JPWO2010090116A1 - Active energy ray-curable resin composition for hard coat and its use - Google Patents

Abstract

Provided is an active energy ray-curable hard coat resin composition having good hardness, high transparency, good elongation and flexibility, and excellent fingerprint resistance visibility and fingerprint wiping properties. thing. A polyfunctional (meth) acrylate compound (A) having three or more (meth) acryloyl groups in the molecule and a polytetramethylene glycol skeleton having a polytetramethylene glycol skeleton portion having a number average molecular weight of 600 or more. A composition containing a (meth) acrylate compound (B) having a refractive index of 1.45 to 1.55, and a contact angle of the cured film of the composition with oleic acid of 25 A resin composition for an active energy ray-curable hard coat that is less than or equal to a degree. [Selection figure] None

Description

  The present invention relates to a resin composition for an active energy ray-curable hard coat that is excellent in scratch resistance, hardness, flexibility, fingerprint visibility and fingerprint wiping property on a plastic surface and can be overcoated. More specifically, the present invention relates to a resin composition for an active energy ray-curable hard coat, which is suitable for application to a plastic surface such as polyester, acrylic, triacetyl cellulose, polycarbonate, etc., is transparent, has excellent scratch resistance, and hardness. The present invention relates to an active energy ray-curable resin composition suitable for a hard coat of a switch panel manufactured by a film used in a touch panel display or in-mold molding because of its excellent visibility and fingerprint wiping property. The fingerprint visibility is the difficulty of seeing the fingerprint imprint, and the fingerprint wiping is the ease of wiping off the attached fingerprint imprint.

  Furthermore, this invention provides the hard coat film which can obtain the molded article which has the said characteristic, without generating a crack in the curved-surface part of a molded article surface part. In addition, since the present invention is particularly excellent in moldability, it is also suitable for a hard coat of a film used for in-mold molding.

  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 a large amount of plastic is used in this way is that, in addition to its processability and transparency, it is lightweight, inexpensive and has excellent optical properties. However, plastic has a drawback that it is softer than glass or the like and the surface is easily damaged. In order to improve these drawbacks, it is a common means to coat a plastic surface with a hard coating agent. As the hard coat agent, a thermosetting hard coat agent such as silicone, acrylic or melamine is used. Of these, silicone hard coat agents are especially used because of their high hardness and excellent quality, but they are long and expensive, and hard coats that are provided for continuously processed films It is not suitable.

  In recent years, photosensitive acrylic hard coating agents have been developed and used (Patent Document 1). Such a photosensitive hard coating agent is immediately cured by irradiation with active energy rays such as ultraviolet rays to form a hard film, so that the processing speed is high, and the hardness, scratch resistance, etc. are excellent. Due to its performance and low total cost, it is now the mainstream of hard coating agents. In particular, it is used for continuous processing of films such as polyester.

  Examples of plastic films that use photosensitive hard coat agents include polyester films, acrylic films, polycarbonate films, vinyl chloride films, triacetyl cellulose films, and polyethersulfone films. Polyester films have various excellent properties. Most widely used. This polyester film is, for example, a glass shatterproof film, an automobile light-shielding film, a whiteboard surface film, a system kitchen surface antifouling film, or a CRT flat TV, touch panel display, liquid crystal display (LCD) in terms of electronic materials. It is widely used as a functional film for plasma displays (PDP), organic EL displays, etc., and for body parts and switch panels of home appliances, casings of mobile phones and personal computers, and automobile interior parts.

  In addition to plastic films, polycarbonate or acrylic sheets and substrates with hard coatings are used as liquid crystal related members around optical disks and backlights.

  Recently, base materials coated with a hard coating agent have been required to have other functions as well as performance as a hard coat called scratch resistance. For example, a display such as a CRT, LCD, PDP, or touch panel provided with a film has a problem that the display screen is difficult to see due to reflection and the eyes are likely to get tired. Processing is required (Patent Document 2).

  In addition, a hard coat provided with an antistatic function using a surfactant or a conductive metal oxide has been developed (Patent Document 3).

  Furthermore, the hard coat may be required to have properties such as elongation and flexibility contrary to characteristics such as scratch resistance and hardness as the hard coat.

  As described above, for example, the use of films is increasing in the field of molding such as casings for mobile phones and personal computers, automotive interior materials such as meter covers, display panels and switch buttons for AV equipment and home appliances, etc. It is coming. In general, plastic products are molded by injection molding using a mold. However, as a method of processing the surface of this product, a method of attaching a film to the inner surface of the mold and attaching it to the surface of the molded product at the same time is proposed. It is called in-mold molding or film insert injection molding. That is, the film function can be imparted simultaneously with molding by sandwiching the film between the molds and simultaneously performing injection molding. Furthermore, cosmetics and functionality such as decoration on the molded product and increased hardness can be imparted by printing a pattern or a pattern on the film to be mounted or using a hard coat film.

  For molding using the hard coat film, a hard coat is applied to the base film, and the hard coat is applied to the film having the release layer and in-mold lamination (IML) in which the hard coat film is integrally formed. And in-mold decoration (IMD) that removes the release film after molding (Patent Document 4).

