JP5557274B2 - Ultraviolet curable hard coat resin composition, hard coat film and hard coat molded article using the same - Google Patents

Description

  The present invention relates to an ultraviolet curable hard coat resin composition, a hard coat film having the cured layer, and a hard coat molded product. More specifically, it is suitable for coating on the surface of a plastic film such as polyester, acrylic, polycarbonate, etc., and obtains a hard coat film capable of obtaining a molded product having excellent pencil hardness without generating cracks on the curved surface portion of the molded product surface portion. In particular, the ultraviolet curable hard coat resin composition is excellent in flexibility and moldability. Therefore, the ultraviolet curable hard coat resin composition suitable for the hard coat of a film used for film insert molding, and its cured layer The present invention relates to a hard coat film and a hard coat molded product.

  At present, plastics are used in large quantities in various industries including the automobile industry, the home appliance industry, and the electrical and electronic industry. The reason why such a large amount of plastic is used is that, in addition to its processability and transparency, it is lightweight, inexpensive and has excellent optical properties. However, it has disadvantages such as being softer than glass and being easily scratched on the surface. In order to improve these drawbacks, it is a common means to coat the surface with a hard coating agent. As the hard coat agent, thermosetting hard coat agents such as silicone paints, acrylic paints, and melamine paints are used. Of these, silicone hard coating agents are particularly frequently used because of their high hardness and excellent quality. However, it has a long curing time, is expensive, and cannot be said to be suitable for a hard coat layer provided on a continuously processed film.

  In recent years, photosensitive acrylic hard coating agents have been developed and used (see Patent Document 1). The photosensitive hard coating agent is cured immediately upon irradiation with radiation such as ultraviolet rays to form a hard film, so that the processing speed is fast, and the performance is excellent in hardness, scratch resistance, etc. Now it has become the mainstream in the hard coat field because it is cheaper. It is particularly suitable for continuous processing of films such as polyester. Examples of plastic films include polyester films, acrylic films, polycarbonate films, vinyl chloride films, triacetyl cellulose films, polyethersulfone films, and cycloolefin polymer films. Polyester films are the most widely used because of their excellent properties. It is used. This polyester film is a glass anti-scattering film, an automobile light-shielding film, a whiteboard surface film, a system kitchen surface antifouling film, and an electronic material such as a CRT flat TV, a liquid crystal display (LCD), a plasma display ( PDP), organic EL displays, functional films such as touch panels are widely used. All of these are coated with a hard coat so as not to scratch the surface.

  Furthermore, the use of films is increasing in the field of molding processing. For example, films have come to be used for molding processing of casings for mobile phones and personal computers, automobile interior materials such as meter covers, display panels and switch buttons for AV equipment and home appliances.

  Plastic products are molded by injection molding using a mold, but as a method of processing the surface of this product, a film is attached to the inner surface of the mold and attached to the surface of the molded product at the same time as molding. Methods have been proposed and are called film insert injection molding, in-mold molding, and the like. Furthermore, it has become possible to impart cosmetics and functionality such as decoration to the molded product and increased hardness by printing a pattern or a pattern on the film to be mounted or by performing a hard coat treatment.

  The hard coat film used for injection molding is coated with a hard coat on a base film and integrally formed with the hard coat film, and applied with a hard coat on a film having a release layer, and then released after molding. In some cases, the film is removed (Patent Document 2).

  Since the hard coat film used for injection molding is on the top surface of the plastic product, it contradicts not only the surface hardness but also the cosmetic properties such as gloss and transparency, and the hardness such as elongation and flexibility that can withstand the molding process. Performance is required. However, with conventional hard coats, increasing surface hardness decreases elongation and flexibility, and improving elongation and flexibility decreases hardness, which is not sufficient for the performance of hard coats used for molding. It was.

  For example, in the hard coat optimum resin composition proposed in the prior art documents 3 and 4, the hardness is sufficient, but the elongation is insufficient, and the required transparency cannot be obtained. From this, it can be seen that in a composition where flexibility is considered, sufficient hardness cannot be obtained due to the influence of inorganic substances, and the required transparency cannot be obtained. In the prior art document 5, transparency is obtained, but the relationship between hardness and elongation is the same as in the prior art document 3 and the prior art document 4. These are not hard coats suitable for molding.

  Prior art document 6 is a hard coat useful for film insert molding, but expensive colloidal silica is an essential component. In high elongation products, the content of colloidal silica is increased in order to maintain hardness. There is a disadvantage of being expensive.

Japanese Patent Laid-Open No. 9-48934 Japanese Patent No. 3007326 JP 2008-81696 A JP 2009-1598 A JP 2008-94929 A JP 2009-24168 A

  The present invention is easily cured by ultraviolet rays, has high hardness, adhesion, transparency, antifouling property and stretchability, and is suitable for a hard coat film material used in film insert molding having a folding process. It is an object of the present invention to provide an ultraviolet curable hard coat resin composition, a hard coat film having a cured layer, and a hard coat molded product.

  As a result of intensive studies to solve the above problems, the present inventors have found that an ultraviolet curable hard coat resin composition containing a specific compound can solve the above problems, and have reached the present invention.

