TW201418379A - Energy ray-curable resin composition, cured product and laminate - Google Patents

Abstract

Provided are: an energy ray-curable resin composition which provides a coating film that has excellent scratch resistance and sufficient flexibility when cured; a cured product; and a laminate. An energy ray-curable resin composition of the present invention contains (A) a polyfunctional urethane (meth)acrylate oligomer that has 10-20 energy ray-curable functional groups, (B) at least one substance that is selected from among (meth)acrylate monomers having a cyclo ring structure and 2-6 energy ray-curable functional groups, (meth)acrylate monomers having 3-15 ethylene oxide chains and (meth)acrylate oligomers having a dendritic structure, and (C) a photopolymerization initiator. The blending ratio by mass of the component (A) to the component (B) is within the range from 60:40 to 95:5.

Description

Energy ray hardening resin composition, hardened material and laminated body

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

Hard coating film has been widely used for display screens of displays, touch panels, mobile phones, etc., especially mobile products such as touch panels, mobile phones, and smart phones are often touched by fingers or pens and other objects. The occurrence of scratches on the surface becomes a problem. From the viewpoint of preventing scratches, it is only necessary to form a coating film excellent in scratch resistance and pencil hardness, but such a coating film lacks flexibility, and thus, when performing press working to form a display, a touch panel, a mobile phone, and wisdom When the shape of the display screen of a mobile phone or the like is changed, cracks occur and the debris accompanying the crack becomes a foreign matter. Therefore, a hard coat film which can maintain hardness and has flexibility has been proposed (Patent Document 1 and Patent Document 2).

Patent Document 1: Japanese Laid-Open Patent Publication No. 2007-46031 (Patent Application No. 1)

Patent Document 2: Japanese Laid-Open Patent Publication No. 2010-70602 (Patent Application No. 1)

However, the hard coat film proposed in Patent Document 1 or Patent Document 2 has improved flexibility, but is insufficient in terms of scratch resistance. Further, as a method of improving the flexibility, it is also considered to reduce the thickness of the coating film, but at this time, there is also a problem that the scratch resistance is lowered.

On the other hand, with the demand for the thinning of recent mobile phones or smart phones, there is a growing demand for a hard coat film which is excellent in scratch resistance and pencil hardness even though it is a film. In the case of a film having a film thickness of 5 μm or less, it is generally difficult to obtain scratch resistance due to polymerization inhibition by oxygen. As a method for eliminating this problem, a method of coating under nitrogen purge is considered, but the method is relatively expensive. Operating costs are not practical in terms of productivity.

Therefore, an object of the present invention is to provide an energy ray-curable resin composition, a cured product, and a laminate which can improve the above-mentioned disadvantages and which can form a coating film which is excellent in scratch resistance at the time of curing and which has sufficient flexibility.

In order to solve the above problems, the present inventors have made an effort to solve the above problems, and as a result, it has been found that the energy ray-curable resin composition containing a specific compound in a specific ratio can solve the above problems, and the present invention has been completed.

That is, the energy ray-curable resin composition of the present invention is as follows:

[1] The energy ray-curable resin composition of the present invention contains: (A) an oligomeric urethane (meth) acrylate oligomer having an energy ray-curable functional group of 10 to 20 (B) a (meth) acrylate monomer having an energy ray-hardening functional group number of 2 to 6 and having a ring structure, and a (meth) acrylate monomer having 3 to 15 ethylene oxide chains; And at least one of (meth) acrylate oligomers having a dendritic structure; and (C) a photopolymerization initiator; the energy ray-curable resin composition characterized by the above (A) component and The blending ratio of the component (B) is in the range of 60:40 to 95:5 by mass ratio.

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

[3] The energy ray-curable resin composition according to [1], which comprises photopolymerization The starting aid is used as the component (D).

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

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

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

The hardened material of the present invention is as follows:

[7] A cured product obtained by curing the energy ray-curable resin composition according to [1].

The layered system of the present invention is as follows:

[8] A laminate comprising a hard coat layer comprising a cured product according to [7] on at least one side of a substrate.

[9] The laminate according to [8], wherein a load of 500 g/3 cm ² is applied to one surface of the hard coat layer using a steel wool of #0000, and 100 times at a speed of 200 mm/sec. In the steel wool resistance test for the round-trip friction, the haze difference (ΔH) before and after the steel wool resistance test was 0.5% or less.

