WO2013191254A1 - Energy ray-curable resin composition, cured product and laminate - Google Patents

Description

Energy ray curable resin composition, cured product and laminate

The present invention relates to an energy ray curable resin composition, a cured product, and a laminate.

Hard coat films are widely used for display screens such as displays, touch panels, and mobile phones. Especially, mobile products such as touch panels, mobile phones, and smartphones come in contact with fingers, pens, and other objects on a daily basis. There are many problems, and scratches on the surface are a problem. From the viewpoint of preventing scratches, it is sufficient to form a coating film excellent in scratch resistance and pencil hardness. However, such a coating film lacks flexibility and is a display, a touch panel, a mobile phone, a smartphone, etc. When the shape of the display screen is punched, there is a problem that cracks are generated and that the fragments accompanying the cracks become foreign matters. For this reason, the hard coat film which has a softness | flexibility, maintaining hardness is proposed (patent document 1, patent document 2).

JP 2007-46031 A (Claim 1) JP 2010-70602 A (Claim 1)

However, although the hard coat films proposed in Patent Document 1 and Patent Document 2 have improved flexibility, they are still insufficient in terms of scratch resistance. As one means for improving the flexibility, it is conceivable to reduce the thickness of the coating film. However, in this case, there is a problem that the scratch resistance is lowered.

On the other hand, with recent demands for thinning of mobile phones and smartphones, there is an increasing demand for hard coat films excellent in scratch resistance and pencil hardness despite being thin. In general, in the case of a thin film having a film thickness of 5 μm or less, it is difficult to obtain scratch resistance due to the polymerization-inhibiting action due to oxygen. As a means for solving this, it is considered to apply under a nitrogen purge. However, it requires a running cost and is not practical in terms of productivity.

Therefore, an object of the present invention is to improve the above-mentioned drawbacks and to form an energy ray-curable resin composition, a cured product, and a laminate that form a coating film having excellent scratch resistance and sufficient flexibility when cured. Is to provide.

As a result of intensive studies to solve the above problems, the present inventors have found that an energy ray curable resin composition containing a specific compound in a specific ratio solves the above problems, and completes the present invention. It came to.

That is, the energy beam curable resin composition of the present invention is
[1] (A) a polyfunctional urethane (meth) acrylate oligomer having an energy ray-curable functional group number in the range of 10 to 20, and (B) a cyclo ring structure having an energy ray-curable functional group number in the range of 2 to 6. At least one selected from (meth) acrylate monomers having 3 to 15 (meth) acrylate monomers having an ethylene oxide chain, and (meth) acrylate oligomers having a dendritic structure, and (C) a photopolymerization initiator, The energy ray-curable resin composition containing the component (A) and the component (B), wherein the mixing ratio of the component (A) and the component (B) is in the range of 60:40 to 95: 5 It is.

[2] The energy ray-curable resin composition according to [1], wherein the component (C) includes a photopolymerization initiator having a melting point of 70 ° C. or higher.

[3] The energy ray-curable resin composition according to [1], which contains a photopolymerization initiation assistant as a component (D).

[4] The energy ray-curable resin composition according to [3], wherein the (D) photopolymerization initiation auxiliary agent is a polyfunctional thiol compound.

[5] The energy ray-curable resin composition according to [3], wherein the content of the component (D) is 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the resin solid content. It is.

[6] The energy ray-curable resin composition according to [1], which contains a polyfunctional (meth) acrylate monomer having a hydrophilic group as the component (E).

The cured product of the present invention is
[7] A cured product obtained by curing the energy beam curable resin composition according to [1].

The laminate of the present invention is
[8] A laminate having a hard coat layer composed of the cured product according to [7] on at least one surface of a substrate.

[9] In a steel wool test in which the surface of the hard coat layer is subjected to 100 reciprocating frictions at a speed of 200 mm / sec while applying a load of 500 g / 3 cm ² with # 0000 steel wool, before and after the steel wool resistance test. The laminate according to [8], wherein a haze difference (ΔH) is 0.5% or less.

[10] When a test piece is obtained by providing a polyethylene terephthalate film having a flexural resistance test value of 50 μm to 188 μm measured by a cylindrical mandrel method according to JIS K5600-5-1: 1999 with the hard coat layer. The laminate according to [8] or [9], which is 16 mm or less.

[11] The laminate according to [8], wherein the thickness of the hard coat layer is 0.5 μm or more and 20 μm or less.

[12] The hard coat layer is the laminate according to [8], wherein the wetting tension measured in accordance with JIS K6768 is 27 mN / m or more and 45 mN / m or less.

