polyolefin resin film of the substrate, and evaluation of the coloring of the coating film.

Claims (7)

A cyclic olefin resin film obtained by coating an ultraviolet curable composition on at least one side of a cyclic olefin resin film, and then irradiating with ultraviolet rays to form a cured coating film; the ultraviolet curable composition contains The ultraviolet curable compound (A) and the compound (B1) having two or more groups represented by the formula (1) in one molecule as the photopolymerization initiator (B) are regarded as essential components thereof. The cyclic olefin resin film according to claim 1, wherein the compound (B1) is 2-(2-oxo-2-phenylethenyloxyethoxy)ethyl oxyphenylacetate. The cyclic olefin resin film according to claim 1 or 2, wherein the ultraviolet curable compound (A) contains a polyfunctional (meth) acrylate (A1). The cyclic olefin resin film according to claim 3, wherein the polyfunctional (meth) acrylate (A1) is selected from the group consisting of dipentaerythritol hexa(meth) acrylate and dipentaerythritol penta (methyl) One or more of the group of acrylate, pentaerythritol tetra(meth)acrylate, and pentaerythritol tri(meth)acrylate. The cyclic olefin resin film according to claim 1 or 2, wherein the ultraviolet curable composition further contains a (meth) acrylate (A4) having a phosphate group. The cyclic olefin resin film of claim 1 or 2, wherein the ultraviolet The wire curable composition further contains an inorganic filler. The cyclic olefin resin film according to claim 1, which is obtained by subjecting at least one surface of the cyclic olefin resin film to electrical treatment in advance, and coating the ultraviolet curable composition on the treated surface, and then The ultraviolet ray is irradiated to form a hardened coating film.