  In addition, since the hard coat used for injection molding is on the top surface of the molded plastic product, not only the surface hardness, but also the cosmetic properties such as gloss and the performance such as elongation and flexibility that can withstand the molding process. Is also necessary. Therefore, when forming a hard coat layer on a substrate film, a method of integrally forming a hard coat film that has been cured (cross-linked), or first forming only a film of a hard coat film, and curing (cross-linking after molding) ).

  For the various display devices, touch panel members, switch buttons of molded products, etc., it has also been required to provide a function in which fingerprints do not adhere to the surfaces or are difficult to adhere, so-called fingerprint resistance. However, at present, it has not been known to provide a function to prevent fingerprints from attaching. Instead, there is a demand for performance that allows easy wiping even if fingerprints are attached.

  As a method for improving the fingerprint wiping property as the fingerprint resistance, for example, there is a method of improving the water repellency / oil repellency of the surface by using a fluorine-based material, silicone oil or the like mixed in the coating composition. However, since fluorine and silicone are low refractive index components, when they are used as a coating on the surface, there is a disadvantage that the difference in refractive index from the fingerprint becomes large, and even a small amount of fingerprint is noticeable. Furthermore, if the wiping is insufficient, in addition to a large difference in refractive index, there are water repellent and oil repellent functions, so that the contact angle with the fingerprint becomes high and the fingerprint becomes more visible. In addition, since IMD performs further printing on the hard coat layer, if a fluorine-based material, silicone oil or the like is mixed in the coating composition, printing ink will be repelled and printing cannot be performed. is there.

  In addition, no hard coat with excellent fingerprint resistance has been known so far.

Japanese Patent Laid-Open No. 9-48934 JP-A-9-145903 JP-A-10-231444 Japanese Patent No. 3007326

  The present invention improves the above-mentioned drawbacks, has good hardness, high transparency, good elongation and flexibility, and is an active energy ray-curable hard disk excellent in fingerprint visibility resistance and fingerprint wiping properties. It aims at providing the resin composition for a coat.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition having a specific physical property range containing a specific compound and a cured product thereof can solve the above problems, and have reached the present invention. did.

That is, the present invention
(1) A polyfunctional (meth) acrylate compound (A) having three or more (meth) acryloyl groups in the molecule and a polytetramethylene glycol skeleton having a polytetramethylene glycol skeleton portion having a number average molecular weight of 600 or more A composition containing a (meth) acrylate compound (B) having a refractive index of 1.45 to 1.55, and a contact angle of the cured film of the composition with oleic acid is Active energy ray-curable hard coat resin composition having a temperature of 25 degrees or less;
(2) The active energy ray-curable hard coat resin composition according to (1), which contains a photopolymerization initiator (C);
(3) The active energy ray-curable hard coat resin composition according to (1) or (2) above, which contains colloidal silica (D) having a primary particle size of 1 nm to 200 nm;
(4) The active energy ray-curable hard coat resin composition according to any one of (1) to (3), which contains a diluent (E);
(5) The active energy ray-curable type according to any one of (1) to (4), which comprises a (meth) acrylic compound (F) having 1 to 2 (meth) acryloyl groups in the molecule. Hard coat resin composition;
(6) A polyfunctional (meth) acrylate compound (A) having three or more (meth) acryloyl groups in the molecule is obtained by reacting a polyfunctional (meth) acrylate compound having active hydrogen with polyisocyanate. The active energy ray-curable hard coat resin composition according to any one of (1) to (5), which is a compound;
(7) A urethane having a (meth) acrylate compound (B) having a polytetramethylene glycol skeleton having a polytetramethylene glycol skeleton having a number average molecular weight of 600 or more and having two or more (meth) acryloyl groups in the molecule. The active energy ray-curable hard coat resin composition according to any one of (1) to (6), which is a (meth) acrylate compound;
(8) The addition amount of the (meth) acrylate compound (B) having a polytetramethylene glycol skeleton having a polytetramethylene glycol skeleton portion having a number average molecular weight of 600 or more is based on 100% by weight of the solid content of the resin composition. The resin composition for an active energy ray-curable hard coat according to any one of (1) to (7), which is 0.1 to 10% by weight;
(9) A film having a cured film of the resin composition for an active energy ray-curable hard coat according to any one of (1) to (8);
(10) A substrate having a cured film of the resin composition for an active energy ray-curable hard coat according to any one of (1) to (8);
(11) A display member having a cured film of the active energy ray-curable hard coat resin composition according to any one of (1) to (8);
(12) A touch panel member having a cured film of the active energy ray-curable hard coat resin composition according to any one of (1) to (8);
(13) A hard coat film for a touch panel having a cured film of the resin composition for an active energy ray-curable hard coat according to any one of (1) to (8);
(14) A hard coat film for display having a cured film of the active energy ray-curable hard coat resin composition according to any one of (1) to (8);
(15) A hard coat film used for in-mold molding having a cured film of the active energy ray-curable hard coat resin composition according to any one of (1) to (8);
(16) A molded article having a cured film of the active energy ray-curable resin composition for hard coat according to any one of (1) to (8);
About.

  According to the present invention, an active energy ray-curable hard coat resin composition having excellent hardness, transparency, scratch resistance, flexibility, fingerprint visibility, fingerprint wiping property, etc., which can be used for in-mold molding. And a cured product thereof.