That is, the present invention
(1) Epoxy (meth) having at least three (meth) acryloyl groups in a molecule obtained by reacting the epoxy resin (a) represented by the general formula (1) and (meth) acrylic acid (b) UV curable hard coat resin composition for molded film used in film insert molding containing acrylate (A), photo radical polymerization initiator (B), and antifouling agent (C),

(In the formula, 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 on average.)
(2) The ultraviolet curable hard coat resin composition according to (1), wherein the antifouling agent (C) is a polysiloxane having a (meth) acryloyl group,
(3) The antifouling agent (C) is a fluorine compound having a (meth) acryloyl group, the ultraviolet curable hard coat resin composition according to (1),
(4) The ultraviolet curable hard coat resin according to any one of (1) to (3), wherein R of the epoxy resin (a) represented by the general formula (1) is a methyl group Composition,
(5) The composition further comprises an ultraviolet curable (meth) acrylate (D) having at least three (meth) acryloyl groups in the molecule other than the component (A). ) To (4), the ultraviolet curable hard coat resin composition according to any one of
(6) Furthermore, it contains epoxy (meth) acrylate (E-1) and / or urethane (meth) acrylate (E-2) having two (meth) acryloyl groups in the molecule ( The ultraviolet curable hard coat resin composition according to any one of 1) to (5).
(7) The ultraviolet curable type according to any one of (1) to (6), further comprising a reactive diluent (F) having 1 to 2 (meth) acryloyl groups. Hard coat resin composition,
(8) The ultraviolet curable hard coat resin composition according to any one of (1) to (7), further comprising a diluent (G),
(9) A hard coat film having a cured layer of the ultraviolet curable hard coat resin composition according to any one of (1) to (8),
(10) A hard coat molded article having a cured layer of the ultraviolet curable hard coat resin composition according to any one of (1) to (8),
About.

  According to the present invention, it is possible to provide an ultraviolet curable hard coat resin composition having excellent hardness, transparency, antifouling property, elongation and flexibility, and further a hard coat film and a hard coat molded article having the cured layer. it can.

  Hereinafter, the present invention will be described in detail.

  The ultraviolet curable hard coat resin composition of the present invention has at least 3 or more molecules in a molecule obtained by reacting the epoxy resin (a) represented by the general formula (1) and (meth) acrylic acid (b). An epoxy (meth) acrylate (A) having a (meth) acryloyl group is used.

(In the formula, 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 on average.)

  In General formula (1), a C1-C4 hydrocarbon group is a C1-C4 saturated hydrocarbon group or a C2-C4 unsaturated hydrocarbon group, a linear or branched chain , Regardless of the ring. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, vinyl group, An allyl group, an isopropenyl group, etc. are mentioned.

  Of the epoxy resins (a) represented by the general formula (1), those in which R is all a hydrogen atom or those having a methyl group are preferred because they are available at low cost. In general, those in which R is all hydrogen atoms are available from Nippon Kayaku as the EPPN-200 series, and those in which R is all methyl groups are also available from Nippon Kayaku at a low price as the EOCN series. Is possible.

  In the present invention, it is more preferable that all Rs of the epoxy resin (a) represented by the general formula (1) are methyl groups. Compared with the case where R is all hydrogen atoms, it is possible to increase the hardness while maintaining high elongation.

  N of the epoxy resin (a) represented by the general formula (1) is 1 to 20 on average. In this invention, it is preferable that n is 1-15, More preferably, it is 5-12.

  In the case of producing an epoxy (meth) acrylate (A) having at least three (meth) acryloyl groups in the molecule, the carboxylation reaction is carried out by adding the total of the (meth) acrylic acid (b) to the epoxy It is preferable that it is 90-120 equivalent% with respect to 1 equivalent of epoxy groups of resin (a). Within this range, it is possible to manufacture under relatively stable conditions. When the amount of (meth) acrylic acid (b) is larger than this, excess (meth) acrylic acid (b) remains, which is not preferable.

  This carboxylation reaction can be carried out without a solvent or diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the carboxylation reaction. The preferred amount of solvent used should be adjusted as appropriate depending on the viscosity and intended use of the resin obtained, but preferably 30 to 90% by mass, more preferably 50 to 80% by mass as the solid content. Use.

  Specific examples of those that can be used as the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane, and decane, and Examples thereof include petroleum ether, white gasoline, and solvent naphtha.

  Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, (Mono or poly) alkylene glycol monoalkyl ether monoacetates such as triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, butylene glycol monomethyl ether monoacetate, dialkyl glutarate, succinic acid Polyalkylates such as dialkyl and dialkyl adipates Ester, and the like can be mentioned.

  Examples of ether solvents 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, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. Glycol ethers, and cyclic ethers such as tetrahydrofuran.

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

  During the reaction, it is preferable to use a catalyst to accelerate the reaction, and the amount of the catalyst used is the amount of the reaction product, that is, the epoxy resin (a), the (meth) acrylic acid (b), and optionally a solvent or the like. It is 0.1-10 mass% with respect to the total amount of the reaction material which added. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, Examples include known general basic catalysts such as zirconium octoate.

  Moreover, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4hydroxytoluene and the like as a thermal polymerization inhibitor.

