TWI486408B - Hard coat resin composition of ultra violet ray curable type, a hard coat film using such hard coat resin composition, and a formed article of hard coat - Google Patents

Description

UV curable hard coat resin composition, hard coat film and hard coat molded product using the same

The present invention relates to an ultraviolet curable hard coat resin composition, a hard coat film having such a hardened layer, and a hard coat formed article. Specifically, it is an ultraviolet curable hard coat resin composition suitable for coating on the surface of a plastic film such as polyester, acrylic, or polycarbonate. The molded article obtained by hardening the resin composition of the present invention does not cause cracks even when the curved surface portion of the surface is curved. Further, the molded article obtained by this hardening has a good pencil hardness. In other words, since the molded article obtained by curing the resin composition of the present invention has excellent flexibility and moldability, it is a hard coat film suitable for use in film insert molding.

At present, plastics are widely used in various industries including the automotive industry, home appliance industry, and electrical and electronics industries. The reason why such a large amount of plastic is used is due to reasons such as light weight, low cost, and good optical properties in addition to workability and transparency. However, since the plastic is softer than glass, there is a disadvantage that the surface is easily scratched. In order to improve these disadvantages, the general method is to apply a hard coating agent on the surface of the plastic. As such a hard coat agent, a thermosetting type hard coat agent such as a polyfluorene type paint, an acrylic type paint, or a melamine type paint is used. Among these, in particular, a polyoxygen-based hard coat agent is used in a large amount because of high hardness and good quality. However, the polyoxygenated hard coat agent has a long hardening time and a high price, and is not suitable for the hard coat layer provided on the continuously processed film.

In recent years, a photosensitive acrylic hard coat agent (photosensitive hard coat agent) has been developed and utilized (see Patent Document 1). The photosensitive hard coat agent is irradiated with radiation such as ultraviolet rays to immediately harden to form a hard film. The faster the processing speed, the better the hardness, scratch resistance, and the like of the cured product. In addition, due to the low total cost of photosensitive hard coat agents, it is currently the mainstream in the field of hard coatings. Photosensitive hard coat agent is especially suitable for continuous processing of plastic film. Although the plastic film has a polyester film, an acrylic film, a polycarbonate film, a vinyl chloride film, a cellulose triacetate film, a polyether ruthenium film, a polycycloolefin film, etc., the polyester film is most used for various excellent properties. widely. This type of polyester film is widely used in the prevention of glass scattering film, or the light-shielding film of automobiles, the surface film of whiteboard, the anti-fouling film of the system kitchen surface, in electronic materials, CRT flat-panel TV, liquid crystal display (LCD), plasma display (PDP), organic EL display, touchpad and other functional films. A hard coat layer is applied to prevent the surface of any of these from being scratched.

Furthermore, the use of diaphragms in the field of forming processing is also increasing. For example, a diaphragm can be used for forming a car exterior material such as a mobile phone and a personal computer such as a rack outer casing or an instrument panel cover, a display panel of an AV device and a home electric appliance, and a switch button.

The molding of plastic products can be injection molded using a mold. As a method of surface processing of a plastic product obtained in this manner, a method of attaching a film to an inner surface of a mold and attaching it to a surface of a molded article simultaneously with plastic molding is called film-embedded injection molding, in-mold (in-mold) ) Forming, etc. Further, by printing a pattern or a pattern on the attached film, it is possible to improve the appearance and the like of the molded article by the hard coat treatment, or to impart functionality.

The hard coat film used for injection molding has a case where the amount of the hard coat layer is applied to the base film and the hard coat film is integrally formed, and the hard coat layer is coated on the film having the release layer and peeled off after the forming process. In the case of a release film (Patent Document 2).

Since the hard coat film used for injection molding becomes the surface of a plastic product, of course, it should have an appearance such as surface hardness, glossiness, transparency, and the like, and the stretchability and flexibility which are necessary to withstand the forming process are opposite to the surface hardness. performance. However, the conventional hard coat agent cannot have both surface hardness (hardness) and ductility and flexibility after hardening. In other words, when the hardness is high, the stretchability and the flexibility are lowered. Conversely, when the stretchability and the flexibility are improved, the hardness is lowered, and it is not sufficient as a hard coat agent used for the forming process.

The conventional hard coat agent can be mentioned as described in the above documents 3 to 5. For example, the hard coat agent disclosed in the above-mentioned Document 3 and the above-mentioned Document 4 has sufficient hardness but insufficient stretchability, and the necessary transparency cannot be obtained. From this, it is understood that the composition which gives priority to flexibility is insufficient in hardness and transparency due to the influence of inorganic substances. Further, the hard coat agent disclosed in the above Document 5 has transparency, but the relationship between hardness and stretchability is also the same as that of the above-mentioned Document 3 and the aforementioned Document 4. Such a hard coat agent is not suitable for forming processing.

Further, the hard coat agent disclosed in the above-mentioned Document 6 is useful for film insert molding, but contains a large amount of colloidal silica in order to have both hardness and stretchability, which is disadvantageous in that it is expensive.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-48934

[Patent Document 2] Japanese Patent No. 3007326

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-81696

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-1598

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2008-94929

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2009-24168

The present invention provides an inexpensive ultraviolet curable hard coat resin composition which can be easily hardened by radiation including ultraviolet rays, hardness, adhesion, transparency, antifouling property, and stretching of a cured product. It is excellent in properties, and is suitable as a material of a hard coat agent used for film insertion molding in a bending step. Further, a hard coat film and a hard coat formed article having the hardened layer are also provided.

In order to solve the above problems, the inventors of the present invention have found that the ultraviolet curable hard coat resin composition containing a specific compound can solve the above problems, and the present invention has been completed.