  The present invention relates to a polyfunctional (meth) acrylate compound (A) having 3 or more (meth) acryloyl groups in the molecule and a polytetramethylene glycol skeleton having a number average molecular weight of 600 or more in the polytetramethylene glycol skeleton portion. A composition containing a (meth) acrylate compound (B) having a refractive index of 1.45 to 1.55, and a contact angle of the cured film of the composition with oleic acid of 25 The present invention relates to a resin composition for an active energy ray-curable hard coat that is less than or equal to a degree. Hereinafter, the present invention will be described in detail.

  As a polyfunctional (meth) acrylate compound (A) having 3 or more, preferably 3 to 12 (meth) acryloyl groups in the molecule contained in the resin composition for an active energy ray-curable hard coat of the present invention. For example, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, epichlorohydrin (ECH) modified glycerol tri (meth) acrylate, ethylene oxide (EO) modified glycerol tri (meth) acrylate, propylene oxide (PO) modified glycerol triacrylate, pentaerythritol tri (meth) acrylate, EO modified phosphate tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, EO modified trimethylo Rupropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) ) Epoxies such as acrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, silicone hexa (meth) acrylate, bisphenol A epoxy di (meth) acrylate Obtained by reacting polyfunctional (meth) acrylate with poly (isocyanate) having active hydrogen with (meth) acrylate That multifunctional urethane (meth) polyester acrylates such as (meth) acrylate, or other urethane (meth) acrylate. These may be used alone or in combination of two or more.

  Examples of the polyfunctional (meth) acrylate having active hydrogen include pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tetra (meth). Pentaerythritols such as acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, methylols such as trimethylolpropane di (meth) acrylate, epoxy acrylates such as bisphenol A diepoxy acrylate, etc. Can be mentioned. Of these, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are preferable. These polyfunctional (meth) acrylates having active hydrogen may be used alone or in admixture of two or more.

  As said polyisocyanate, the polyisocyanate comprised by a chain | strand-shaped saturated hydrocarbon, cyclic saturated hydrocarbon (alicyclic), and aromatic hydrocarbon can be used. Examples of such polyisocyanates include chain saturated hydrocarbon polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and methylenebis (4-cyclohexyl). Isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, etc., cyclic saturated hydrocarbon (alicyclic) polyisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene Diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate Aromatic polyisocyanates such as 1,5-naphthalene diisocyanate. Of these, isophorone diisocyanate and hexamethylene diisocyanate are preferable. 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 active hydrogen with a polyisocyanate. The polyisocyanate is usually in the range of 0.1 to 50 equivalents, preferably in the range of 0.1 to 10 equivalents as the isocyanate group equivalent, relative to 1 equivalent of the active hydrogen group in the polyfunctional (meth) acrylate having active hydrogen. is there. The reaction temperature is usually 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction is the time when the polyisocyanate calculated by the method of reacting residual isocyanate with excess n-butylamine and back titrating with 1N hydrochloric acid is 0.5% by weight or less.

  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 triethylamine, diethylamine, dibutylamine, and ammonia, phosphines such as tributylphosphine and triphenylphosphine, pyridine, pyrrole, and the like.

  Examples of the acidic catalyst include metal salts such as copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, trititanium tetrabutoxide, zirconium tetrabutoxide, Lewis acids such as aluminum chloride, 2-ethylhexanetin, Examples thereof include tin compounds such as octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate.

  When these catalysts are used, the amount added can be usually about 0.1 to 1 part by weight per 100 parts by weight 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 used is 0.01 weight with respect to the reaction mixture. % To about 1% by weight, preferably about 0.05% to 0.5% by weight. The reaction temperature is 60 to 150 ° C, preferably 80 to 120 ° C.

  The content of the polyfunctional (meth) acrylate compound (A) having three or more (meth) acryloyl groups in the molecule in the resin composition for an active energy ray-curable hard coat of the present invention is the solid content of the resin composition. When the content is 100% by weight, it is usually 20.0% to 99.9% by weight, preferably 45.0% to 90.0% by weight.

  As the (meth) acrylate compound (B) having a polytetramethylene glycol skeleton in which the number average molecular weight of the polytetramethylene glycol skeleton portion contained in the resin composition for an active energy ray-curable hard coat of the present invention is 600 or more, Examples thereof include polyester (meth) acrylate of polytetramethylene glycol, epoxy (meth) acrylate of polytetramethylene glycol, urethane (meth) acrylate of polytetramethylene glycol, and the like. Among these, urethane (meth) acrylate of polytetramethylene glycol is preferable. The number average molecular weight of the polytetramethylene glycol skeleton is preferably about 600 to 10,000.

  Examples of the polyester (meth) acrylate of the polytetramethylene glycol and the epoxy (meth) acrylate of the polytetramethylene glycol include compounds shown in the following synthesis examples.

Examples of urethane (meth) acrylates of polytetramethylene glycol include polytetramethylene glycol having a polytetramethylene glycol skeleton number-average molecular weight of 600 or more, hexamethylene diisocyanate, alicyclic polyisocyanate, and tolylene diisocyanate. Organic polyisocyanates such as xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, Reaction products with hydroxyl group-containing ethylenically unsaturated compounds such as ε-caprolactone-modified 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are exemplified. Polytetramethylene glycol, organic polyisocyanates, and hydroxyl group-containing ethylenically unsaturated compounds may be used alone or in admixture of two or more.
Other polyols may be used together with polytetramethylene glycol. Examples of other polyols include polyether polyols other than polytetramethylene glycol, ethylene glycol, 1,4-butanediol, neopentyl glycol, polycaprolactone polyol, polyester polyol, and polycarbonate diol.