[13] A laminate according to [8], wherein the laminate has at least one layer including a metal vapor deposition layer, a printing layer, and an adhesive layer on at least the other surface of the substrate.

According to the present invention, it is possible to provide an energy beam curable resin composition, a cured product, and a laminate that form a coating having scratch resistance and sufficient flexibility when cured.

Hereinafter, although each form of the energy beam curable resin composition, the cured product, and the laminate of the present invention will be specifically described, the present invention is not limited to the following forms and does not depart from the gist of the present invention. It is within the scope of the present invention to appropriately modify and improve the following embodiments based on the ordinary knowledge of those skilled in the art.

<Energy beam curable resin composition>
The energy ray-curable resin composition of the present invention comprises (A) a polyfunctional urethane (meth) acrylate oligomer having an energy ray-curable functional group number in the range of 10 to 20, and (B) a functional group number in the range of 2 to 6. At least one selected from a (meth) acrylate monomer having a cyclo ring structure, a (meth) acrylate monomer having 3 to 15 ethylene oxide chains, and a (meth) acrylate oligomer having a dendritic structure, and (C) light It contains a polymerization initiator, (D) a photopolymerization initiation assistant added as necessary, and (E) a polyfunctional monomer having a hydrophilic group. Each component will be described in detail below.

[(A) component]
In the energy ray curable resin composition of the present invention, it is essential to use (A) a polyfunctional urethane (meth) acrylate oligomer having an energy ray curable functional group in the range of 10 to 20. By using such a polyfunctional urethane (meth) acrylate oligomer, a high degree of crosslinking can be achieved, so that necessary hardness and scratch resistance can be obtained. By setting the number of energy ray-curable functional groups of the polyfunctional urethane (meth) acrylate oligomer to 10 or more, the crosslinking density can be increased and the hardness can be increased, and particularly the scratch resistance can be dramatically increased. . Further, by setting the number of functional groups to 20 or less, preferably 16 or less, it is possible to suppress steric hindrance due to an excessively high crosslinking density and to prevent a decrease in hardness due to inhibition of curing.

Such a urethane (meth) acrylate is a reaction product of an isocyanate compound obtained by reacting a polyol and a diisocyanate and a (meth) acrylate monomer having a hydroxyl group. Examples of the polyol include a polyester polyol and a polyether polyol. And polycarbonate diol. These may be used alone or in combination of two or more. In addition, (meth) acrylate shows an acrylate or a methacrylate.

The manufacturing method of the polyester polyol used for preparation of urethane (meth) acrylate ligomer is not specifically limited, A well-known manufacturing method can be employ | adopted. For example, the diol and dicarboxylic acid or dicarboxylic acid chloride may be subjected to a polycondensation reaction, or the diol or dicarboxylic acid may be esterified and subjected to an ester exchange reaction. Examples of the dicarboxylic acid include adipic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, maleic acid, terephthalic acid, isophthalic acid, and phthalic acid. Examples of the diol include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, and tetrapropylene glycol. These may be used alone or in combination of two or more.

The polyether polyol is preferably a polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide random copolymer having a number average molecular weight of less than 600. If it is 600 or more, the cured product may be too flexible and hard coat performance may not be obtained.

Polycarbonate diols include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, Examples include 2-ethyl-1,3-hexanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, and polyoxyethylene glycol. These may be used alone or in combination of two or more.

As the diisocyanate, a linear or cyclic aliphatic diisocyanate is used. Of course, aromatic diisocyanates can also be used, and it is possible to easily obtain excellent hard coat properties such as hardness and scratch resistance. On the other hand, polyfunctional oligomers are the main components that form the hard coat skeleton. This is because when the component is used, the light resistance is lowered, and yellowing easily occurs upon exposure to light, so that the function as a transparent hard coat is impaired in practical use. Typical examples of the linear or cyclic aliphatic diisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylylene diisocyanate. These may be used alone or in combination of two or more.

[Component (B)]
The energy ray curable resin composition of the present invention is a (meth) acrylate monomer having a cyclo ring structure having an energy ray curable functional group number in the range of 2 to 6, and a (meth) acrylate having 3 to 15 ethylene oxide chains. It is essential to use at least one selected from monomers and (meth) acrylate oligomers having a dendritic structure. By using these materials, it is possible to obtain a cured product having excellent flexibility while maintaining the hardness, particularly the scratch resistance performance.