  The end point of this reaction is the time when the acid value of the sample is 5 mgKOH / g or less, preferably 2 mgKOH / g or less, while sampling appropriately.

  As a preferable molecular weight range of the epoxy (meth) acrylate (A) having at least three (meth) acryloyl groups in the molecule thus obtained, a polystyrene-reduced mass average molecular weight in GPC is 1,000 to 30,000. It is a range, More preferably, it is 5,000-15,000. These may be used alone or in combination.

  In the ultraviolet curable hard coat resin composition of the present invention, the content of the component (A) is the total amount of the components (A), (B), (C), (D), (E) and (F) ( Hereinafter, it is generally 5-99.9% by mass, preferably 10-99% by mass, in 100% by mass). When component (D) and / or (E) and / or (F) and / or (G) are not used, it is usually 80 to 99.9% by mass, preferably 90 to 90% by mass. 99% by mass. When using a postscript component (D) and / or (E) component, and / or (F) component, and / or (G) component, it is 5-95 mass% normally, Preferably it is 10-90 mass. %.

  The ultraviolet curable hard coat resin composition of the present invention uses a radical photopolymerization initiator (B). Examples of the photo radical polymerization initiator (B) include benzoins such as 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 phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- ( Acetophenones such as 4-morpholinyl) -1-propanone; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethyl Thioxanthones such as oxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone And phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Further, from the market, Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) and Irgacure 907 (2-methyl-1- (4- (methylthio) phenyl) -2- (4- Morpholinyl) -1-propanone), lucillin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) manufactured by BASF, etc. can be easily obtained. Moreover, these may be used independently or may be used in mixture of 2 or more types.

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

  A sensitizer can be used in combination with the ultraviolet curable hard coat resin composition of the present invention as necessary. Sensitizers that can be used are anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 2-ethyl-9,10-di (methoxyethoxy) anthracene, fluorene, pyrene, stilbene, 4'-nitrobenzyl-9,10-dimethoxy Anthracene-2-sulfonate, 4′-nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, 4′-nitrobenzyl-9,10-dipropoxyanthracene-2-sulfonate, etc. Compatibility with UV curable hard coat resin composition In particular 2-ethyl-9,10-di (methoxyethoxy) anthracene are preferable.

  When using these sensitizers, the usage-amount is 1-200 mass% with respect to 100 mass% of this radical photopolymerization initiator (B), Preferably it is 5-150 mass%.

  An antifouling agent (C) is used in the ultraviolet curable hard coat resin composition of the present invention. Examples of the antifouling agent (C) include silicone compounds, fluorine compounds, acrylic compounds, and the like. The antifouling function of the antifouling agent (C) imparts water repellency and oil repellency and improves magic wiping property and fingerprint wiping property. In addition to the antifouling function, leveling, slipperiness, and scratch resistance for improving processability, and acrylic compounds are further imparted with repaintability.

  As the silicone compound of the antifouling agent (C), it is more preferable to use polysiloxane having a (meth) acryloyl group. The polysiloxane having a (meth) acryloyl group may be referred to as silicone acrylate, organic modified silicone, organic modified polysiloxane, reaction-bonded organic modified silicone acrylate, or the like. Examples of the polysiloxane having a (meth) acryloyl group include those in which a part of a linear dimethylsiloxane is organically modified with an alkyl or polyether, and an acrylate group is added to the modified terminal. By increasing the length of siloxane, it is possible to impart surface slipperiness, mold release properties, blocking resistance, magic wiping properties, fingerprint wiping properties, and the like. Moreover, compatibility, repaintability (recoatability), and printability can be improved by increasing the organic modification rate. Further, by introducing an acryloyl group, reactive bonding can be achieved, and migration to the interface can be reduced. By reacting with the base resin, long-term performance stability is also improved. Furthermore, chemical resistance (alkaline solution, organic solvent, etc.) can be improved. Commercially available products may be used as these polysiloxanes having a (meth) acryloyl group. For example, BYK-UV3500, BYK-UV3570 (both manufactured by BYK Chemie), TEGO Rad2100, 2200N, 2250, 2500, 2600, 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, X-22-164C (all manufactured by Shin-Etsu Chemical Co., Ltd.) Door can be. These may be used alone or in combination of two or more.

  The molecular weight of these polysiloxanes having (meth) acryloyl groups and the number of (meth) acryloyl groups are not particularly defined, but the number of (meth) acryloyl groups is preferably 1 to 6 in one molecule, more preferably 1 to 3 It is.

  As the fluorine compound of the antifouling agent (C), it is more preferable to use a fluorine compound having a (meth) acryloyl group. As a fluorine compound which has a (meth) acryloyl group, what gave the (meth) acryloyl group to the terminal of modified | denatured perfluoropolyether is mentioned, for example. By increasing the length of the fluorocarbon and increasing the fluorine content, surface slipperiness, mold release, blocking resistance, fingerprint resistance, magic wiping properties, fingerprint wiping properties, etc. can be imparted. . Moreover, compatibility, repaintability (recoatability), and printability can be improved by increasing the organic modification rate. In addition, by introducing a (meth) acryloyl group, it is possible to form a reactive bond, to reduce the migration to the interface, and to improve long-term performance stability by reacting with the base resin. Furthermore, chemical resistance (alkaline solution, organic solvent, etc.) can be improved. Examples of commercially available fluorine compounds having a (meth) acryloyl group include, for example, OPTOOL DAC, OPTOOL DAC-HP, R-1110, R-1210, R-1420, R-1620, manufactured by Daikin Industries, Ltd. R-1820, R-2020, R-5210, R-5410, R-5610, R-5810, R-7210, R-7310, etc. can be mentioned. These may be used alone or in combination of two or more.