In other words, the present invention relates to (1) an ultraviolet curable hard coat resin composition for a formed film comprising an epoxy resin (a) represented by the general formula (1) and (meth)acrylic acid (b) An epoxy (meth) acrylate (A) having at least three (meth) acrylonitrile groups in the molecule obtained by the reaction, a photoradical polymerization initiator (B), and an antifouling agent (C) ,

(wherein R is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and n represents a positive number of 1 to 20;); (2) ultraviolet rays as described in the above (1) The hardening type hard coat resin composition, wherein the antifouling agent (C) is a polyoxyalkylene having a (meth) acrylonitrile group; (3) the ultraviolet curable hard coat resin as described in the above (1) The composition, wherein the antifouling agent (C) is a fluorine-containing compound having a (meth) acrylonitrile group; (4) the ultraviolet curable hard coat resin according to any one of the above (1) to (3) In the epoxy resin (a) of the formula (1), R is a methyl group; (5) The ultraviolet curable hard coat resin according to any one of the above (1) to (4) The composition contains an ultraviolet curable (meth) acrylate (D) having at least three (meth) acrylonitrile groups in a molecule other than the component (A); (6) as described in (1) above (5) The ultraviolet curable hard coat resin composition according to any one of the present invention, which further comprises an epoxy (meth) acrylate (E-1) having two (meth) acrylonitrile groups in the molecule and / or polyurethane (meth) acrylate (E-2); (7) The ultraviolet curable hard coat resin composition according to any one of the above (1), which further comprises a reactive diluent (F) having 1 to 2 (meth) acrylonitrile groups; (8) The ultraviolet curable hard coat resin composition according to any one of the above (1) to (7), which further comprises a diluent (G); (9) a hard coat film having the foregoing (1) A hard coat layer of the ultraviolet curable hard coat resin composition according to any one of (1) to (8), wherein A hardened layer of the ultraviolet curable hard coat resin composition.

According to the present invention, it is possible to provide an ultraviolet curable hard coat resin composition which has good hardness, transparency, antifouling property, stretchability, and flexibility. Further, a hard coat film having such a hardened layer and a hard coat formed article are also provided. The ultraviolet curable hard coat resin composition of the present invention is suitably used as a formed film for film insert molding.

Hereinafter, the present invention will be described in detail.

The ultraviolet curable hard coat resin composition (hereinafter referred to as "resin composition") of the present invention is obtained by reacting the epoxy resin (a) represented by the general formula (1) and (meth)acrylic acid (b). An epoxy (meth) acrylate (A) having at least three (meth) acrylonitrile groups in the molecule.

(wherein R is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and n represents a positive number of the average of 1 to 20.)

The hydrocarbon group having 1 to 4 carbon atoms in the formula (1) may be a saturated hydrocarbon group having 1 to 4 carbon atoms or an unsaturated hydrocarbon group having 2 to 4 carbon atoms, which may be a straight chain, a branched chain or a cyclic group. Specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, cyclopropyl, cyclobutyl, vinyl, Propylene, isopropenyl and the like.

In the epoxy resin (a) represented by the formula (1), all of R is a hydrogen atom or a methyl group. In general, those in which R is a hydrogen atom can be obtained by the Japanese chemical EPPN-200 series, and all R are methyl groups, and the same can be obtained by the Japanese chemical EOCN series.

In the present invention, it is preferred that all of R of the epoxy resin (a) represented by the formula (1) is a methyl group. Compared with those in which R is all a hydrogen atom, the cured product maintains a good elongation on one side while achieving high hardness.

The average value of n of the epoxy resin (a) represented by the formula (1) is from 1 to 20. In the present invention, n is preferably from 1 to 15, more preferably from 5 to 12.

The carboxylic acid esterification reaction of the epoxy (meth) acrylate (A) having at least three (meth) acrylonitrile groups in the molecule used in the production of the present invention, relative to 1 equivalent of epoxy resin (a The epoxy group and the (meth)acrylic acid (b) are preferably 90 to 120 equivalent% in total. Within this range, it can be manufactured under relatively stable conditions. When the amount of (meth)acrylic acid (b) is too large, the excess (meth)acrylic acid (b) remains and is therefore unsatisfactory.

The carboxylic acid esterification reaction can be carried out without a solvent or by solvent dilution. The solvent which can be used in the present invention is not particularly limited as long as it is a solvent which is inactive to the carboxylic acid esterification reaction. The solvent usage amount is preferably adjusted depending on the viscosity and use of the obtained resin, but the solid content (epoxy (meth) acrylate (A) having at least three (meth) acrylonitrile groups in the molecule) The solvent is used in such a manner that 30 to 90% by mass, preferably 50 to 80% by mass, is used.

Specific examples of the solvent user include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, and aliphatic hydrocarbon solvents such as hexane, octane, and decane, and Such mixtures of petroleum ether, white gasoline, and solvent naphtha.

Further, examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as γ-butyrolactone; and ethylene glycol monomethyl ether acetate; Ethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoester, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, And butanediol monomethyl ether monoacetate (single or multiple) alkyl glycol monoalkyl ether monoacetate, dialkyl glutarate, dialkyl succinate, and adipate dioxane A polycarboxylic acid alkyl ester or the like.

Further, examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and triethyl ethane. Glycol dimethyl ether, glycol ethers such as triethylene glycol diethyl ether, and cyclic ethers such as tetrahydrofuran.

Further, examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

In the reaction, in order to promote the reaction, it is preferred to use a catalyst, and the use of the total amount of the catalyst relative to the reactants, that is, the epoxy resin (a), the (meth)acrylic acid (b), and the solvent other additives are used. The amount is from 0.1 to 10% by mass. The reaction temperature at this time is from 60 to 150 ° C, and the reaction time is preferably from 5 to 60 hours. Specific examples of the catalyst which can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethyl iodide. Known general alkaline catalysts such as ammonium, triphenylphosphine, triphenylstibine, methyltriphenylphosphonium, chromium octoate, and zirconium octoate.

In addition, the thermal polymerization inhibitor uses hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, and 3,5-di-t-butyl-4-cresol is preferred.

In the present reaction, the acid value of the sample is set to be 5 mgKOH/g or less, preferably 2 mgKOH/g or less, as an end point.

A preferred molecular weight range of the epoxy (meth) acrylate (A) having at least 3 (meth) acrylonitrile groups in the molecule thus obtained, by GPC (gel permeation chromatography) polystyrene The converted mass average molecular weight is in the range of 1,000 to 30,000, preferably 5,000 to 15,000. In addition, these may be used singly or in combination of plural kinds.

In the ultraviolet curable hard coat resin composition of the present invention, the total amount of (A), (B), (C), (D), (E) and (F) components is 100% by mass (hereinafter referred to as " In the total amount"), the content of the above component (A) is usually from 5 to 99.9% by mass, preferably from 10 to 99% by mass. When the component (D), and/or the component (E), and/or the component (F), and/or (G) are not used, the content of the component (A) is usually 80 to 99.9% by mass, and 90 to 99. The mass % is better. When the component (D), and/or the component (E), and/or the component (F), and/or (G) described later are used, it is usually 5 to 95% by mass, preferably 10 to 90% by mass.