[10] The laminated body according to [8] or [9], wherein the hard coat layer is formed of a polyethylene terephthalate film of 50 μm to 188 μm as a test piece, and the use basis is used. The value of the bending resistance test measured by the cylindrical mandrel method of JIS K5600-5-1:1999 is 16 mm or less.

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

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

[13] The laminate according to [8], wherein at least one of the metal vapor-deposited film, the printed layer, and the adhesive layer is provided on at least one other surface of the substrate.

According to the present invention, it is possible to provide an energy ray-curable resin composition, a cured product, and a laminate which can form a coating film having scratch resistance and sufficient flexibility at the time of curing.

Hereinafter, each aspect of the energy ray-curable resin composition, the cured product, and the laminated body of the present invention will be specifically described. However, the present invention is not limited to the following aspects, and it is usually within the scope of the gist of the present invention. It is also within the scope of the invention to appropriately change, improve, etc. the following embodiments.

<Energy ray hardening type resin composition>

The energy ray-curable resin composition of the present invention contains: (A) a polyfunctional amine ester (meth) acrylate oligomer having an energy ray-curable functional group number of 10 to 20; and (B) a functional group selected from the group consisting of a (meth) acrylate monomer having a ring structure in the range of 2 to 6, a (meth) acrylate monomer having 3 to 15 ethylene oxide chains, and a (meth) acrylate oligomerization having a dendritic structure (C) a photopolymerization initiator; (D) a photopolymerization initiation aid; and (E) a polyfunctional monomer having a hydrophilic group. Each component will be described in detail below.

[(A) ingredient]

In the energy ray-curable resin composition of the present invention, it is necessary to use (A) a polyfunctional amine ester (meth) acrylate oligomer having an energy ray-curable functional group of 10 to 20. By using such a polyfunctional amine ester (meth) acrylate oligomer, a high degree of crosslinking can be achieved, so that the desired hardness and scratch resistance can be obtained. When the number of the energy ray-curable functional groups of the polyfunctional amine ester (meth) acrylate oligomer is 10 or more, the crosslinking density can be increased and the hardness can be improved, and in particular, the scratch resistance can be drastically improved. In addition, when the number of functional groups is 20 or less, preferably 16 or less, it is possible to suppress steric hindrance due to an excessively high crosslinking density, and it is possible to prevent a decrease in hardness due to hardening inhibition.

Such an amine ester (meth) acrylate is a reaction product of an isocyanate compound obtained by reacting a polyhydric alcohol with a diisocyanate and a (meth) acrylate monomer having a hydroxyl group, and examples of the polyhydric alcohol include a polyester polyol. Polyether polyol, polycarbonate diol, and the like. These may be used alone or in combination of two or more. Further, (meth) acrylate means acrylate or methacrylate.

The method for producing the polyester polyol for producing the amine ester (meth) acrylate oligomer is not particularly limited, and a known production method can be employed. For example, the diol may be subjected to a polycondensation reaction with a dicarboxylic acid or a dicarboxylic acid chloride, or a diol or a dicarboxylic acid may be esterified to carry out a transesterification reaction. Examples of the dicarboxylic acid include adipic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, sebacic acid, maleic acid, terephthalic acid, isophthalic acid, and o-benzene. Formic acid, etc. 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. Wait. These dicarboxylic acids or diols may be used alone or in combination of two or more.

As the polyether polyol, a polyethylene oxide, a polypropylene oxide, an ethylene oxide-propylene oxide random copolymer, and a number average molecular weight of less than 600 are preferable. The reason for this is that if it is 600 or more, the cured product may be excessively soft and the hard coat performance may not be obtained.

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

As the diisocyanate, a linear or cyclic aliphatic diisocyanate is used. The reason for this is that the aromatic diisocyanate can of course be used, and it is possible to more easily obtain excellent hard coat properties such as hardness and scratch resistance, but on the other hand, in the main component of the skeleton forming the hard coat layer, When the aromatic component is used for a polyfunctional oligomer, the light resistance is lowered, and yellowing is likely to occur due to exposure to light, so that the function as a transparent hard coat layer is impaired in practical use. Typical examples of the linear or cyclic aliphatic diisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated methylphenyl diisocyanate, and hydrogenation. Stretching diisocyanate and the like. These may be used alone or in combination of two or more.