[(Meth) acrylate monomer having a cyclo ring structure in which the number of energy ray-curable functional groups is 2 to 6]
As described above, in the present invention, since the (meth) acrylate monomer having the energy ray-curable functional group in the range of 10 to 20 is used as the component (A), the crosslinking density is higher than that of a general hard coat cured product. On the other hand, it becomes easy to obtain a cured product having high hardness, but on the other hand, since the crosslink density is high, flexibility tends to decrease. However, since a (meth) acrylate monomer having a cyclo ring structure can be used as the component (B) in the present invention, when the cured product is obtained by crosslinking the component (B) and the component (A). In order to suppress the crosslinking density from becoming too high and to reduce the rigidity of the cured product whose cyclo-ring structure has increased the crosslinking density, it is flexible while maintaining the hardness, especially the scratch resistance performance when cured. Can be granted. The (meth) acrylate monomer having such a cyclo ring structure needs to have 2 or more and 6 or less energy ray-curable functional groups. By setting the number of energy ray-curable functional groups to 2 or more, the component (A) and the component (B), or the component (B) can be sufficiently cross-linked with each other. Flexibility can be imparted without reducing the properties. By setting the number of energy ray-curable functional groups to 6 or less, it is possible to suppress steric hindrance caused by excessively high crosslinking density and to prevent a decrease in hardness.

The cyclo ring constituting the (meth) acrylate monomer having a cyclo ring structure having a number of energy ray-curable functional groups in the range of 2 to 6 is at least one selected from the group consisting of carbon, nitrogen, oxygen and silicon. It is preferably composed of an element and is a 5-membered ring or a 6-membered ring. By using a 5-membered ring or a 6-membered ring, the rigidity of the cured product having a higher crosslink density can be relaxed, and flexibility can be easily imparted while maintaining the hardness, particularly the scratch resistance performance. Specific examples of the cyclo ring structure include cycloolefins such as cyclopentene and cyclohexene, tetrahydrofuran, 1,3-dioxane, ε-caprolactone, ε-caprolactam, silacyclopentene, cyclodecane, isobonyl and the like. Examples of such (meth) acrylate monomers having a cyclo ring structure include ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, ε-caprolactone-modified tris- (2-hydroxyethyl) isocyanurate, dimethylol. Tricyclodecane di (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, tricyclodecane dimethanol di (meth) acrylate, tricyclodecane diethanoldi Examples include (meth) acrylate, tetracyclododecanedi (meth) acrylate, and bicyclohexyl (meth) acrylate. These may be used alone or in combination of two or more.

[(Meth) acrylate monomer having 3 to 15 ethylene oxide chain]
Next, the case where a (meth) acrylate monomer having 3 to 15 ethylene oxide chains is used as the component (B) will be described. When a (meth) acrylate monomer having 3 to 15 ethylene oxide chains is used as the component (B), the crosslinking density when the cured product is obtained by crosslinking the component (B) and the component (A). In order to reduce the rigidity of the cured product with the ethylene oxide chain being increased in crosslink density while suppressing excessive increase in hardness, it provides flexibility while maintaining hardness, especially scratch resistance performance when cured. can do. The (meth) acrylate monomer having such an ethylene oxide chain needs to have an ethylene oxide chain of 3 or more and 15 or less. By setting the ethylene oxide chain to 3 or more, the rigidity of the cured product having a high crosslinking density can be relaxed, so that flexibility is imparted without reducing the hardness, particularly the scratch resistance, when the cured product is made. can do. By setting the ethylene oxide chain to 15 or less, it is possible to prevent the crosslinking density from being lowered excessively, and to prevent the hardness, particularly the scratch resistance, of the cured product from being lowered.

Examples of such (meth) acrylates having 3 to 15 ethylene oxide chains include polyethylene glycol (meth) acrylate, ethylene oxide modified products of dipentaerythritol hexaacrylate, pentaerythritol tri (meth) acrylate ethylene oxide modified products, Examples include methylolpropane tri (meth) acrylate ethylene oxide modified products. These may be used alone or in combination of two or more.

[(Meth) acrylate oligomer having dendritic structure]
Next, the case where a (meth) acrylate oligomer having a dendritic structure is used as the component (B) will be described. The dendritic structure means a shape in which monomers are polymerized while branching radially from one nucleus and spread radially. When a (meth) acrylate oligomer having a dendritic structure is used as the component (B), the crosslinking density becomes too high when the cured product is obtained by crosslinking the component (B) and the component (A). In addition, the rigidity of the cured product in which the radial structure has a high crosslink density is suppressed, and thus flexibility can be imparted while maintaining the hardness, particularly the scratch resistance performance, when the cured product is formed. Commercially available products can be used as the (meth) acrylate oligomer having a dendritic structure, and examples thereof include Viscoat V # 1000, V # 5020, and STAR-501 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.). These may be used alone or in combination of two or more.