The ultraviolet curable hard coat resin composition of the present invention is a photoradical polymerization initiator (B). The photoradical polymerization initiator (B) may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl Phenylketone, and acetophenones such as 2-methyl-1-(4-(methylthio)phenyl)-2-(4-morpholinyl)-1-propanone; 2-ethylhydrazine, 2-tertium butyl hydrazine, 2-chloro hydrazine, and 2-pentyl hydrazine, etc.; 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone, and 2- Thioxanthone such as chlorothioxanthone; ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzylidene-4'-methyl Diphenyl sulfide, and benzophenones such as 4,4'-bismethylaminobenzimidazole; oxidized 2,4,6-trimethylbenzhydryldiphenylphosphine, and oxidized bis ( A phosphine oxide such as 2,4,6-trimethylbenzylidene)-phenylphosphine. Further, specifically, IRGACURE 184 (1-hydroxycyclohexyl phenyl ketone) and IRGACURE 907 (2-methyl-1-(4-(methylthio)phenyl)-2, which are manufactured by Ciba Speciaity Chemical Co., Ltd., are readily available on the market. -(4-morpholinyl)-1-propanone) and Lucirin TPO (2,4,6-trimethylbenzhydryldiphenylphosphine oxide) manufactured by BASF Corporation. Further, these may be used singly or in combination of two or more.

In the ultraviolet curable hard coat resin composition of the present invention, the content of the component (B) is usually from 0.1 to 20% by mass, preferably from 1 to 10% by mass, based on the total amount.

In the ultraviolet curable hard coat resin composition of the present invention, a sensitizer may be used in combination if necessary. Sensitizers which can be used include, for example, anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 2-ethyl -9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-ethyl-9,10-dipropoxyfluorene, 2-ethyl-9,10- Bis(methoxyethoxy)anthracene, anthracene, anthracene, stilbene, 4'-nitrobenzyl-9,10-dimethoxyindole-2-sulfonate, and 4'-nitro Benzyl-9,10-diethoxyindole-2-sulfonate, and 4'-nitrobenzyl-9,10-dipropoxyindole-2-sulfonate, etc., by solubility Further, 2-ethyl-9,10-bis(methoxyethoxy)anthracene is preferred from the viewpoint of compatibility with the ultraviolet curable hard coat resin composition.

When the sensitizer is used, it is used in an amount of from 1 to 200% by mass, preferably from 5 to 150% by mass, based on 100% by mass of the photoradical polymerization initiator (B).

The ultraviolet curable hard coat resin composition of the present invention contains an antifouling agent (C). Examples of the antifouling agent (C) include a polyfluorene-based compound, a fluorine-based compound, and an acrylic compound. By the antifouling function of the antifouling agent, it is possible to impart water repellency, oil repellency, etc., to improve trace wiping property and fingerprint wiping property. Further, in addition to the antifouling function, the smoothness, smoothness, and scratch resistance of the workability are improved, and the acrylic compound can impart recoatability and the like.

The polyoxonium compound of the antifouling agent (C) is preferably a polyalkylene oxide having a (meth) acrylonitrile group. The polyalkylene oxide having a (meth) acrylonitrile group is also referred to as polyfluorene oxyacrylate, organically modified polyfluorene oxide, organically modified polydecane oxygen, or a reaction-bound organically modified polyoxy acrylate. The polyalkylene oxide having a (meth) acrylonitrile group may, for example, be an organic modification of a part of a linear dimethylpolydecane oxygen, such as an alkyl group or a polyether, and the acrylate group is imparted to the modified terminal. . By extending the length of the decane oxygen, the surface can be smoothed, and the release property, blocking resistance and the like can be imparted. Others, the wiping of traces and fingerprints has also become easier. Further, by improving the organic reforming ratio (degree of (meth) acrylate modification and polyether upgrading), compatibility, recoatability (recoatability), and printability can be improved. Further, by introducing an acrylonitrile group, it becomes reactively bondable, and the mobility toward the interface can be lowered, and the long-term performance stability can be improved by reacting with the base resin. Furthermore, chemical resistance (alkaline solution, organic solvent, etc.) can be improved. As such polyoxyalkylene having a (meth) acrylonitrile group, for example, BYK-UV3500, BYK-UV3570 (all manufactured by BYK-Chemie Co., Ltd.), 2100, 2200N, 2250, 2500, 2600 of the TEGO Rad series, 2700 (all manufactured by Degussa), X-22-2445, X-22-2455, X-22-2457, X-22-2458, X-22-2459, X-22-1602, X-22-1603 , X-22-1615, X-22-1616, X-22-1618, X-22-1619, X-22-2404, X-22-2474, X-22-174DX, X-22-8201, X -22-2426, X-22-164A and X-22-164C (all manufactured by Shin-Etsu Chemical Co., Ltd.) can be obtained from the market, but not limited to these. Further, these may be used singly or in combination of two or more.

The molecular weight of the (meth) acrylonitrile-based polydecane oxygen and the number of (meth) acrylonitrile groups are not particularly limited, and the number of (meth) acrylonitrile groups is preferably 1 to 6 in 1 molecule, 1 to 3 are better.

In the case where a fluorine-based compound is used as the antifouling agent (C) in the present invention, it is preferred to use a fluorine compound having a (meth)acrylonium group. Examples of the fluorine compound having a (meth) acrylonitrile group include those in which a (meth) acrylonitrile group is added to the terminal of the modified perfluoropolyether. By extending the length of the perfluorocarbon and increasing the fluorine content, the surface smoothness can be improved, and the release property and the blocking resistance can be imparted. In addition, even if the touch surface is not easy to leave fingerprints, the marks and fingerprints attached to the surface become easy to wipe off. Moreover, by improving the organic reforming ratio (degree of (meth) acrylate reformability and polyether reformability), compatibility, recoatability (recoatability), and printability can be improved. Further, by introducing a (meth) acrylonitrile group, it becomes reactively bondable, and the mobility toward the interface can be lowered, and the long-term performance stability can be improved by reacting with the base resin. Furthermore, chemical resistance (alkaline solution, organic solvent, etc.) can be improved. As such a product of a fluorine compound having a (meth) acrylonitrile group, for example, Optool DAC, Optool DAC-HP, R-1110, R-1210, R-1420 manufactured by Daikin Industries Co., Ltd. , R-1620, R-1820, R-2020, R-5210, R-5410, R-5610, R-5810, R-7210 and R-7310. Further, these may be used singly or in combination of two or more.