[(B) ingredients]

The energy ray-curable resin composition of the present invention must use a (meth) acrylate monomer having a ring structure of an energy ray-curable functional group of 2 to 6 and having a ring structure, and having 3 to 15 ethylene oxide chains ( At least one of a methyl acrylate monomer and a (meth) acrylate oligomer having a dendritic structure. By using these ingredients, it is possible to maintain hardness, especially It is a cured product with excellent scratch resistance and excellent flexibility.

[(meth)acrylate monomer having an energy ray-hardening functional group number of 2 to 6 and having a ring structure]

As described above, in the present invention, a (meth) acrylate monomer having an energy ray-curable functional group of 10 to 20 is used as the component (A), so that it is easy to obtain a cured product compared with a general hard coat cured product. Although a cured product having a high density and a high hardness is crosslinked, on the other hand, there is a tendency that the flexibility is lowered due to a high crosslinking density. However, in the present invention, a (meth) acrylate monomer having a ring structure can be used as the component (B). Therefore, by crosslinking the component (B) with the component (A), it is possible to suppress the formation of a cured product. The joint density becomes too high, and the ring structure can alleviate the rigidity of the cured product having a high crosslink density, so that the hardness, particularly the scratch resistance property can be maintained and the softness can be imparted when the cured product is formed. In such a (meth) acrylate monomer having a ring structure, the number of energy ray-curable functional groups must be 2 or more and 6 or less. When the number of energy ray-curable functional groups is 2 or more, the component (A), the component (B), or the component (B) can be sufficiently cross-linked, so that the hardness can be prevented, especially when the cured product is formed. Softness is imparted when the scratch resistance is lowered. When the number of energy ray-curable functional groups is 6 or less, it is possible to suppress steric hindrance due to excessively high crosslinking density, and it is possible to prevent a decrease in hardness.

The ring system constituting the (meth) acrylate monomer having a ring-structure of the energy ray-curable functional group of 2 to 6 and containing at least 1 selected from the group consisting of carbon, nitrogen, oxygen, and hydrazine It is composed of various elements, preferably a 5-member ring or a 6-member ring. By forming a 5-membered ring or a 6-membered ring, the rigidity of the cured product having a high crosslinking density can be alleviated, and the hardness, particularly the scratch resistance, can be maintained and the flexibility can be easily imparted. Specific examples of the ring structure include cycloolefins such as cyclopentene and cyclohexene, tetrahydrofuran, and 1,3-diene. Alkane, ε-caprolactone, ε-caprolactam, silacyclopentene, cyclodecane, isodecyl, and the like. Examples of the (meth) acrylate monomer having the above ring structure include ε-caprolactone-modified tris(2-propenyl methoxyethyl) trimeric isocyanate and ε-caprolactone modified three ( 2-hydroxyethyl)trimeric isocyanate, dimethyloltricyclodecane di(meth)acrylate, isodecyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-propene oxime Ethyl hexahydrophthalic acid, tricyclodecane dimethanol di(meth) acrylate, tricyclodecane diethanol di(meth) acrylate, tetracyclododecane di(meth) acrylate Etham, (meth)acrylic acid, dicyclohexyl ester, and the like. These may be used alone or in combination of two or more.

[(meth)acrylate monomer having 3 to 15 ethylene oxide chains]

Next, a 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), crosslinking of the component (B) and the component (A) can be suppressed, and formation of a cured product can be suppressed. The crosslinking density becomes too high, and the oxyethylene chain can relax the rigidity of the cured product having a high crosslinking density, so that the hardness, particularly the scratch resistance property can be maintained and the flexibility can be imparted when the cured product is formed. In such a (meth) acrylate monomer having an oxyethylene chain, the oxyethylene chain must be three or more and 15 or less. When the number of the oxyethylene chains is three or more, the rigidity of the cured product having a high crosslinking density can be alleviated, so that when the cured product is formed, flexibility can be imparted without lowering the hardness, particularly the scratch resistance. By setting the oxyethylene chain to 15 or less, it is possible to prevent the crosslinking density from being excessively lowered, and it is possible to prevent the hardness, particularly the scratch resistance, from being lowered when the cured product is formed.

As such a (meth) acrylate having 3 to 15 ethylene oxide chains, for example, oxidation of polyethylene glycol (meth) acrylate or dipentaerythritol hexaacrylate is exemplified. Ethylene modified body, neopentyl alcohol tri(meth) acrylate ethylene oxide modified body, trimethylolpropane tri(meth) acrylate ethylene oxide modified body, and the like. These may be used alone or in combination of two or more.