  As a compound preferable as urethane (meth) acrylate of polytetramethylene glycol, for example, a reaction product (acryloyl group: 2) of polytetramethylene glycol having a molecular weight of 1000 to 2000, isophorone diisocyanate, and 2-hydroxyethyl acrylate, etc. Can be mentioned.

  The urethane (meth) acrylate of polytetramethylene glycol is preferably 1.1 to 2.0 equivalents, preferably 70 to 90 ° C., of isocyanate groups of organic polyisocyanates per one equivalent of hydroxyl groups of polytetramethylene glycol. Next, the reaction can be carried out by reacting 1.0 to 1.5 equivalents of the hydroxyl group-containing ethylenically unsaturated compound per equivalent of the reaction product. The urethane (meth) acrylate of the polytetramethylene glycol is preferably a compound in which an acryloyl group is bonded to two or more terminal portions of the molecule.

  The content of the (meth) acrylate compound (B) having a polytetramethylene glycol skeleton in which the number average molecular weight of the polytetramethylene glycol skeleton portion in the resin composition for an active energy ray-curable hard coat of the present invention is 600 or more is: When the solid content of the resin composition is 100% by weight, it is usually 0.1% to 10% by weight, preferably 1% to 5% by weight. When the amount of the (meth) acrylate compound (B) is small, the fingerprint wiping property is deteriorated, and when the amount is too large, the hard coat property tends to be lowered.

  The active energy ray-curable hard coat resin composition of the present invention may contain a photopolymerization initiator (C). Examples of the photopolymerization initiator (C) 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-morpholinopro Acetophenones such as pan-1-one, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, anthraquinones such as 2-amylanthraquinone, 2,4-diethylthioxanthone, 2- Thioxanthones such as sopropylthioxanthone and 2-chlorothioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and 4,4′-bismethylaminobenzophenone Phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. In addition, Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) and Irgacure 907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-produced by Ciba Specialty Chemicals, Inc., which are easily available from the market ON), and Lucylin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) manufactured by BASF. These may be used alone or in combination of two or more.

  The content of the photopolymerization initiator (C) in the resin composition for an active energy ray-curable hard coat of the present invention is about 0% by weight to 10% by weight when the solid content of the resin composition is 100% by weight. Preferably, it is about 1 to 7% by weight.

  Moreover, the said photoinitiator (C) can also be used together with a hardening accelerator. Examples of the curing accelerator include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid isoamyl ester, EPA and other amines, and 2-mercaptobenzoic acid. Examples include hydrogen donors such as thiazole. The content of the curing accelerator in the active energy ray-curable hard coat resin composition of the present invention is about 0% by weight to 5% by weight when the solid content of the resin composition is 100% by weight.

  The active energy ray-curable hard coat resin composition of the present invention may contain colloidal silica (D) having a primary particle size of 1 nm to 200 nm. The colloidal silica (D) may be used as a colloidal solution dispersed in a solvent, or may be used as finely divided silica containing no dispersion solvent. Examples of the dispersion solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, diacetone alcohol, polyhydric alcohols such as ethylene glycol or derivatives thereof, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylacetamide, and the like. Ketones, esters such as ethyl acetate and n-butyl acetate, nonpolar solvents such as toluene and xylene, acrylates such as 2-hydroxyethyl acrylate, other general organic solvents, water and the like can be used. The amount used is usually 100% to 900% by weight with respect to 100% by weight of colloidal silica.

  The colloidal silica can be produced by a method known in the literature, or a commercially available product can be used. Examples of the colloidal silica include organosilica sol MEK-ST manufactured by Nissan Chemical Industries.

  Moreover, you may use what gave the reactive group by processing the silica surface with a silane coupling agent etc.

  In the present invention, the primary particle diameter means the smallest particle diameter of the particles when the aggregation is broken, and can be measured as an average particle diameter of the BET method.

  As said colloidal silica (D), that whose primary particle diameter is 1 nm-200 nm, Preferably it is 1 nm-100 nm, More preferably, the thing of 1 nm-50 nm can be used. In particular, in the case of 1 nm to 100 nm, transparency is secured, and in the case of 1 nm to 50 nm, sufficiently good results are obtained with transparency and haze.

  When the active energy ray-curable hard coat resin composition of the present invention contains colloidal silica (D) having a primary particle size of 1 nm to 200 nm, the content is 100% by weight of the solid content of the resin composition. In this case, the solid content excluding the dispersion medium is 0 to 70% by weight, preferably 5 to 50% by weight.

  The active energy ray-curable hard coat resin composition of the present invention may contain a diluent (E). For example, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α- Lactones such as acetyl-γ-butyrolactone and ε-caprolactone, dioxane, 1,2-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, Ethers such as triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, ethylene carbonate Carbonates such as propylene carbonate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone, phenols such as phenol, cresol and xylenol, ethyl acetate, n-butyl acetate, ethyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate , Esters such as carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, hydrocarbons such as toluene, xylene, diethylbenzene, cyclohexane, halogenated hydrocarbons such as trichloroethane, tetrachloroethane, monochlorobenzene, petroleum ether , Organic solvents such as petroleum solvents such as petroleum naphtha, fluorine alcohol such as 2H, 3H-tetrafluoropropanol And fluoro ethers such as perfluorobutyl methyl ether and perfluorobutyl ethyl ether, alcohols such as methanol, ethanol, isopropanol and n-propanol, and diacetone alcohol having both the performance of ketone and alcohol. It is done. These may be used alone or in combination of two or more.