Such a component (B) includes (meth) acrylate monomers having a cyclo ring structure in which the number of energy ray-curable functional groups ranges from 2 to 6, (meth) acrylate monomers having 3 to 15 ethylene oxide chains, and dendritic What is necessary is just at least 1 sort (s) selected from the (meth) acrylate oligomer which has a structure, and each may be used independently and may be used in combination.

The blending ratio of the component (A) and the component (B) described above needs to be in the range of 60:40 to 95: 5 by mass ratio. When the addition ratio of the component (A) is 60 or more, preferably 70 or more, a cured product having sufficient hardness can be obtained when the energy beam curable resin composition of the present invention is cured, and fingerprints are obtained. The effect of wiping off can be obtained. Moreover, by making the addition ratio of (A) component 95 or less, Preferably it is 90 or less, it can suppress that a crosslinking density becomes high too much and it can be set as the hardened | cured material which has a softness | flexibility.

[(E) component]
Moreover, in this invention, the polyfunctional (meth) acrylate monomer which has a hydrophilic group can also be contained as a (E) component as needed. By using a polyfunctional (meth) acrylate monomer having a hydrophilic group, the fingerprint wiping property can be further improved. Examples of the hydrophilic group include a hydroxyl group, a carboxyl group, an amino group, a carbonyl group, a sulfonyl group, and an ether group. As the polyfunctional (meth) acrylate monomer having such a hydrophilic group, for example, pentaerythritol tri (meth) Examples include acrylate, dipentaerythritol hexa (meth) acrylate, and trimethylolpropane (meth) acrylate. These may be used alone or in combination of two or more. The content of the component (E) in the energy beam curable resin composition of the present invention is preferably in the range of 30% by mass or less in the total resin solid content.

[Component (C)]
The photopolymerization initiator (C) used in the present invention is not particularly limited as long as radicals are generated by the action of light. For example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2- Acetophenones such as methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, -Anthraquinones such as ethyl anthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2 Thioxanthones such as chlorothioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone, 2,4, Examples thereof include phosphine oxides such as 6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. These may be used alone or in combination of two or more.

Among them, it is preferable to use a photopolymerization initiator having absorption bands in UVB (wavelength region of 280 nm or more and less than 315 nm) and UVC (wavelength region of 200 nm or more and less than 280 nm). By using a photopolymerization initiator having an absorption band in such a wavelength region, it is possible to increase the efficiency of radical polymerization reaction, and from the viewpoint of improving the scratch resistance because the crosslinking reaction proceeds in the coating surface region. It can be preferably used. Further, such a photopolymerization initiator preferably has a melting point of 70 ° C. or higher, more preferably 80 ° C. or higher. By using a photopolymerization initiator having a melting point of 70 ° C. or higher, it is possible to prevent the storage stability of the energy ray curable resin composition from being lowered. In the case where the solvent added as needed is thermally dried, it is also preferable from the viewpoint of workability that the heating temperature can be set higher.

The content of the component (C) in such an energy ray curable resin composition of the present invention is 0.5 parts by mass or more, further 1 part by mass as a lower limit with respect to 100 parts by mass of the energy ray curable resin solid content. Preferably, the upper limit is 10 parts by mass or less, and more preferably 7 parts by mass or less.

Such (C) component can use a commercial item, for example, Irgacure 184,651,500,907,369,784,2959, Darocur 1116,1173, Lucyrin TPO (made by BASF), Ubekrill P36 (UCB) Co., Ltd.), Isacure KIP150, KIP100F, ONE (Lamberti Co., Ltd.) and the like.

[(D) component]
It is preferable to add a photopolymerization initiation assistant as the component (D) to the energy beam curable resin composition of the present invention. By adding the photopolymerization initiation aid, when the energy ray curable resin composition of the present invention is cured by irradiation with energy rays, it is possible to prevent oxygen inhibition from occurring on the cured product surface. A cured product having high hardness can be obtained. Examples of such photopolymerization initiation assistants include amine compounds, carboxylic acid compounds, and polyfunctional thiol compounds. Such photopolymerization initiation assistants may be used alone or in combination of two or more. However, since the efficiency of radical polymerization reaction can be further improved, the polyfunctional thiol It is preferably used so as to contain a compound.

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4- 2-ethylhexyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) Mention may be made of aromatic amine compounds such as benzophenone.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, Aromatic heteroacetic acids such as N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid can be mentioned.