The molecular weight of the fluorine compound having a (meth) acrylonitrile group and the number of (meth) acrylonitrile groups are not particularly limited, and it is preferred that the number of (meth) acrylonitrile groups is 1 to 2 in one molecule.

When the polyalkylene oxide having a (meth) acrylonitrile group is used in the resin composition of the present invention, the ease of fingerprint wiping on the surface of the cured product is compared with the case of using a fluorine compound having a (meth) acrylonitrile group. It is slightly worse, but the wiping surface marks are easy to wipe. Furthermore, the smoothness is also good, and the surface of the cured product is not easily scratched. When a fluorine compound having a (meth) acrylonitrile group is used in the resin composition of the present invention, the oil repellency (the property against oil quality) is good when compared with the polyalkylene oxide having a (meth) acrylonitrile group.

In the ultraviolet curable hard coat resin composition of the present invention, the content of the component (C) is usually from 0.01 to 10% by mass, preferably from 0.05 to 5% by mass, based on 100% by mass of the total amount. It is more preferably 3 mass%.

The ultraviolet curable hard coat resin composition of the present invention may be an ultraviolet curable (meth) acrylate (D) having at least three (meth) acrylonitrile groups in a molecule other than the component (A). .

As the ultraviolet curable (meth) acrylate (D) having at least three (meth) acrylonitrile groups in the molecule, it is a polyfunctional group having 3 to 15 (meth) acryl fluorenyl groups in the molecule ( A methyl acrylate is preferred, for example, a polyfunctional amine ester (meth) acrylate or tris(meth) acrylate having a reaction of a polyfunctional (meth) acrylate compound having a hydroxyl group and a polyisocyanate compound. Trimethylolpropane ester, trimethylolpropane triethoxylate (meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tris(tetra)methacrylate Poly (meth) acrylates such as methylolpropane ester, dipentaerythritol hexa(meth)acrylate, and tricobalt octa(meth)acrylate, and cis (ethyl acrylate) isocyanate Wait.

Examples of the polyfunctional (meth) acrylate compound having a hydroxyl group include pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tetrakis(methyl). Pentaerythritol esters such as dipentaerythritol acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, and trimethylolpropane di(methyl) Epoxy (meth) acrylates such as hydroxymethyl esters such as acrylates and bisphenol A digoxy (meth) acrylates. Preferable examples thereof include neopentyl glycol tri(meth)acrylate and di neopentaerythritol penta(meth)acrylate. These polyfunctional (meth) acrylate compounds may be used singly or in combination of two or more.

The polyisocyanate may, for example, be a polyisocyanate having a basic structure of a chain saturated hydrocarbon, a cyclic saturated hydrocarbon or an aromatic hydrocarbon. Examples of such polyisocyanates include chain saturated saturated isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate. a cyclic saturated hydrocarbyl isocyanate such as dicyclohexylmethyl diisocyanate, methylene bis(4-cyclohexyl isocyanate), hydrogenated diphenylmethyl diisocyanate, hydrogenated xylene diisocyanate or hydrogenated toluene diisocyanate, 2, 4 -tolyl diisocyanate, 1,3-benzenedimethyl diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylene diisocyanate, 6-isopropyl An aromatic polyisocyanate such as 1,3-phenyl diisocyanate or 1,5-naphthalene diisocyanate. Preferable examples thereof include isophorone diisocyanate and hexamethylene diisocyanate. These polyisocyanates may be used singly or in combination of two or more.

The polyfunctional amine ester (meth) acrylate can be obtained by reacting the aforementioned polyfunctional (meth) acrylate having a hydroxyl group with the aforementioned polyisocyanate. The equivalent of the isocyanate group in the polyisocyanate is usually in the range of 0.1 to 50 equivalents, preferably in the range of 0.1 to 10 equivalents, per equivalent of the hydroxyl group in the ultraviolet curable polyfunctional (meth)acrylate having a hydroxyl group.

The reaction temperature is usually from 30 to 150 ° C, preferably from 50 to 100 ° C. The reaction end point is the reaction of the residual isocyanate with an excess of n-butylamine, and the unreacted n-butylamine is calculated by a reverse titration method using 1 N hydrochloric acid to determine the amount of residual isocyanate, and when the polyisocyanate compound is 0.5% by mass or less, the reaction is terminated. .

A catalyst may also be added for the purpose of shortening the reaction time. The catalyst may use either an alkaline catalyst or an acidic catalyst. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine, and phosphines such as ammonium, tributylphosphine and triphenylphosphine. Further, examples of the acidic catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, tetrabutoxytrititanium, tetrabutoxyzirconium, and the like. A Lewis compound such as a metal alkoxide or a Lewis acid such as aluminum chloride, 2-ethylhexyltin, octyltin trilaurate, dibutyltin dilaurate or octyltin diacetate. The amount of these catalysts added is usually 0.1% by mass or more and 1% by mass or less based on 100% by mass of the polyisocyanate.

Further, in the reaction, a polymerization inhibitor (for example, p-Methoxyphenol, hydroquinone, methyl hydroquinone, phenothiazine, etc.) for preventing polymerization in the reaction is used. In the reaction mixture, the polymerization inhibitor is used in an amount of 0.01% by mass or more and 1% by mass or less, preferably 0.05% by mass or more and 0.5% by mass or less.

In the ultraviolet curable hard coat resin composition of the present invention, when the component (D) is used, it may be used singly or in combination of two or more.

In the ultraviolet curable hard coat resin composition of the present invention, the content of the component (D) is usually from 0 to 80% by mass, and preferably from 10 to 60% by mass, based on 100% by mass of the total amount.

As the ultraviolet curable hard coat resin composition of the present invention, (meth) acrylate (E) having two (meth) acrylonitrile groups in the molecule can also be used. Among them, epoxy (meth) acrylate (E-1) and/or urethane (meth) acrylate (E-2) is preferably used.