  The active energy ray-curable hard coat resin composition of the present invention may contain a (meth) acrylic compound (F) having 1 to 2 (meth) acryloyl groups in the molecule, and the (meth) The acrylic compound (F) is a compound other than the component (B), such as polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ε-caprolactone adduct of neopentyl glycol hydroxypivalate. (Meth) acrylate (for example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.), di (meth) acrylate of EO addition product of bisphenol A, 1,4-butanediol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) ) Acrylate, alicyclic (meth) acrylates (tricyclodecane (meth) acrylate, dicyclopentadieneoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantane (meth) acrylate Etc.), phenylglycidyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acryloylmorpholine, (meth) acrylates having a hydroxyl group (2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like), ethyl carbitol (meth) acrylate and the like. These may be used alone or in combination of two or more.

  The content of the (meth) acrylic compound (F) having 1 to 2 (meth) acryloyl groups in the molecule in the resin composition for an active energy ray-curable hard coat of the present invention is the solid content of the resin composition. Is 100 wt%, 0 wt% to 20.0 wt%, preferably 1.0 wt% to 10.0 wt%.

  Furthermore, the active energy ray-curable hard coat resin composition of the present invention of the present invention includes a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, if necessary. It is also possible to add inorganic fine particles other than the cross-linking agent and colloidal silica (D), fillers, and the like to impart the intended functionality.

  As the leveling agent, it is preferable to use an acrylic or high-boiling-point solvent that does not interfere with fingerprint resistance.

  Examples of ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, and triazine compounds. Examples of light stabilizers include hindered amine compounds and benzoate compounds. Examples of antioxidants include phenol compounds. Is mentioned.

  Examples of the polymerization inhibitor include methoquinone, methylhydroquinone, hydroquinone and the like, and examples of the crosslinking agent include the polyisocyanates and melamine compounds.

  Examples of inorganic fine particles include zinc antimonate, gallium-doped zinc oxide, aluminum-doped zinc oxide, tin oxide, antimony-doped tin oxide, phosphorus-doped tin oxide, and indium-doped tin oxide, and other conductive metal oxides such as titanium oxide and zirconium oxide. Examples thereof include metal oxides for adjusting the refractive index.

  Examples of the filler include silica having an average particle size of micron order, acrylic beads, urethane beads, and the like, and can be used for the purpose of forming irregularities on the coating film surface.

  The active energy ray-curable hard coat resin composition of the present invention comprises the component (A), the component (B), and optionally the component (C), the component (D), the component (E), and the component (F). And other ingredients in any order.

  The active energy ray-curable hard coat resin composition of the present invention has a refractive index of 1.45 to 1.55 at 25 ° C. when the solid content is 100% (excluding the refractive index of the diluent). It is the resin composition which is the range. If the refractive index is out of this range, the difference in refractive index from the attached fingerprint imprint will be too large and the fingerprint imprint will tend to be very visible.

  The active energy ray-curable hard coat resin composition of the present invention thus obtained is stable over time.

  The active energy ray-curable hard coat resin composition of the present invention is applied onto a base film so that the thickness of the resin composition after drying is usually 0.1 μm to 50 μm, preferably 1 μm to 20 μm. A film obtained by irradiating an active energy ray after drying to form a cured film is also included in the present invention. By bringing the resin composition for an active energy ray-curable hard coat of the present invention to the outermost layer, it can also be used as a multilayer coat film.

  The base film is not particularly limited, and examples thereof include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetylcellulose, polyethersulfone, and cycloolefin polymer. The film to be used may be a film provided with a handle, an easy-adhesion layer, a base layer, a surface treatment such as a corona treatment, or a mold release treatment.

  Examples of the application method of the active energy ray-curable hard coat resin composition include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, and micro reverse. Examples include gravure coater coating, die coater coating, dip coating, spin coat coating, and spray coating.

  Examples of the active energy ray for curing the active energy ray-curable hard coat resin composition of the present invention include ultraviolet rays and electron beams.

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 amount of light, 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 120 W / cm ² .

  When curing with an electron beam, it is preferable to use an electron beam accelerator having an energy of 100 to 500 eV, and the photopolymerization initiator (D) may not be used.

  The contact angle of the cured film obtained by curing the active energy ray-curable hard coat resin composition of the present invention with oleic acid is preferably 25 degrees or less, more preferably 23 degrees or less. If it is 30 degrees or more, even if the refractive index falls within the range of 1.45 to 1.55, the attached fingerprint imprint becomes easy to see. Since oleic acid is a substance close to the component of the fingerprint imprint, it is expected that the fingerprint imprint will be difficult to see if the contact angle with oleic acid is lowered.

  A substrate having a cured film of the resin composition for an active energy ray-curable hard coat of the present invention is also included in the present invention. Moreover, the display member and touch panel member which have this cured film are also contained in this invention.

  Furthermore, the present invention includes a hard coat film for a touch panel having the cured film, a hard coat film for a display, and a hard coat film used for in-mold molding, and molded products such as a touch panel and a display having the cured film are also included in the present invention. included.