Examples of the polyfunctional thiol compound include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhiol. Glycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, 1,3,5-tris (3-Mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trishydroxyethyltristhiopropione DOO, pentaerythritol tetrakis (3-mercapto butanoate), 1,4-bis (3-mercapto-butoxy) can be mentioned butane. Among these, the secondary thiol compound 1,3,5-tris (3-mercapubutbutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is It is preferable at the point which is excellent in storage stability.

The content of the component (D) in the energy beam curable resin composition of the present invention is 0.1 parts by mass or more as a lower limit with respect to 100 parts by mass of the energy beam curable resin solid content, and 5 as an upper limit. It is preferable that the amount is not more than 3 parts by mass, more preferably not more than 3 parts by mass.

Furthermore, the energy beam curable resin composition of the present invention may contain other resins, solvents, leveling agents, antifoaming agents, ultraviolet absorbers, light stabilizers, as necessary, as long as the effects of the present invention are not impaired. Agent, antioxidant, polymerization inhibitor, crosslinking agent, pigment, antifouling agent, lubricant, fluorescent whitening agent, antistatic agent, flame retardant, antibacterial agent, antifungal agent, plasticizer, flow regulator, dispersant Additives such as mold release agents can be added to impart the desired functionality.

The solvent agent is not particularly limited, and any solvent agent that does not contain a functional group capable of reacting with the component (A), the component (B), and the component (E) can be preferably used. Preferred solvents include aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate and methoxypropyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; diethyl ether Ether solvents such as dibutyl ether, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and the like. The type of organic solvent to be used is determined in consideration of the solubility of the resulting resin and the polymerization temperature, but the boiling point of methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, etc. is 120 ° C. or less in terms of the difficulty of remaining the residual solvent during drying. The organic solvent is preferable. These may be used alone or in combination of two or more. The amount of solvent used is not particularly limited, but is preferably adjusted so that the viscosity of the composition is suitable for the coating method employed. A preferred use amount is 5 to 90% by mass, more preferably 10 to 85% by mass, and still more preferably 20 to 80% by mass of the entire energy ray curable resin composition.

Examples of leveling agents include fluorine compounds, silicone compounds, acrylic compounds, and the like. Examples of the antioxidant include phenolic compounds. Examples of the polymerization inhibitor include methoquinone, methylhydroquinone, hydroquinone and the like, and examples of the crosslinking agent include polyisocyanates and melamine compounds. Examples of the pigment include inorganic fine particles such as silica and calcium carbonate, and organic fine particles such as polymethyl methacrylate and polystyrene. The antifouling agent can include a fluorine compound, a silicon compound, or a mixture thereof, and a fluorine compound is preferred from the antifouling performance.

The energy beam curable resin composition of the present invention includes the above-described components (A), (B), and (C), and if necessary, (D) component, (E) component, solvent, and additives. Can be obtained in any order.

<Hardened product>
Next, the cured product of the present invention will be described. The cured product of the present invention can be obtained by applying the above-described energy beam curable resin composition of the present invention to a desired application target and curing it. As an object to be coated, a substrate for which scratch resistance is desired. The aspect of the substrate that can be used in the present embodiment is not particularly limited, and may have any thickness such as a film shape, a sheet shape, or a plate shape. Further, the surface of the substrate may have, for example, an uneven shape or a three-dimensional shape having a three-dimensional curved surface.

The material of the base material is not particularly limited and may be a hard base material such as a glass plate, but in the present embodiment, a flexible resin base material is preferable. The kind of resin which comprises a resin base material is not specifically limited. For example, as a resin when forming a resin substrate in the form of a film or a sheet, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, poly Vinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluorine resin, nylon, acrylic, A cycloolefin etc. can be mentioned. Examples of the resin when forming the resin base material in a plate shape include acrylic, polycarbonate, polyvinyl chloride, and the like.

In addition, for the purpose of improving the adhesion with the energy ray curable resin composition, surface unevenness treatment by sandblasting method or solvent treatment method, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, plasma treatment Further, surface treatment such as ozone / ultraviolet irradiation treatment, formation of a subbing easy adhesion layer, and the like may be performed. Before applying the energy ray curable resin composition to the base material, one side or both sides may be preliminarily provided with a pressure-sensitive adhesive layer or printing or coating for imparting design properties.

In addition, the base material contains additives similar to the additives that can be contained in the energy ray-curable resin composition of the present embodiment, including pigments and ultraviolet absorbers, as long as the effects of the present invention are not impaired. You may make it contain.

For application of the energy beam curable resin composition to the substrate, known methods such as gravure coating, bar coating, knife coating, roll coating, blade coating, die coating, spin coating, and flow coating are used. Method, dip coating method, spray coating method, screen printing method, brush coating and the like can be used.