  The molecular weight of the fluorine compound having the (meth) acryloyl group and the number of (meth) acryloyl groups are not particularly defined, but the number of (meth) acryloyl groups is preferably 1 to 2 in one molecule.

  The polysiloxane having a (meth) acryloyl group has an equivalent magic wiping property compared to a fluorine compound having a (meth) acryloyl group, but has an equivalent magic wiping property, and more slippery. Excellent and scratch resistance is further improved. In addition, a fluorine compound having a (meth) acryloyl group is inferior in scratch resistance compared to a polysiloxane having a (meth) acryloyl group, but has an equivalent magic wiping property, more oil repellency, and fingerprints. The wiping property is further improved.

  In the ultraviolet curable hard coat resin composition of the present invention, the content of the component (C) is usually 0.01 to 10% by mass, preferably 0.05 to 5% by mass in the total amount of 100% by mass. More preferably, it is 0.1-3 mass%.

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

  As the ultraviolet curable (meth) acrylate (D) having at least 3 or more (meth) acryloyl groups in the molecule, a polyfunctional (meth) acrylate having 3 to 15 (meth) acryloyl groups in the molecule may be used. Preferably, for example, polyfunctional urethane (meth) acrylates, which are a reaction product of a polyfunctional (meth) acrylate compound having a hydroxyl group and a polyisocyanate compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) Polyester (meth) acrylates such as acrylates, the use of tris (acryloyloxyethyl) isocyanurate are also possible.

  Examples of the polyfunctional (meth) acrylate compound having a hydroxyl group include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, Mention may be made of pentaerythritol esters such as dipentaerythritol di (meth) acrylate, methylol esters such as trimethylolpropane di (meth) acrylate, and epoxy (meth) acrylates such as bisphenol A diepoxy (meth) acrylate. Preferable examples include pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate. These polyfunctional (meth) acrylate compounds may be used alone or in combination of two or more.

  Examples of the polyisocyanate include polyisocyanates mainly composed of chain saturated hydrocarbons, cyclic saturated hydrocarbons, and aromatic hydrocarbons. Examples of such polyisocyanates include chain saturated hydrocarbon isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and methylenebis (4-cyclohexylisocyanate). Cyclic saturated hydrocarbon isocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl -4,4'-diphenylene diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate, 1,5 And aromatic polyisocyanates such as naphthalene diisocyanate. Preferable examples include isophorone diisocyanate and hexamethylene diisocyanate. These polyisocyanates may be used alone or in combination of two or more.

  The polyfunctional urethane (meth) acrylate is obtained by reacting the polyfunctional (meth) acrylate having a hydroxyl group with the polyisocyanate. The polyisocyanate is usually in the range of 0.1 to 50 equivalents as the isocyanate group equivalent, preferably 0.1 to 10 equivalents of the hydroxyl group in the ultraviolet curable polyfunctional (meth) acrylate having a hydroxyl group. Use within a range.

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

  A catalyst may be added for the purpose of shortening the reaction time. As the catalyst, either a basic catalyst or an acidic catalyst is used. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine, and phosphine such as ammonia, tributylphosphine and triphenylphosphine. Examples of the acidic catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, metal alkoxides such as tributoxyaluminum, trititanium tetrabutoxide, and zirconium tetrabutoxide, Lewis acids such as aluminum chloride, and 2-ethylhexane. Tin compounds such as tin, octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate can be exemplified. The addition amount of these catalysts is usually 0.1% by mass or more and 1% by mass or less with respect to 100% by mass of the polyisocyanate.

  Further, in the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, phenothiazine, etc.) in order to prevent polymerization during the reaction, and the amount of the polymerization inhibitor used is based on the reaction mixture. It is 0.01 mass% or more and 1 mass% or less, Preferably it is 0.05 mass% or more and 0.5 mass% or less.

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

  The ultraviolet curable hard coat resin composition of the present invention may use (meth) acrylate (E) having two (meth) acryloyl groups in the molecule. Among these, it is preferable to use epoxy (meth) acrylate (E-1) and / or urethane (meth) acrylate (E-2).

  Specific examples of the epoxy (meth) acrylate (E-1) include, for example, a polyglycidyl compound (bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, trisphenol methane type epoxy resin, polyethylene glycol). (Diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, etc.) and epoxy (meth) acrylates which are a reaction product of (meth) acrylic acid. In particular, epoxy (meth) acrylate which is a reaction product of bisphenol A type epoxy resin and acrylic acid is preferable. Epoxy (meth) acrylates having bisphenol A repeating units greater than 1 are more preferred.