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

Synthesis example 1
1395.1 parts of polytetramethylene glycol (PTG-2000SN manufactured by Hodogaya Chemical Industry; molecular weight 1993) and 311.2 parts of isophorone diisocyanate were placed in a drying container, and the temperature was gradually raised to 80 ° C. while stirring. It was made to react with. When the ratio of isocyanate is in the range of 6.7 to 7.2%, 167.4 parts of 2-hydroxyethyl acrylate and 0.5 parts of methoquinone are added, and the temperature is gradually raised to 80 ° C. again, and then for 5 hours. The reaction was allowed to proceed with stirring, and then 0.15 part of dibutyltin laurate was added, and the reaction was further continued until the isocyanate ratio became 0.1% or less and the reaction was almost quantitatively completed. The synthesized urethane acrylate of polytetramethylene glycol had two acryloyl groups.

Synthesis example 2
595.0 parts of polytetramethylene glycol (PTG-850SN manufactured by Hodogaya Chemical Co., Ltd .; molecular weight 850) and 311.2 parts of isophorone diisocyanate were placed in a drying container, and the temperature was gradually raised to 80 ° C. while stirring. It was made to react with. When the isocyanate ratio falls within the range of 6.7 to 7.2%, 167.4 parts of 2-hydroxyethyl acrylate and 0.5 parts of methoquinone are added, and the temperature is gradually raised again to 80 ° C. The reaction was continued with stirring for a period of time, and then 0.15 part of dibutyltin laurate was added, and the reaction was further continued until the isocyanate ratio became 0.1% or less and the reaction was almost quantitatively completed. The synthesized urethane acrylate of polytetramethylene glycol had two acryloyl groups.

Synthesis example 3
In a drying container, 2030.0 parts of polytetramethylene glycol (PTG-2900 manufactured by Hodogaya Chemical Co., Ltd .; molecular weight 2900) and 311.2 parts of isophorone diisocyanate were placed, and the temperature was gradually raised to 80 ° C. while stirring. It was made to react with. When the ratio of isocyanate is in the range of 6.7 to 7.2%, 167.4 parts of 2-hydroxyethyl acrylate and 0.5 parts of methoquinone are added, and the temperature is gradually raised to 80 ° C. again, and then for 5 hours. The reaction was allowed to proceed with stirring, and then 0.15 part of dibutyltin laurate was added, and the reaction was further continued until the isocyanate ratio became 0.1% or less and the reaction was almost quantitatively completed. The synthesized urethane acrylate of polytetramethylene glycol had two acryloyl groups.

Synthesis example 4
In a drying container, 1395.1 parts of polytetramethylene glycol (PTG-2000SN manufactured by Hodogaya Chemical Industry; molecular weight 1993) and 235.2 parts of hexamethylene diisocyanate were placed, and the temperature was gradually raised to 80 ° with stirring. The reaction was carried out at ° C. When the ratio of isocyanate is in the range of 6.7 to 7.2%, 184.7 parts of 2-hydroxypropyl acrylate and 0.5 part of methoquinone are added, and the temperature is gradually raised again to 80 ° C. for 5 hours. The reaction was allowed to proceed with stirring, and then 0.15 part of dibutyltin laurate was added, and the reaction was further continued until the isocyanate ratio became 0.1% or less and the reaction was almost quantitatively completed. The synthesized urethane acrylate of polytetramethylene glycol had two acryloyl groups.

Synthesis example 5
In a dry container, 1300.0 parts of polytetramethylene glycol diglycidyl ether (Epogosei manufactured by Yokkaichi Chemical Co., Ltd .; molecular weight 650), 146.9 parts of acrylic acid, 0.5 parts of TMAC (tetramethylammonium chloride), BHT ( 0.5 part of dibutylhydroxytoluene) was added, and the temperature was gradually raised to 98 ° C. and reacted at 98 ° C. The synthesized polytetramethylene glycol epoxy acrylate had an epoxy equivalent of 15800, an acid value of 0.73, and two acryloyl groups.

Synthesis Example 6
1000.0 parts of polytetramethylene glycol (Hodogaya Chemical PTG-2000SN; molecular weight 1993), 86.4 parts of acrylic acid, 0.4 parts of phenothiazine, 0.8 parts of sulfuric acid, 1000 ml of n-heptane The distillate was charged into a flask and air diluted with nitrogen was blown, and the distillate was separated into a water layer and a heptane layer by a stationary layer, and reacted while returning the heptane layer to the flask. The reaction was stopped when the amount of distilled water reached a theoretical amount, and the reaction solution was dropped into water to precipitate the product, followed by filtration to obtain polytetramethylene glycol diacrylate.

Synthesis example 7
1395.1 parts of polypropylene glycol (PPG-2000SN manufactured by Hodogaya Chemical Co., Ltd .; molecular weight 2000) and 235.2 parts of hexamethylene diisocyanate were placed in a drying container, and the temperature was gradually raised to 80 ° C. while stirring, And reacted. When the ratio of isocyanate is in the range of 6.7 to 7.2%, 184.7 parts of 2-hydroxypropyl acrylate and 0.5 part of methoquinone are added, and the temperature is gradually raised again to 80 ° C. for 5 hours. The reaction was allowed to proceed with stirring, and then 0.15 part of dibutyltin laurate was added, and the reaction was further continued until the isocyanate ratio became 0.1% or less and the reaction was almost quantitatively completed. The synthesized urethane acrylate of polytetramethylene glycol had two acryloyl groups.