Specific examples of the epoxy (meth) acrylate (E-1) include polyglycidyl compounds (bisphenol A type epoxy resin, bisphenol F type epoxy resin, and novolac novolac type ring). Epoxy resin (reactive resin, phenolic methyl epoxy resin, polyethylene glycol diglycidyl ether, glycerol polyether ether, trimethylolpropane polyglycidyl ether, etc.) and (meth)acrylic acid Methyl) acrylic. In particular, epoxy (meth) acrylate which is a reaction product of a bisphenol A type epoxy resin and acrylic acid is preferred. The repeating unit of bisphenol A is preferably an epoxy (meth) acrylate having more than one.

These polyglycidyl compounds have a large number of repeating units, and since they have two (meth) acrylonitrile groups, they are excellent in flexibility. Therefore, when the epoxy (meth) acrylate (E-1) is used as the component (E) of the ultraviolet curable hard coat resin composition of the present invention, the ultraviolet curable hard coat resin composition of the present invention can be imparted. Stretchability and softness.

The carboxylation reaction of the epoxy resin with (meth)acrylic acid can be obtained in the same manner as the epoxy (meth)acrylate (A).

Specific examples of the amine ester (meth) acrylate (E-2) include, for example, ethylene glycol, 1,4-butanediol, polytetramethylene glycol, neopentyl glycol, and polycaprolactone. Polyols such as alcohols, polyester polyols, and polycarbonate diols, and hexamethylene diisocyanate, alicyclic polyisocyanate, benzyl diisocyanate, benzodimethyl diisocyanate, 4,4'-di Organic polyisocyanates such as phenylmethyl diisocyanate, with 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate A reactant of a hydroxyl group-containing ethylenically unsaturated compound such as an ester, an ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate, or a neopentyl alcohol tri(meth) acrylate. The polyols, the organic polyisocyanates, and the ethylenically unsaturated compounds having a hydroxyl group may be used singly or in combination of plural kinds.

Preferred examples of such an amine ester (meth) acrylate (E-2) include polytetramethylene glycol, neopentyl glycol, isophorone diisocyanate, and 2-hydroxyethyl group. Acrylate reactants, etc. Such an amine ester has many bonds, and has two (meth)acryl fluorenyl groups, so it is rich in flexibility. Therefore, when the amine ester (meth) acrylate (E-2) is used as the component (E) of the ultraviolet curable hard coat resin composition of the present invention, the ultraviolet curable hard coat resin composition of the present invention can be imparted. Stretchability and softness.

The amine ester (meth) acrylate (E-2) is preferably reacted with from 1.1 to 2.0 equivalents of an organic polyisocyanate isocyanate group per 1 equivalent of the hydroxyl group of the polyol, preferably at 70 to 90 ° C, and then each A reaction product of 1 equivalent of a polyol and an organic polyisocyanate is obtained by reacting 1 to 1.5 equivalents of a hydroxyl group-containing ethylenically unsaturated compound.

In the ultraviolet curable hard coat resin composition of the present invention, when the component (E) is used, the component (E-1) and/or the component (E-2) may be used singly or in combination of two or more.

In the ultraviolet curable hard coat resin composition of the present invention, the content of the component (E) is usually from 0 to 60% by mass, and preferably from 5 to 40% by mass, based on 100% by mass of the total amount.

The ultraviolet curable hard coat resin composition of the present invention may also use a reactive diluent (F) having 1 to 2 (meth) acrylonitrile groups.

Examples of the reactive diluent include polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and ε-caprolactone adduct of hydroxytrimethylacetic acid neopentyl glycol. Di(meth)acrylate (for example, manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX-220, HX-620, etc.), bis(meth)acrylate of EO adduct of bisphenol A, and 1,4-butylene glycol methacrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclo(meth)acrylate癸alkyl ester, dicyclopentadienyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, isobutyl (meth)acrylate, adamantyl (meth)acrylate, etc. (meth)acrylates (meth)acrylates having an aromatic ring such as alicyclic (meth) acrylates, phenyl dehydroglyceryl (meth) acrylates, and benzyl (meth) acrylates Heterocyclic (meth) acrylates such as tetrahydrofuran ester and (meth)acrylic acid morpholine ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (methyl) a 4-hydroxybutyl acrylate or the like having a hydroxyl group (methyl) Acrylates, ethyl carbitol (meth)acrylate, and the like. These may be used alone or in combination of two or more.

In the ultraviolet curable hard coat resin composition of the present invention, the content of the component (F) is usually from 0 to 50% by mass, and preferably from 5 to 30% by mass, based on 100% by mass of the total amount.

A diluent (G) can also be used in the ultraviolet curable hard coat resin composition of the present invention. Examples of the diluent include γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptanolactone, α-ethinyl-γ-butyrolactone, and ε-caprolactone. Lactones; Alkane, 1,2-methoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether , ethers such as triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, and tetraethylene glycol diethyl ether; carbonates such as ethyl carbonate and propyl carbonate; butanone, methyl isobutyl ketone , ketones such as cyclohexanone and acetophenone; phenols such as phenol, cresol, and xylenol; ethyl acetate, butyl acetate, ethyl lactate, ethyl cellulose acetate, butyl cellulose acetate Esters such as esters, carbitol acetate, butyl ketone acetate, and propylene glycol monomethyl ethyl acetate; hydrocarbons such as toluene, xylene, diethylbenzene, and cyclohexane; trichloroethane; Organic solvents such as tetrachloroethane and halogenated hydrocarbons such as monochlorobenzene, petroleum ethers, petroleum solvents such as petroleum naphtha, and fluorine such as 2,2,3,3-tetrafluoropropanol Hydrofluoroethers such as alcohols, perfluorobutyl methyl ethers, and perfluorobutyl ethyl ether; alcohols such as methanol, ethanol, isopropanol, and n-propanol; both ketone and alcohol properties Diacetone alcohol (diacetone alcohol) and the like. These may be used alone or in combination of two or more.

In the ultraviolet curable hard coat resin composition of the present invention, the content of the component (G) is usually from 0 to 900% by mass, and preferably from 40 to 300% by mass, based on 100% by mass of the total amount.

In the ultraviolet curable hard coat resin composition of the present invention, colloidal ruthenium oxide (H) having an average particle diameter of 1 nm or more and 200 nm or less can be added for the purpose of improving hardness as necessary. The colloidal cerium oxide (H) can be used as a colloidal solution for dispersing colloidal cerium oxide in a solvent or as a fine powder cerium oxide containing no dispersing solvent.