  Since these have many repeating units of a polyglycidyl compound and two (meth) acryloyl groups, they are rich in flexibility. Therefore, when the ultraviolet curable hard coat resin composition using the epoxy (meth) acrylate (E-1) as the component (E) is used for injection molding or the like, it is stretched and given flexibility.

  The carboxylation reaction between the epoxy resins and (meth) acrylic acid can be obtained by the same production method as that for the epoxy (meth) acrylate (A).

  Specific examples of the urethane (meth) acrylate (E-2) include, for example, ethylene glycol, 1,4-butanediol, polytetramethylene glycol, neopentyl glycol, polycaprolactone polyol, polyester polyol, polycarbonate diol, polytetra Polyols such as methylene glycol, organic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2-hydroxyethyl (meth) acrylate, Ε-caprola of 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate Ton adducts, can be mentioned a reaction product of pentaerythritol tri (meth) hydroxyl group-containing ethylenically unsaturated compounds such as acrylates. Polyols, organic polyisocyanates, and hydroxyl group-containing ethylenically unsaturated compounds may be used alone or in combination.

  Preferable examples of such urethane (meth) acrylate (E-2) include polytetramethylene glycol, neopentyl glycol, isophorone diisocyanate, and a reaction product of 2-hydroxyethyl acrylate. Since these have many urethane bonds and two (meth) acryloyl groups, they are rich in flexibility. Accordingly, when the ultraviolet curable hard coat resin composition using urethane (meth) acrylate (E-2) as the component (E) is used for injection molding or the like, it is stretched and given flexibility.

  The urethane (meth) acrylate (E-2) is preferably obtained by reacting an isocyanate group of an organic polyisocyanate at 1.1 to 2.0 equivalents, preferably 70 to 90 ° C., with respect to one equivalent of a hydroxyl group of a polyol, and then polyol. It can be obtained by reacting 1 to 1.5 equivalents of a hydroxyl group-containing ethylenically unsaturated compound per equivalent of the reaction product of the organic polyisocyanate and the organic polyisocyanate.

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

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

  In the ultraviolet curable hard coat resin composition of the present invention, a reactive diluent (F) having 1 to 2 (meth) acryloyl groups may be used.

  Examples of the reactive diluent (F) include polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and di (meth) acrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate (for example, Manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX-220, HX-620, etc.), bisphenol A EO adduct di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentadieneoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobonyl (meth) Acrylate, Adamant Alicyclic (meth) acrylates such as tan (meth) acrylate, (meth) acrylates having an aromatic ring such as phenylglycidyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholine Heterocyclic (meth) acrylates such as (meth) acrylate, (meth) acrylates having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate And ethyl carbitol (meth) acrylate. These may be used alone or in admixture of two or more.

  In the ultraviolet curable hard coat resin composition of the present invention, the content of the component (F) is usually 0 to 50% by mass in the total amount of 100% by mass, or 5 to 30% by mass when used. preferable.

  Diluent (G) may be used in the ultraviolet curable hard coat resin composition of the present invention. Examples of the diluent (G) include lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, and ε-caprolactone; -Ethers such as dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether Carbonates such as ethylene carbonate and propylene carbonate; methyl ethyl ketone Ketones such as methyl isobutyl ketone, cyclohexanone, acetophenone; phenols such as phenol, cresol, xylenol; ethyl acetate, butyl acetate, ethyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl Esters such as ether acetate; hydrocarbons such as toluene, xylene, diethylbenzene, cyclohexane; halogenated hydrocarbons such as trichloroethane, tetrachloroethane, and monochlorobenzene; and organic solvents such as petroleum solvents such as petroleum ether and petroleum naphtha , Fluorinated alcohols such as 2,2,3,3-tetrafluoropropanol, perfluorobutyl methyl ether, perfluorobutyl ethyl Hydrofluoroethers such as ether; methyl alcohol, ethyl alcohol, isopropyl alcohol, and n- propyl alcohol; and diacetone alcohol combines ketone and both alcohol performance thereof. These may be used alone or in admixture of two or more.

  In the ultraviolet curable hard coat resin composition of the present invention, the content of the component (G) is usually 0 to 900% by mass with respect to the total amount of 100% by mass, and when used, 40 to 300% by mass. Is preferred.

  To the ultraviolet curable hard coat resin composition of the present invention, colloidal silica (H) having an average particle diameter of 1 nm or more and 200 nm or less can be added for the purpose of improving the hardness, if necessary. The colloidal silica (H) can be used as a colloidal solution in which colloidal silica is dispersed in a solvent or as finely divided silica containing no dispersion solvent.

  Examples of the colloidal silica (H) dispersion medium include water, methanol, ethanol, isopropanol, n-butanol, diacetone alcohol and other polyhydric alcohols such as ethylene glycol and derivatives thereof, methyl ethyl ketone, and methyl isobutyl ketone. , Ketones such as cyclohexanone and dimethylacetamide, esters such as ethyl acetate and n-butyl acetate, nonpolar solvents such as toluene and xylene, acrylates such as 2-hydroxyethyl acrylate, and general organic solvents can be used. The amount of the dispersion medium is usually 100 to 900% by mass with respect to 100% by mass of colloidal silica.