Synthesis Example 8
1395.1 parts polytetramethylene glycol (PTG-2000SN manufactured by Hodogaya Chemical Co., Ltd .; molecular weight 1993) and 235.2 parts hexamethylene diisocyanate were placed in a drying container and gradually heated to 80 ° C. while stirring. The reaction was carried out at ° C. When the ratio of isocyanate is in the range of 6.7 to 7.2%, 425.7 parts of pentaerythritol triacrylate and 0.5 part of methoquinone are added, and the temperature is gradually raised to 80 ° C. and stirred for 5 hours. Then, 0.15 part of dibutyltin laurate was added, and the reaction was further advanced until the proportion of isocyanate became 0.1% or less and the reaction was almost quantitatively completed. The synthesized urethane acrylate of polytetramethylene glycol had 6 acryloyl groups.

Synthesis Example 9
In a drying container, 2030.0 parts of polytetramethylene glycol (PTG-2900 manufactured by Hodogaya Chemical Co., Ltd .; molecular weight 2900) and 235.2 parts of hexamethylene diisocyanate were placed, and the temperature was gradually raised to 80 ° C. while stirring. The reaction was carried out at ° C. When the ratio of isocyanate is in the range of 6.7 to 7.2%, 425.7 parts of pentaerythritol triacrylate and 0.5 part of methoquinone are added, and the temperature is gradually raised to 80 ° C. and stirred for 5 hours. Then, 0.15 part of dibutyltin laurate was added, and the reaction was further advanced until the proportion of isocyanate became 0.1% or less and the reaction was almost quantitatively completed. The synthesized urethane acrylate of polytetramethylene glycol had 6 acryloyl groups.

Synthesis Example 10
1395.1 parts polytetramethylene glycol (PTG-2000SN manufactured by Hodogaya Chemical Co., Ltd .; molecular weight 1993) and 235.2 parts hexamethylene diisocyanate were placed in a drying container and gradually heated to 80 ° C. while stirring. The reaction was carried out at ° C. When the ratio of isocyanate is in the range of 6.7 to 7.2%, 744.1 parts of dipentaerythritol triacrylate and 0.5 parts of methoquinone are added, and the temperature is gradually raised to 80 ° C., and the temperature is increased for 5 hours. The reaction was allowed to proceed with stirring, and then 0.15 part of dibutyltin laurate was added, and the reaction was further continued until the isocyanate ratio became 0.1% or less and the reaction was almost quantitatively completed. The synthesized urethane acrylate of polytetramethylene glycol had 10 acryloyl groups.

Examples 1-14 and Comparative Examples 1-5
A resin composition containing the components shown in Table 1 was applied onto a readily adhesive-treated PET (polyethylene terephthalate) film (100 μm) with a bar coater, dried at about 80 to 100 ° C., and then an ultraviolet irradiator. (Harrison Toshiba Lighting Co., Ltd .: KUV-40151-1XKA-DM) High-pressure mercury lamp: 80 W / cm; Lamp height: 10 cm; Conveyor speed: 5 m / min × 3 passes (Energy: about 200 mW / cm ² , about 360 mJ / cm ² ) to obtain a hard coat film having a thickness of about 4 μm. In Table 1, the unit represents “part”.

(note)
* 1: Dipentaerythritol pentaacrylate / hexaacrylate mixture * 2: Pentaerythritol triacrylate / tetraacrylate mixture * 3: KAYARAD DPHA-40H (10 functional urethane acrylate) manufactured by Nippon Kayaku Co., Ltd.
* 4: Ciba Specialty Chemicals, 1-hydroxycyclohexyl phenyl ketone * 5: Organosilica sol, solid content 30%, MEK (methyl ethyl ketone) dispersion (average particle size: 10 nm to 15 nm) manufactured by Nissan Chemical Industries
* 6: Organosilica sol manufactured by Nissan Chemical Industries Ltd., solid content 30%, MIBK (methyl isobutyl ketone) dispersion (average particle size: 10 nm to 15 nm)
* 7: Tetrahydrofurfuryl acrylate * 8: Zinc antimonate sol, solid content 60%, methanol dispersion * 9: BYK306, silicon-based BYK306

  The following items were evaluated for the hard coat films obtained in Examples 1 to 14 and Comparative Examples 1 to 5, and the results are shown in Table 2.

(Pencil hardness)
According to JIS K 5600, the pencil hardness of the coated film having the above composition was measured using a pencil scratch tester. Specifically, a pencil was set on a polyester film having a cured film to be measured at an angle of 45 degrees, scratched about 5 mm by applying a load of 750 g from the top, and the hardness of the pencil that was not damaged more than 4 times out of 5 times. I expressed it.

(Fingerprint visibility-1)
The artificial fingerprint liquid described later was imprinted on the coated film having the above composition with a resin mold having a pitch of 50 to 100 μm, and the imprint was confirmed by haze measurement.

(Fingerprint visibility-2)
The imprint of (Fingerprint resistance visual recognition-1) was visually confirmed.
○: Almost invisible △: Slightly visible ×: Clearly visible

(Fingerprint wiping ability-1)
The imprint of (fingerprint visibility-1) was wiped by reciprocating 10 times with a load of 200 g / cm ² , and the remaining state of the trace was confirmed by haze measurement.