As the dispersion medium of the colloidal cerium oxide (H), for example, alcohols such as methanol, ethanol, isopropanol, n-butanol, and diacetone alcohol, polyhydric alcohols such as ethylene glycol and derivatives thereof, butanone, and methyl can be used. Ketones such as isobutyl ketone, cyclohexanone, and dimethylacetamide; esters such as ethyl acetate and n-butyl acetate; non-polar solvents such as toluene and xylene; and acrylates such as 2-hydroxyethyl acrylate. Classes and general organic solvents. The amount of the dispersion medium is usually from 100 to 900% by mass based on 100% by mass of the colloidal cerium oxide.

These colloidal cerium oxide (H) can be produced by a conventional method or commercially available. For example, ORGA NOSILICASOL manufactured by Nissan Chemical Industries Co., Ltd.: GMEK-ST. The average particle diameter is preferably 1 nm or more and 200 nm or less, more preferably 5 nm or more and 100 nm or less, and still more preferably 10 nm or more and 50 nm or less. 5 nm or more and 100 nm or less can ensure transparency, and 10 nm or more and 50 nm or less of transparency and size can give good results.

Further, the average particle diameter means that the minimum particle diameter of the particles can be maintained when the aggregate is disintegrated, and the average particle diameter of the colloidal cerium oxide (H) can be measured by a BET method, a dynamic light scattering method, an electron microscope observation or the like. .

In the ultraviolet curable hard coat resin composition of the present invention, the content of the component (H) is usually from 0 to 100% by mass based on 100% by mass of the total amount.

Further, in the ultraviolet curable hard coat resin composition of the present invention, an ultraviolet absorber, a light stabilizer, an antioxidant, an antifoaming agent, and polymerization inhibition may be added to the ultraviolet curable hard coat resin composition as necessary. Agents, cross-linking agents, etc., can impart functionality for each purpose. Ultraviolet absorbers such as benzotriazole-based compounds, benzophenone-based compounds, and three a compound or the like, a photostabilizer such as a hindered amine compound or a benzoate compound, an antioxidant such as a phenol compound, and a polymerization inhibitor such as p-methoxyphenol, methyl hydroquinone or p-phenylene Examples of the phenol and the like include an antifoaming agent such as a polyoxonium compound, and a crosslinking agent such as the above polyisocyanate or a melamine compound.

Further, in the ultraviolet curable hard coat resin composition of the present invention, the dye or the pigment may be dispersed as necessary, and coloring may occur.

In the ultraviolet curable hard coat resin composition of the present invention, the component (A), the component (B), the component (C), the component (D), the component (E), and the component (F) may be used as necessary. (G) component and complex (H) component and other components are obtained by mixing in any order.

The ultraviolet curable hard coat resin composition of the present invention thus obtained has a stability over time.

The hard coat film of the present invention is obtained by providing a hardened layer of the ultraviolet curable hard coat resin composition of the present invention on a substrate film. Specifically, the hard coat film of the present invention can be applied to the substrate film by drying the ultraviolet curable hard coat resin composition of the present invention to a thickness of usually 0.1 μm or more and 50 μm or less, and 1 μm or more and 20 μm or less. Preferably, it is preferably 2 μm or more and 10 μm or less, and after drying, it is obtained by irradiating ultraviolet rays or electron beams to form a cured film.

The base film which can be used in the present invention may, for example, be polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, cellulose triacetate, polyether oxime or cycloolefin polymer. The film to be used may be a person who is provided as an easy-to-layer layer, a soft coater, a person who applies a pattern or a color, a person who imparts light resistance and antistatic property, a surface treatment such as a corona treatment, or a release type.

Examples of the coating method on the base film of the ultraviolet curable hard coat resin composition of the present invention include bar coating, wire bar coating, air knife coating, gravure coating, reverse gravure coating, and micro gravure coating. , micro-reverse gravure coating, die coating, slot die coating, vacuum die coating, dip coating, spin coating and spray coating.

In the curing of the ultraviolet curable hard coat resin composition of the present invention, ultraviolet rays, electron beams or the like can be used. When the ultraviolet curable hard coat resin composition of the present invention is cured by ultraviolet rays, an ultraviolet irradiation device such as a xenon lamp, a high pressure mercury lamp or a metal halide lamp can be used as a light source, and if necessary, it can be adjusted in accordance with the amount of light, the arrangement of the light source, and the like. When a high-pressure mercury lamp is used, it is preferred to harden at a moving speed of 5 to 60 m/min with respect to a lamp having an energy of 80 to 240 W/cm ² . On the other hand, when the ultraviolet curable hard coat resin composition of the present invention is cured by electron beam, it is preferred to use an electron beam acceleration device having an energy of 100 to 500 eV.

Further, the ultraviolet curable hard coat resin composition of the present invention is usually hardened in the air, and is preferably hardened by radiation irradiation in an environment substituted with an inert gas. When the inert gas is replaced, the oxygen concentration at the time of curing is 1% by volume or less, preferably 0.5% by volume or less. The inert gas is not particularly limited as long as it does not affect the hardening of the ultraviolet curable hard coat resin composition of the present invention, and among them, nitrogen gas is particularly preferable.

Further, the hard coat film of the present invention comprises a multilayer coating of the ultraviolet curable hard coat resin composition of the present invention which is coated with a plurality of layers on a substrate. The hard coat film of the present invention having a higher hardness can be obtained by multilayer coating.

The hard coat film of the present invention thus obtained has a stable change over time, and has good adhesion, transparency, and antifouling properties, and particularly has a good balance between hardness and elongation. Therefore, it is suitable as a material of the hard coat film used for insert molding of the film in the bending step, and is particularly suitable for the integrally formed hard coat film.

The molded article used in the hard coat molded article of the present invention can be produced by a conventional method. Specifically, for example, mold injection molding or the like can be mentioned. Specific examples of the material to be used include plastic materials such as polyethylene, polypropylene, polyester, polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS), and polymethacrylate (PMMA). . Other, a metal material can also be used for the molded article used in the hard coat molded article of the present invention.

The hard coat layer of the present invention can be obtained by integrally forming a hard coat film of the present invention together with a base film and the above-mentioned molded product, or by peeling off the base film of the hard coat film, and transferring the hard coat layer to the aforementioned forming. Obtained by the method of things.