  As these colloidal silica (H), those produced by a known method and commercially available can be used. For example, an organosilica sol: MEK-ST manufactured by Nissan Chemical Industries, Ltd. may be mentioned. It is necessary to use an average particle diameter of 1 nm to 200 nm, preferably 5 nm to 100 nm, more preferably 10 nm to 50 nm. When the thickness is 5 nm or more and 100 nm or less, transparency can be secured, and when the thickness is 10 nm or more and 50 nm or less, sufficiently good results are obtained in both transparency and haze.

  The average particle diameter means the smallest particle diameter of the particles when the aggregation is broken. The average particle diameter of colloidal silica (H) is measured by BET method, dynamic light scattering method, electron microscope observation, or the like. Can be measured.

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

  Furthermore, the ultraviolet curable hard coat resin composition of the present invention may contain an ultraviolet absorber, a light stabilizer, an antioxidant, an antifoaming agent, a polymerization inhibitor, a crosslinking agent and the like, if necessary. It can also be added to the coating resin composition to impart desired functionality. As UV absorbers, benzotriazole compounds, benzophenone compounds, triazine compounds, etc., as light stabilizers, hindered amine compounds, benzoate compounds, etc., as antioxidants, phenol compounds, etc., as polymerization inhibitors , Methoquinone, methylhydroquinone, hydroquinone, etc., examples of antifoaming agents include silicone compounds, and examples of crosslinking agents include the polyisocyanates and melamine compounds.

  Furthermore, the ultraviolet curable hard coat resin composition of the present invention can be colored by dispersing a dye or pigment as necessary.

  The ultraviolet curable hard coat resin composition of the present invention comprises the component (A), component (B), component (C), and component (D), component (E), component (F), It can be obtained by mixing the component G) and, if necessary, the component (H) and other components in any order.

  The ultraviolet curable hard coat resin composition of the present invention thus obtained is stable over time.

  The hard coat film of the present invention can be obtained by providing a cured layer of the ultraviolet curable hard coat resin composition on a base film (base film). The ultraviolet curable hard coat resin composition is applied onto a base film so that the film thickness after drying is usually 0.1 μm to 50 μm, preferably 1 μm to 20 μm, more preferably 2 μm to 10 μm, and drying. It can be obtained by irradiating a post-ultraviolet ray to form a cured film.

  Examples of the base film include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetyl cellulose, polyether sulfone, and cycloolefin polymer. Films used are those with an easy adhesion layer, those with a soft coat layer, those with pattern printing or coloring, those with light resistance and antistatic properties, and those with surface treatment such as corona treatment Alternatively, a release treatment may be performed.

  Examples of the method for applying the ultraviolet curable hard coat resin composition of the present invention include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, and micro reverse gravure. Examples include coater coating, die coater coating, slot die coater coating, vacuum die coater coating, dip coating, spin coating coating, and spray coating.

Although ultraviolet rays are irradiated for curing, an electron beam or the like can also be used. In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp or the like is used as a light source, and the light amount, the arrangement of the light source, etc. are adjusted as necessary. When using a high-pressure mercury lamp, it is preferable to cure at a conveying speed of 5 to 60 m / min for one lamp having an energy of 80 to 240 W / cm ² . On the other hand, when curing with an electron beam, it is preferable to use an electron beam accelerator having an energy of 100 to 500 eV.

  Moreover, it is more preferable to cure by irradiation with radiation in an environment substituted with an inert gas, and the oxygen concentration at the time of curing is preferably 1% by volume or less, and more preferably 0.5% by volume or less. Nitrogen gas is preferably used as the inert gas.

  Furthermore, the hard coat film of the present invention can be multilayer coated on the substrate with the ultraviolet curable hard coat resin composition. Higher hardness can be obtained by applying a multilayer coating.

  The hard coat film thus obtained is stable over time, has good adhesion, transparency and antifouling properties, and particularly has a good balance between hardness and elongation. Therefore, it is suitable as a material for a hard coat film used in film insert molding having a folding process, and particularly suitable for hard coat film integral molding.

  The molded product used for the hard coat molded product of the present invention is produced by a known method. Specific examples include mold injection molding. Specific examples of the material used include plastic materials such as polyethylene, polypropylene, polyester, polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS), and polymethyl methacrylate (PMMA).

  The hard coat molded product of the present invention is a system in which the hard coat film is integrally molded with the molded product together with the base film, or the hard coat film is peeled off and the hard coat layer is formed into the molded product. It can be obtained by a transfer method.

  The hard coat molded product thus obtained has no cracks in the hard coat layer on the uneven portions and curved portions of the molded product, has a glossy feeling and transparency, has antifouling properties, and high surface hardness.

  In addition, the hard coat molded product of the present invention can be directly coated on the molded product with the ultraviolet curable hard coat resin composition. Examples of the application method at that time include dip coating, spin coating, and spray coating. Curing at that time can be performed by the same method as the curing of the ultraviolet curable hard coat resin composition of the present invention described above.

  Moreover, the hard coat molded product of the present invention is not limited to a molded product using the plastic material, and can be used for various molded products such as metals.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by these Examples. Moreover, unless otherwise indicated in an Example, a part shows the mass%.