(Fingerprint wipe-2)
The remaining state of the trace of (fingerprint wiping property-1) was visually confirmed.
○: No trace left △: Some remaining left ×: Remaining noticeable

<Artificial fingerprint solution>
It was prepared and used at the following composition ratio.
Oleic acid: 6.1%
Olive oil: 29.3%
Jojoba oil: 47.5%
Squalene: 17.1%

(Contact angle)
The contact angle of the coating film having the above composition was measured using an automatic contact angle meter (DM500 manufactured by Kyowa Interface Science Co., Ltd.). Specifically, oleic acid was dropped on a polyester film having a cured film to be measured.

(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 50 mm per minute at room temperature, and the stretching ratio when a crack was visually observed was shown. . For example, the stretch ratio of a film having cracks at 75 mm is (75-50) / 50 = 50%.

  As is apparent from the results in Table 2, the film having the cured film of the active energy ray-curable hard coat resin composition of the present invention had good hardness, fingerprint resistance and fingerprint wiping properties. In Comparative Example 1 not containing the component (B), the hardness was good, but the fingerprint resistance visibility and the fingerprint wiping property were poor. Further, in Comparative Example 2 in which the skeleton of the component (B) is polypropylene glycol, the fingerprint resistance visibility and the fingerprint wiping property were inferior.

  Even if the skeleton portion is polytetramethylene glycol, Comparative Example 3 having no di (meth) acryloyl group has poor fingerprint wiping properties. Further, Comparative Example 4 having a refractive index of more than 1.55 has poor fingerprint visibility-2 (viewing), and Comparative Example 5 having a contact angle of oleic acid of more than 30 degrees has fingerprint resistance and fingerprint wiping properties. It was extremely bad.

  In Examples 12 to 14 including the component (B) having a polyfunctional acryloyl group, the hardness was further improved.

  The hard coat film obtained by using the active energy ray-curable hard coat resin composition of the present invention has high hardness and good fingerprint visibility and fingerprint wiping properties. The resin composition also has a good stretch ratio. Accordingly, the resin composition for an active energy ray-curable hard coat of the present invention is suitable for a hard coat of a film used for a touch panel display, and is also suitable as a material for a hard coat film used for forming such as having a folding process.

Claims (16)

  A polyfunctional (meth) acrylate compound (A) having three or more (meth) acryloyl groups in the molecule and a polytetramethylene glycol skeleton having a polytetramethylene glycol skeleton number average molecular weight of 600 or more (meth) A composition containing an acrylate compound (B), wherein the refractive index of the composition is 1.45 to 1.55, and the contact angle of the cured film of the composition with oleic acid is 25 degrees or less. An active energy ray-curable hard coat resin composition.   The resin composition for active energy ray hardening-type hard coats of Claim 1 containing a photoinitiator (C).   The resin composition for active energy ray hardening-type hard-coats of Claim 1 or 2 containing the colloidal silica (D) whose primary particle size is 1 nm-200 nm.   The resin composition for active energy ray hardening-type hard-coats as described in any one of Claims 1-3 containing a diluent (E).   The resin composition for active energy ray hardening-type hard-coats as described in any one of Claims 1-4 containing the (meth) acrylic compound (F) which has 1-2 (meth) acryloyl groups in a molecule | numerator. .   A polyfunctional (meth) acrylate compound (A) having three or more (meth) acryloyl groups in the molecule is a compound obtained by reacting a polyfunctional (meth) acrylate compound having active hydrogen with a polyisocyanate. The resin composition for active energy ray hardening-type hard-coats as described in any one of Claims 1-5.   The (meth) acrylate compound (B) having a polytetramethylene glycol skeleton having a polytetramethylene glycol skeleton portion having a number average molecular weight of 600 or more is a urethane (meth) having two or more (meth) acryloyl groups in the molecule. It is an acrylate compound, The active energy ray hardening-type resin composition for hard-coats as described in any one of Claims 1-6.   The addition amount of the (meth) acrylate compound (B) having a polytetramethylene glycol skeleton having a polytetramethylene glycol skeleton portion having a number average molecular weight of 600 or more is 0.1% relative to 100% by weight of the solid content of the resin composition. It is 1-10 weight%, The resin composition for active energy ray hardening-type hard-coats as described in any one of Claims 1-7.   The film which has a cured film of the resin composition for active energy ray hardening-type hard-coats as described in any one of Claims 1-8.   The base material which has a cured film of the resin composition for active energy ray hardening-type hard-coats as described in any one of Claims 1-8.   The display member which has a cured film of the active energy ray hardening-type resin composition for hard-coats as described in any one of Claims 1-8.   The touch panel member which has a cured film of the resin composition for active energy ray hardening-type hard-coats as described in any one of Claims 1-8.   The hard-coat film for touchscreens which has the cured film of the resin composition for active energy ray hardening-type hardcoats as described in any one of Claims 1-8.   The hard coat film for a display which has a cured film of the resin composition for active energy ray hardening-type hard coats as described in any one of Claims 1-8.   The hard coat film used for the in-mold shaping | molding which has a cured film of the resin composition for active energy ray hardening-type hard coats as described in any one of Claims 1-8.   The molded article which has a cured film of the resin composition for active energy ray hardening-type hard-coats as described in any one of Claims 1-8.