When the energy curable resin composition contains a solvent, it is necessary to dry after application. The drying temperature may be determined in consideration of the length of the drying line, the line speed, the coating amount, the residual solvent amount, the type of substrate, and the like. If the substrate is a polyethylene terephthalate film, the general drying temperature is 50 to 150 ° C. When there are a plurality of dryers in one line, each dryer may be set to a different temperature and wind speed. In order to obtain a coating film having a good coating appearance, it is preferable that the drying condition on the inlet side is mild. The coating thickness is not particularly limited, but the film thickness after drying is 0.5 μm or more, further 1 μm or more, further 2 μm or more as the lower limit, and 20 μm or less, further 15 μm or less, further 10 μm or less as the upper limit. Is preferred.

Examples of active energy rays for curing the energy ray curable 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 conveyance speed of 5 to 60 m / min for one lamp having an energy of 80 to 160 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.

<Laminated body>
The laminated body of this invention has a hard-coat layer comprised from the hardened | cured material mentioned above on the at least one surface of a base material. Such a laminate of the present invention is a steel wool test in which the surface of the hard coat layer is subjected to 100 reciprocal frictions at a speed of 200 mm / sec while applying a load of 500 g / 3 cm ² with # 0000 steel wool. The haze difference (ΔH) before and after the steel wool resistance test is 0.5% or less. Thus, in the laminate of the present invention, the hard coat layer is extremely excellent in scratch resistance.

In addition, the laminate of the present invention is a laminate in which the hard coat layer is provided on a polyethylene terephthalate film having a bending resistance value measured by a cylindrical mandrel method according to JIS K5600-5: 1: 1999 and having a value of 50 μm to 188 μm. When it is set as a test piece, it is 16 mm or less. Thus, in the laminate of the present invention, the hard coat layer has a high scratch resistance performance and also has flexibility.

The thickness of the hard coat layer is not particularly limited, but considering the above-mentioned scratch resistance and flexibility, the lower limit is 0.5 μm or more, further 1 μm or more, and further 2 μm or more. Is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less.

Furthermore, in the laminate of the present invention, the hard coat layer has a wet tension measured in accordance with JIS K6768 of 27 mN / m or more and 45 mN / m or less. In particular, when the energy beam curable resin composition of the present invention described above contains a polyfunctional (meth) acrylate monomer having a hydrophilic group as the component (E), the wetting tension measured according to JIS K6768 is high. It can be set to 30 mN / m or more and 40 mN / m or less, and more excellent fingerprint wiping property can be obtained. The reason why the wettability of the fingerprint is improved by setting the wet tension in such a range is not necessarily clear, but when the wet tension is set to 27 mN / m or more, the aqueous component in the fingerprint is appropriately adjusted to the surface of the hard coat layer. It becomes easier, and it is considered that when the fingerprint component is wiped off, the oily component hardly remains on the surface of the hard coat layer and the fingerprint wiping property is improved. In addition, by setting the wetting tension to 40 mN / m or less, the aqueous component in the fingerprint does not become too familiar, so when wiping off the fingerprint component, the aqueous component is less likely to remain on the surface of the hard coat layer. Is thought to improve.

The laminate of the present invention has at least one layer including a metal vapor-deposited layer, a printed layer and an adhesive layer on at least one surface of the substrate. That is, as a configuration of the laminate in the present invention, for example, any one of a metal vapor-deposited layer, a printed layer, and an adhesive layer on a substrate on the surface opposite to the surface having the hard coat layer of the substrate, or these A structure in which any two or more layers are laminated, one of a metal vapor-deposited layer, a printed layer, and an adhesive layer on one hard coat layer having a hard coat layer on both sides of the substrate, or any of these The structure which laminated | stacked two or more layers, and also the structure which has a metal vapor deposition layer or a printing layer in one side of a base material, has a hard-coat layer in the upper layer, and also has an adhesive layer in the upper layer can be mentioned. However, the laminate of the present invention is not limited to these configurations.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Moreover, unless otherwise indicated, in an Example, a part shows a mass part.

(hardness)
The pencil scratch value on the surface of the hard coat layer of the laminate of the present invention was measured by a method based on JIS K5400.

(Abrasion resistance)
As a steel wool resistance test, a steel wool of # 0000 covered with a 3 cm ² cylindrical jig was placed on the hard coat layer of the present invention, and the load was applied to a weight of 500 g and reciprocated 100 times at a speed of 200 mm / sec. The state of the hard coat layer was observed. As a result, the case where there were no scratches was indicated as ◯, the case where there were several scratches as Δ, and the case where there were dozens of scratches as X.