The softening point and epoxy equivalent were measured under the following conditions.
1) Epoxy equivalent: Measured by a method according to JIS K 7236: 2001.
2) Softening point: measured by a method according to JIS K 7234: 1986
3) Acid value: measured by a method according to JIS K 0070: 1992 4) GPC measurement conditions are as follows.
Model: TOSOH HLC-8220GPC
Column: TSKGEL Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml per minute, temperature 40 ° C
Detector: Differential refractometer Molecular weight standard: Polystyrene

Example 1: Preparation of epoxy (meth) acrylate (A) As epoxy resin (a), an epoxy resin described in Table 1 (all manufactured by Nippon Kayaku Co., Ltd.), an epoxy equivalent, and R represented by the general formula (1), And n have average values described in Table 1, and 72 g of acrylic acid (abbreviation AA, Mw = 72) was added as (meth) acrylic acid (b).
3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so as to have a solid content of 70% by mass and reacted at 100 ° C. for 50 hours to obtain an epoxy acrylate (A) solution.
The reaction end point was determined by the solid content acid value (AV), and after confirming that it was 3 mgKOH / g or less, the reaction was terminated. The acid value was measured with a reaction solution and converted to an acid value as a solid content.
The molecular weights listed in Table 1 were based on polystyrene-reduced mass average molecular weight values by GPC.

Comparative Example 1: Preparation of bisphenol-type carboxylate compound The bisphenol-type epoxy resin described in Table 1 as the epoxy resin (a), the epoxy equivalent is described in Table 1, and acrylic acid (abbreviated as AA, as (meth) acrylic acid (b)) 72 g of Mw = 72) was added.
3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added to a solid content of 70% by mass and reacted at 100 ° C. for 50 hours to obtain an epoxy acrylate solution.
The reaction end point was determined by the solid content acid value (AV), and the reaction was terminated after confirming that it was 2 mgKOH / g or less. The acid value was measured with a reaction solution and converted to an acid value as a solid content.
The molecular weights listed in Table 1 were based on polystyrene-reduced mass average molecular weight values by GPC.

Table 1
Example (a) RnWPE (g / eq.) Wt (g) Mw
Example 1-1 EOCN-102S Methyl group 4 210 210 3500
Example 1-2 EOCN-103S methyl group 6 215 215 6000
Example 1-3 EOCN-104S Methyl group 8 220 220 9000
Example 1-4 EPPN-201 Hydrogen atom 5 190 190 6800
Comparative Example 1-1 EPPN-502 − − 175 175 3500
Comparative Example 1-2 NER-1202 − − 280 280 6000

Abbreviations in Table: EOCN-102S: Nippon Kayaku cresol novolak type epoxy resin EOCN-103S: Nippon Kayaku cresol novolak type epoxy resin EOCN-104S: Nippon Kayaku cresol novolak type epoxy resin EPPN-201: Nippon Kayaku Phenol novolac type epoxy resin EPPN-502: Nippon Kayaku trisphenol methane (TPM) type epoxy resin NER-1220: Nippon Kayaku polyfunctional bisphenol A (Bis-A) type epoxy resin

Examples 2-8 and Comparative Examples 2-14
The resin composition containing the materials shown in Table 2, Table 3, and Table 4 is about 3 μm after solvent drying on a 100 μm-thick PET film (Toray Industries, Inc .; Lumirror U46). After coating with a bar coater and drying at about 80-100 ° C., a high-pressure mercury lamp: 120 W / cm; lamp height: 10 cm using an ultraviolet irradiator (JAPAN STORAGE BATTERY CO, LTD .: CS30L-1-1); A hard coat film was obtained by curing under conditions of conveyor speed: 10 m / min (energy: about 300 mW / cm ² , about 200 mJ / cm ² ). In Table 2, Table 3, and Table 4, the unit represents “part by mass”.

(note)
* 1: 1-hydroxycyclohexyl phenyl ketone * 2: TEGO Rad 2250 (bifunctional silicone acrylate) manufactured by Degussa
* 3: OPTOOL DAC (acrylate modified perfluoropolyether, solid content 20% by mass) manufactured by Daikin Industries, Ltd.
* 4: Reaction product of pentaerythritol triacrylate and isophorone diisocyanate (hexafunctional urethane acrylate)
* 5: Bisphenol A epoxy acrylate (bifunctional, theoretical molecular weight of about 2,100)
* 6: Reaction product of polytetramethylene glycol and ethylene glycol, isophorone diisocyanate and hydroxyethyl acrylate (bifunctional urethane acrylate)
* 7: Phenoxyethyl acrylate * 8: Methyl ethyl ketone * 9: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate * 10: Reaction product 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 Hux Itec Co., Ltd. GK-40, solid content 30%, PGM (propylene glycol monomethyl ether) dispersion * 15: Phosphorus-doped tin oxide manufactured by Nissan Chemical Industries, Ltd. Product name: Celnax CX-S200IP, solid Concentration 20%, IPA (isopropyl alcohol) sol

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

(Pencil hardness)
According to JIS K 5600, the pencil hardness of the coated film was measured using a pencil scratch tester. Specifically, on a film having a cured film to be measured, a pencil is applied at a 45 degree angle, and a load of 750 g is applied from the top to scratch about 5 mm. did.