In the hard-coated article of the present invention thus obtained, the hard coat layer such as the uneven portion or the curved portion of the molded article has no crack and has a glossy feeling and a transparent feeling. In addition, even if there are traces or fingerprints on the surface, it is easy to wipe, and it has antifouling properties such as oil repellency, and has a high surface hardness.

Further, the hard coat molded article of the present invention can directly apply the ultraviolet curable hard coat resin composition of the present invention to a molded article. The method of coating at this time may, for example, be dip coating, spin coating, spray coating or the like. At the time of hardening, the same method as the hardening of the ultraviolet curable hard coat resin composition of the present invention described above can be used.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. Further, in the examples, unless otherwise stated, the parts represent the mass%.

The softening point and the epoxy equivalent were measured under the following conditions.

1) Epoxy equivalent: Measured according to the method of JIS K 7236:2001.

2) Softening point: Measured according to the method of JIS K 7234:1986.

3) Acid value: Measured according to the method of JIS K 0070:1992.

4) The GPC measurement conditions are as follows.

Model: TOSOH HLC-8220GPC

Column: TSKGEL Super HZM-N

Dissolved solution: THF (tetrahydrofuran); 0.35 ml 1 minute, temperature 40 ° C

Detector: differential refractometer

Molecular weight standard: polystyrene

Example 1: Preparation of Epoxy (meth) acrylate (A)

The epoxy resin described in Table 1 as the epoxy resin (a) (all of which are made of Nippon Kayaku Co., Ltd., the epoxy equivalent, and the average values of R and n represented by the formula (1) are described in In Table 1), 72 g of acrylic acid (abbreviated as AA, Mw = 72) as (meth)acrylic acid (b) was added.

Next, 3 g of triphenylphosphine as a catalyst and monoacetic acid propylene glycol monomethyl ethyl ester as a solvent were added, and the solid content (calculated amount of the obtained epoxy acrylate (A)) was 70% by mass at 100 ° C. The reaction was carried out for 50 hours to obtain an epoxy acrylate (A) solution.

The end point of the reaction is determined by the solid acid value (AV), and when it is confirmed to be 3 mg KOH/g or less, the reaction is terminated. The acid value is determined by measuring the reaction solution and converting it to the acid value of the solid fraction.

The molecular weights shown in Table 1 are based on the value of the GPC polystyrene-converted mass average molecular weight.

Comparative Example 1: Preparation of a bisphenol type carboxylate compound

In the bisphenol type epoxy resin described in Table 1 as the epoxy resin (a) (epoxy equivalent is described in Table 1), acrylic acid as (meth)acrylic acid (b) (abbreviated as AA, Mw) = 72) 72g.

Then, 3 g of triphenylphosphine as a catalyst and monoacetic acid propylene glycol monomethyl ethyl ester as a solvent were added, and the solid content (calculated amount of the obtained bisphenol type carboxylate compound) was 70% by mass at 100 ° C. The reaction was carried out for 50 hours to obtain an epoxy acrylate solution.

The reaction end point is determined by the solid content acid value (AV), and it is confirmed that the reaction is completed when it reaches 2 mg KOH/g or less. The acid value was measured by the reaction solution and converted into the acid value of the solid component.

The molecular weights shown in Table 1 are based on the value of the mass average molecular weight of GPC in terms of polystyrene.

Abbreviation

EOCN-102S: Japanese chemical cresol novolac type epoxy resin

EOCN-103S: Japanese chemical cresol novolac type epoxy resin

EOCN-104S: Japanese chemical cresol novolac type epoxy resin

EPPN-201: Japanese chemical phenolic novolac type epoxy resin

EPPN-502: Japanese chemical phenolic methyl (TPM) epoxy resin

NER-1202: Polyfunctional bisphenol A (Bis-A) epoxy resin manufactured by Nippon Kayaku

Examples 2 to 8 and Comparative Examples 2 to 14

The materials shown in Tables 2, 3, and 4 were mixed, and the resin compositions of Examples 2 to 8 and Comparative Examples 2 to 14 were easily treated with a thickness of 100 μm. The PET film (manufactured by Toray Co., Ltd., Lumirror U46) The film was dried by solvent drying to a thickness of about 3 μm by a bar coater, dried at about 80 to 100 ° C, and then passed through a UV irradiator (JAPAN STORAGE BATTERY CO, LTD.: CS30L-1-1) high pressure mercury lamp: 120 W/ The resulting hard coat film was hardened under the conditions of cm, lamp height: 10 cm, relative speed: 10 m/min (energy: about 300 mW/cm ² , about 200 mJ/cm ² ). Further, the units in Tables 2, 3, and 4 indicate "parts by mass".

(Note)

※1:1-hydroxycyclohexyl phenyl ketone

*2: Made by Degussa, TEGO Rad 2250 (2-functional polyoxy acrylate)

*3: manufactured by Daikin Industries Co., Ltd., Optool DAC (acrylate modified perfluoropolyether, acrylate modified perfluoropolyether: 20% by mass)

*4: Reaction of pentaerythritol triacrylate with isophorone diisocyanate (6-functional amine ester acrylate)

*5: Bisphenol A epoxy acrylate (2-functional, theoretical molecular weight about 2,100)

*6: Reactant of polytetramethylene glycol with ethylene glycol and isophorone diisocyanate and hydroxyethyl acrylate (2-functional amine ester acrylate)

*7: Phenoxyethyl acrylate

※8: Butanone

*9: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate

*10: Reactant of dipentaerythritol pentaacrylate and hexamethylene diisocyanate

※11: 2-Methyl-1-(4-(methylthio)phenyl)-2-(4-morpholinyl)-1-propanone

*12: tetrahydrofurfuryl acrylate

※13: Propylene glycol monomethyl ether

*14: Gallium-doped zinc oxide manufactured by Hakusui tec Co., Ltd.; Pazet GK-40, gallium-doped zinc oxide: 30% by mass, PGM (propylene glycol monomethyl ether) dispersion

*15: Nissan Chemical Industry Co., Ltd. produces phosphorus-doped tin oxide; CELNAX CX-S200IP, phosphorus-doped tin oxide: 20% by mass, IPA (isopropanol) sol

The hard coat films obtained in Examples 2 to 8 and Comparative Examples 2 to 14 were evaluated by the following items, and the results are shown in Table 4.