Further, the haze before and after the steel wool resistance test of the laminate of the present invention was measured using a turbidimeter (haze meter NDH4000: manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K7136 to obtain a haze difference (ΔH). It was. In the measurement, light was incident from the surface having the hard coat layer.

(Flexibility)
The value of the bending resistance test of the laminate of the present invention measured by the cylindrical mandrel method according to JIS K5600-5-1: 1999 was recorded.

(Fingerprint wiping)
The wetting tension of the hard coat layer of the laminate of the present invention was measured by a method based on JIS-K6768. In addition, the surface of the hard coat layer of the laminate of the present invention is wiped by applying a load of 500 g / cm ² using a soft cloth with a human-made fingerprint, and the number of times the fingerprint cannot be visually confirmed is measured. The fingerprint wiping property was determined as follows. Those that were within 3 round trips were marked with ◯, and those with 4 round trips or more.

(Surface condition of hard coat layer)
About the surface state of the hard-coat layer of the laminated body of this invention, the hard-coat layer side was visually observed from diagonally under the three wavelength fluorescent lamp. As a result, ◎ if the wave is completely mirrored without any undulations, ◯ if the wave is almost mirrorless without any undulations, and the surface flatness is slightly worse with undulations confirmed. Δ.

The components (A) to (E) used in the examples and comparative examples are as follows.

Component (A1): Aliphatic urethane acrylate oligomer (trade name: Art Resin UN-904, manufactured by Negami Kogyo Co., Ltd., number of energy ray-curable functional groups: 10).

(A2) component: aliphatic urethane acrylate oligomer (trade name: Art Resin UN-3320HS, manufactured by Negami Kogyo Co., Ltd., number of energy ray-curable functional groups: 15).

(B1) component: ethylene oxide-modified dipentaerythritol hexaacrylate monomer (trade name: NK ester ADPH12E, manufactured by Shin-Nakamura Chemical Co., Ltd., number of ethylene oxide chains: 12).

(B2) component: isocyanuric acid ethylene oxide modified triacrylate monomer (trade name: Aronix M315, manufactured by Toagosei Co., Ltd., cyclo ring structure, number of ethylene oxide chains: 3).

(B3) component: dendritic polyfunctional polyester acrylate oligomer (trade name: Viscote V # 1000, manufactured by Osaka Organic Chemical Industry Co., Ltd., number of energy ray-curable functional groups: 3).

Component (C1): 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by BASF, melting point: 70 to 75 ° C.)

Component (C2): 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name: Irgacure 2959, manufactured by BASF Corporation, melting point: 87-92 ° C)

Component (D): 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (trade name: Karenz MT NR1, manufactured by Showa Denko).

(E) component: pentaerythritol triacrylate monomer (trade name: NK ester A-TMM-3LM, manufactured by Shin-Nakamura Chemical Co., Ltd., hydrophilic group: hydroxyl group, number of energy ray-curable functional groups: 3).

Other resin 1: Aliphatic urethane acrylate monomer (trade name: Purple light UV7600B, manufactured by Nippon Synthetic Chemical Co., Ltd., number of energy ray-curable functional groups: 6).

Other resin 2: ethylene oxide-modified glycerin triacrylate monomer (trade name: NK ester A-gly-20E, manufactured by Shin-Nakamura Chemical Co., Ltd., number of ethylene oxide chains: 20).

Leveling agent: Polyether-modified polydimethylsiloxane (trade name: BYK-331, manufactured by Big Chemie Japan)

Example 1
(A1) 80 parts by mass, (B1) 20 parts by mass, (C1) 3 parts by mass, (D) 1 part by mass, methyl ethyl ketone (MEK) 75 parts by mass, propylene glycol monomethyl ether (PGM) 75 parts by mass, and stirring The energy ray-curable resin composition of Example 1 having a solid content of 41% was prepared by adding.

Next, this energy ray curable resin composition was applied to the surface of a polyethylene terephthalate film (trade name: Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 188 μm as a base material using a Baker type applicator, and 140 ° C. Was dried for 2 minutes, and a hard coat layer having a film thickness of 6 μm was formed by effecting irradiation with ultraviolet rays of 300 mJ / cm ² to obtain a laminate of Example 1. Table 1 shows the composition of the energy beam curable resin composition and the evaluation results of the laminate.