(Abrasion resistance)
A load of 250 g / cm ² was applied to Steel Wool # 0000 for 10 reciprocations, and the condition of the scratch was judged visually.
Evaluation Grade 5: No scratch Grade 4: Generation of 10 to 10 scratches Grade 3: Generation of 10 to 30 scratches Grade 2: Generation of 30 or more scratches Grade 1: Scratches or peeling occurred on the entire surface

(Stretch rate)
Using a tensile tester (RTM-250 manufactured by Orientec Co., Ltd.), a film having a width of 10 mm and a length of 50 mm was stretched at a speed of 10 mm per minute at room temperature, and expressed as a stretch ratio at the point where a crack occurred visually. For example, a thickness of 50 mm to 75 mm is expressed as a stretching ratio of 50%.
This evaluation is used as an index indicating moldability. The higher the stretch ratio, the better the moldability.

(Adhesion)
According to JIS K5600, 25 grids are made by making 6 vertical and horizontal cuts at 2 mm intervals on the surface of the film having the cured film to be measured. After the cellophane tape was brought into close contact with the surface, the number of cells remaining without peeling was shown.

(Magic wipeability)
Using black / red magic ink, letters were written on the coated surface, wiped with a Kimwipe, and the wipeability was judged visually.
Evaluation A: Wipe 10 or more times at the same location B: Wipe 5-9 times at the same location C: Wipe 1 to 4 times at the same location

(Fingerprint wiping)
Automatic contact angle meter Measures the contact angle of hexadecane (HD) using CA-V model manufactured by Kyowa Interface Science Co., Ltd.
Used as an evaluation of oil repellency. A higher contact angle is preferable. HD is used as an index of fingerprint wiping property, and the higher the contact angle, the better the fingerprint wiping property. A contact angle of HD = 50 ° or more is preferable.

(Total light transmittance)
Haze meter Measured using TC-H3DPK manufactured by Tokyo Denshoku Co., Ltd.

(Haze)
Haze meter Measured using TC-H3DPK manufactured by Tokyo Denshoku Co., Ltd.

  As is clear from the results of Examples 2 to 8 in Table 5, the film having the cured layer of the resin composition of the present invention has a very good balance between hardness and stretch ratio, and has good antifouling properties. It is. In Comparative Example 2 in which the component (A) was changed, the hardness was good, but the film was hardly stretched. In Comparative Example 3, the stretching ratio was good, but the hardness was significantly inferior. In Comparative Examples 4 to 5 in which the component (A) is not used, the stretch ratio is good, but the hardness is significantly inferior. It was a result inferior compared with the film which has a hardened layer of a resin composition. Moreover, in the comparative example 8 which does not use (C) component, antifouling property was inferior. Further, Comparative Examples 9 to 14 were performed with reference to Examples of Patent Document 4 and Patent Document 5. In Comparative Examples 9 and 10 in which the resin component described in Examples of Patent Document 4 and Patent Document 5 is replaced with the component (A) of the present invention, the hardness is equal to or higher than that of the present invention. It did not grow. In Comparative Examples 11 and 13 carried out with the blends described in Examples of Patent Document 4 and Patent Document 5, the film hardly grows and the antifouling property is insufficient. Furthermore, in Comparative Examples 12 and 14 in which the resin components of the blends described in Examples of Patent Document 4 and Patent Document 5 were replaced with the component (A) of the present invention, hardness and antifouling properties were insufficient.

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

Claims (8)

Epoxy (meth) acrylate (A) having at least three (meth) acryloyl groups in the molecule obtained by reacting the epoxy resin (a) represented by the general formula (1) and (meth) acrylic acid (b) ), A photo radical polymerization initiator (B), and an antifouling agent (C), an ultraviolet curable hard coat resin composition for molded films used in film insert molding (however, a polymer obtained by polymerizing a methacrylate ester) The resin composition containing

(In the formula, 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 on average.) The ultraviolet curable hard coat resin composition according to claim 1, wherein the antifouling agent (C) is a polysiloxane having a (meth) acryloyl group. The ultraviolet curable hard coat resin composition according to claim 1, wherein the antifouling agent (C) is a fluorine compound having a (meth) acryloyl group. The ultraviolet curable hard coat resin composition according to any one of claims 1 to 3, wherein R of the epoxy resin (a) represented by the general formula (1) is a methyl group. 5. The ultraviolet curable (meth) acrylate (D) having at least 3 or more (meth) acryloyl groups in the molecule other than the component (A) is further contained. The ultraviolet curable hard coat resin composition according to any one of the above. Furthermore, it contains epoxy (meth) acrylate (E-1) and / or urethane (meth) acrylate (E-2) having two (meth) acryloyl groups in the molecule. The ultraviolet curable hard coat resin composition according to claim 5. A hard coat film having a cured layer of the ultraviolet curable hard coat resin composition according to any one of claims 1 to 6 . A hard coat molded article having a cured layer of the ultraviolet curable hard coat resin composition according to any one of claims 1 to 6 .