(pencil hardness)

The pencil hardness of the hard coat film obtained in Examples 2 to 8 and Comparative Examples 2 to 14 was measured in accordance with JIS K 5600 using a pencil stroke tester. In detail, on the hard coat films obtained in Examples 2 to 8 and Comparative Examples 2 to 14, the pencil was cut at an angle of 45 degrees, and the weight of the load of 750 g was about 5 mm, and 4 out of 5 No scratches above the number indicates the hardness of the pencil.

(scratch resistance)

On the steel wood #0000, the hard coat film obtained in Examples 2 to 8 and Comparative Examples 2 to 14 was loaded with a weight of 250 g/cm ² 10 times to visually determine the scratch condition.

Evaluation level 5: no scratches

Level 4: 1 to 10 scratches

Level 3: produces 10 to 30 scratches

Level 2: Produce more than 30 scratches

Level 1: full scratching or spalling

(stretching rate)

The hard coat film obtained in Examples 2 to 8 and Comparative Examples 2 to 14 having a width of 10 mm × a length of 50 mm was pulled at a temperature of 10 mm per minute at a normal temperature by a tensile tester (RTM-250, manufactured by Orientec Co., Ltd.). Stretch, showing the stretch rate by visually showing the cracked point. For example, a tensile rate of 50% is recorded from 50 mm to 75 mm.

At the same time, this assessment is also used as an indicator of formability. The higher the elongation, the better the formability.

(adhesiveness)

According to JIS K5600, the surface of the hard coat film obtained in Examples 2 to 8 and Comparative Examples 2 to 14 was cut at a distance of 2 mm, and 25 squares were cut in the vertical and horizontal directions to make 25 checkers. It indicates the number of lattices that remain without peeling off after a breath is peeled off on the surface.

(marks wipe off)

The black/red trace ink was used to write the characters on the coated surfaces of the hard coat films obtained in Examples 2 to 8 and Comparative Examples 2 to 14, and wiped with a paper towel, and the wiping property was visually judged.

Evaluation A: You can wipe more than 10 times in the same place

B: You can wipe 5 to 10 times in the same place.

C: Can be wiped 1 to 4 times in the same place

(fingerprint wipeability)

The automatic contact angle meter was measured using the CA-V type manufactured by Concord Interface Science Co., Ltd. to measure the contact angle of hexadecane (HD). Using HD as an indicator of fingerprint wiping, the higher the contact angle, the better the fingerprint wiping. A contact angle of HD = 50 or more is preferred.

(full light penetration rate)

The haze meter was measured by TC-H3DPK, manufactured by Tokyo Denshoku Co., Ltd.

(haze value)

The haze meter was measured by TC-H3DPK, manufactured by Tokyo Denshoku Co., Ltd.

From the results of Examples 2 to 8 of Table 5, it is clear that the hard coat film of the present invention can obtain a very good balance between hardness and elongation, and antifouling property (mark wiping property and fingerprint wiping property). Also good. In Comparative Example 2 in which the component (A) was changed, although the hardness was good, there was almost no stretching, and in Comparative Example 3, the elongation was good, but the hardness was largely deteriorated. In Comparative Examples 4 to 5 in which the component (A) was not used, although the elongation was good, the hardness was largely lowered, and Comparative Examples 6 to 7 had a slight balance of hardness and elongation, but compared with the hard coat film of the present invention. The result is poor. Further, Comparative Example 8 in which the component (C) was not used was inferior in antifouling property.

The examples of Patent Document 4 and Patent Document 5 are referred to as Comparative Examples 9 to 14. In Comparative Examples 9 and 10 in which the resin components described in the examples of Patent Document 4 and Patent Document 5 were replaced with the components (A) of the invention, the hardness was equal to or higher than that of the present invention, but there was almost no stretching. In Comparative Examples 11 and 13 prepared in the examples of Patent Document 4 and Patent Document 5, there was almost no stretching, and the antifouling property was also insufficient. In addition, in Comparative Examples 12 and 14 in which the compounding resin component described in the examples of Patent Document 4 and Patent Document 5 was replaced with the component (A) of the present invention, the hardness and the antifouling property were insufficient.

(industrial availability)

The hard coat film of the present invention is inexpensive, and has good adhesion, transparency, and antifouling properties, and particularly has a good balance between hardness and stretchability. Therefore, the ultraviolet curable hard coat resin composition of the present invention is suitable as a material of a hard coat film used for insert molding of a film such as a bending step.

Claims (10)

An ultraviolet curable hard coat resin composition for forming a film comprising at least 3 molecules obtained by reacting an epoxy resin (a) represented by the general formula (1) and (meth)acrylic acid (b) More than one (meth) acrylonitrile-based epoxy (meth) acrylate (A) 10 to 99% by mass, a photoradical polymerization initiator (B), and an antifouling agent (C), (wherein R is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and n represents a positive number of the average of 1 to 20). The ultraviolet curable hard coat resin composition according to claim 1, wherein the antifouling agent (C) is a polyoxyalkylene having a (meth) acrylonitrile group. The ultraviolet curable hard coat resin composition according to claim 1, wherein the antifouling agent (C) is a fluorine compound having a (meth) acrylonitrile group. The ultraviolet curable hard coat resin composition according to any one of claims 1 to 3, wherein R in the epoxy resin (a) represented by the formula (1) is a methyl group. The ultraviolet curable hard coat resin composition according to any one of claims 1 to 3, which further comprises at least three or more (meth) acrylonitriles in a molecule other than the component (A). Base of ultraviolet hard Form (meth) acrylate (D). The ultraviolet curable hard coat resin composition according to claim 5, which further comprises an epoxy (meth) acrylate (E-1) having two (meth) acrylonitrile groups in the molecule and / or polyurethane (meth) acrylate (E-2). The ultraviolet curable hard coat resin composition according to claim 6, which further comprises a reactive diluent (F) having 1 to 2 (meth) acrylonitrile groups. The ultraviolet curable hard coat resin composition according to claim 7, which further comprises a diluent (G). A hard coat film is a hardened layer of the ultraviolet curable hard coat resin composition according to any one of claims 1 to 4 or 8. A hard-coated article, which is a hardened layer of the ultraviolet curable hard coat resin composition according to any one of claims 1 to 4 or 8.