Examples 2 to 15
Using each of the energy ray curable resin compositions having the compositions shown in Tables 1 to 3, a laminate was produced in the same manner as in Example 1. In Examples 11 to 13, the thickness of the hard coat layer was 3 μm. Moreover, about the laminated body of Example 14, the base material was made into a 100-micrometer-thick polyethylene terephthalate film (brand name: Cosmo Shine A4300, Toyobo Co., Ltd.), and the film thickness of the hard-coat layer was 10 micrometers. The evaluation results of these laminates are also shown in the same table.

Comparative Examples 1-7
Using each of the energy ray curable resin compositions having the compositions shown in Tables 3 and 4, laminates were produced in the same manner as in Example 1. The composition of these energy beam curable resin compositions and the evaluation results of the laminate are shown in the same table.

From Tables 1 to 3, it can be seen that any of Examples 1 to 15 is excellent in pencil hardness, scratch resistance, and flexibility. In particular, in Examples 11 to 13, it can be understood that even though the hard coat layer is a thin film of 3 μm, it is a laminate excellent in scratch resistance. Moreover, about Example 14, although the film thickness of a hard-coat layer is 10 micrometers and it is a thick film compared with another Example, it can understand that it is a laminated body excellent in the softness | flexibility.

In Examples 1 to 14, since the wetting tension was 27 mN / m or more and 45 mN / m or less, the lamination was excellent in fingerprint wiping property as compared with Example 15 in which the wetting tension was less than 22.6 mN / m. I can understand that it is a body.

As can be seen from Tables 3 and 4, in Comparative Examples 1, 3, and 5, since the blending ratio of the component (A) is small, the scratch resistance is inferior. It can be understood that Comparative Examples 2 and 6 are inferior in flexibility because of the large proportion of component (A). In Comparative Example 4, since a resin having a large number of ethylene oxide chains is used, it can be understood that the flexibility is good but the scratch resistance is poor.

In Comparative Examples 2 to 7, the component (A) or the component (B) was not contained, or the blending ratio was outside the range of 60:40 to 95: 5 by mass ratio. It can be understood that it is not satisfactory. As for Comparative Example 7, since the wetting tension of the hard coat layer was less than 22.6 mN / m, it is not shown in the table. The fingerprint wiping property was remarkably inferior compared with Examples 1 to 14 and Comparative Examples 2 to 6.

Claims (13)

(A) a polyfunctional urethane (meth) acrylate oligomer having an energy ray-curable functional group number in the range of 10 to 20 and (B) a cyclo ring structure having an energy ray-curable functional group number in the range of 2 to 6 ( Contains at least one selected from a (meth) acrylate monomer, a (meth) acrylate monomer having 3 to 15 ethylene oxide chains, and a (meth) acrylate oligomer having a dendritic structure, and (C) a photopolymerization initiator An energy ray curable resin composition characterized in that a blending ratio of the component (A) and the component (B) is in a range of 60:40 to 95: 5 by mass ratio. Resin composition. The energy ray curable resin composition according to claim 1, wherein the component (C) contains a photopolymerization initiator having a melting point of 70 ° C or higher. 2. The energy ray-curable resin composition according to claim 1, comprising a photopolymerization initiation assistant as component (D). The energy ray-curable resin composition according to claim 3, wherein the (D) photopolymerization initiation assistant is a polyfunctional thiol compound. The energy ray curable resin composition according to claim 3, wherein the content of the component (D) is 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the resin solid content. The energy ray-curable resin composition according to claim 1, comprising a polyfunctional (meth) acrylate monomer having a hydrophilic group as the component (E). A cured product obtained by curing the energy beam curable resin composition according to claim 1. A laminate having a hard coat layer composed of the cured product according to claim 7 on at least one surface of a substrate. In the steel wool test in which the surface of the hard coat layer is subjected to 100 reciprocating friction at a speed of 200 mm / sec while applying a load of 500 g / 3 cm ² with # 0000 steel wool, the difference in haze before and after the steel wool resistance test The laminate according to claim 8, wherein (ΔH) is 0.5% or less. When the test piece is a polyethylene terephthalate film having a flexural resistance test value of 50 μm to 188 μm measured by a cylindrical mandrel method according to JIS K5600-5-1: 1999, the test piece is 16 mm or less. The laminate according to claim 8 or 9, wherein there is a laminate. The laminate according to claim 8, wherein the hard coat layer has a thickness of 0.5 μm or more and 20 μm or less. The laminate according to claim 8, wherein the hard coat layer has a wet tension measured in accordance with JIS K6768 of 27 mN / m or more and 45 mN / m or less. 9. The laminate according to claim 8, wherein the laminate has at least one layer including a metal vapor-deposited layer, a printed layer, and an adhesive layer on at least the other surface of the substrate.