[(meth)acrylate oligomer having a dendritic structure]

Next, a case where a (meth) acrylate oligomer having a dendritic structure is used as the component (B) will be described. The dendritic structure refers to a shape in which a monomer is polymerized from one core to a radial branch to expand into a radial shape. When a (meth) acrylate oligomer having a dendritic structure is used as the component (B), crosslinking of the component (B) and the component (A) can be suppressed, and crosslinking density at the time of forming a cured product can be suppressed. It becomes too high, and the radiation-like structure can relax the rigidity of the cured product having a high crosslinking density, so that the hardness, particularly the scratch resistance property can be maintained and the softness can be imparted 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.

The component (B) is a (meth) acrylate monomer having a ring structure selected from the group consisting of energy ray-curable functional groups of 2 to 6 and having a ring structure, and a (meth) acrylate having 3 to 15 ethylene oxide chains. At least one of a monomer and a (meth) acrylate oligomer having a dendritic structure may be used alone or in combination.

The blending ratio of the component (A) and the component (B) described above must be in the range of 60:40 to 95:5 by mass. When the addition ratio of the component (A) is 60 or more, and preferably 70 or more, when the energy ray-curable resin composition of the present invention is cured, a cured product having sufficient hardness can be obtained, and fingerprint erasability can be obtained. effect. Also, by making the component (A) When the addition ratio is 95 or less, preferably 90 or less, the crosslinking density can be suppressed from becoming too high, and a cured product having flexibility can be formed.

[(E) component]

Further, in the present invention, a polyfunctional (meth) acrylate monomer having a hydrophilic group may be contained as the component (E) as needed. The fingerprint erasability can be further improved by using a polyfunctional (meth) acrylate monomer having a hydrophilic group. Examples of the hydrophilic group include a hydroxyl group, a carboxyl group, an amine group, a carbonyl group, a sulfonyl group, an ether group and the like. Examples of the polyfunctional (meth) acrylate monomer having such a hydrophilic group include neopentyl alcohol tris(methyl). Acrylate, dipentaerythritol hexa(meth) acrylate, trimethylolpropane (meth) acrylate, and the like. These may be used alone or in combination of two or more. The content of the component (E) in the energy ray-curable resin composition of the present invention is preferably in the range of 30% by mass or less based on the total resin solid content.

[(C) ingredient]

The photopolymerization initiator used as the component (C) of the present invention is not particularly limited as long as it can generate a radical by the action of light. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether and other benzoin; 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- Acetophenones such as (methylthio)phenyl]-2-morpholinopropan-1-one; 2-ethylhydrazine, 2-tris-butylphosphonium, 2-chloroindole, 2-pentyl Equivalent oxime; 2,4-diethyl thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone and other thioxanthones; phenyl Ketals such as ketodimethyl ketal and diphenylethylenedione dimethyl ketal; diphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, 4,4'-double Diphenyl ketones such as methylaminodiphenyl ketone; 2,4,6-trimethyl benzophenone A phosphine oxide such as decyldiphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide. These may be used alone or in combination of two or more.

Among them, a photopolymerization initiator having an absorption band 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) is preferably used. By using a photopolymerization initiator having an absorption band in the above wavelength range, the efficiency of the radical polymerization reaction can be increased, and the crosslinking reaction progresses in the surface region of the coating film, so that the scratch resistance is improved, and in view of this, Good to use. Further, such a photopolymerization initiator is preferably one having a melting point of 70 ° C or higher and further 80 ° C or higher. By using a photopolymerization initiator having a melting point of 70 ° C or higher, the storage stability of the energy ray-curable resin composition can be prevented from being lowered, and further, when the cured product is formed, the energy ray-curable resin composition is observed. In the case where the solvent to be added is thermally dried, it is also preferable from the viewpoint of setting the heating temperature to a high workability.

The content of the component (C) in the energy ray-curable resin composition of the present invention is preferably 0.5 parts by mass or more, more preferably 1 part by mass based on 100 parts by mass of the energy ray-curable resin solid content component. The upper limit is preferably 10 parts by mass or less, more preferably 7 parts by mass or less.

A commercially available product can be used as the component (C), and examples thereof include Irgacure 184, 651, 500, 907, 369, 784, 2959, Darocur 1116, 1173, Lucirin TPO (manufactured by BASF Corporation), and Uvecryl P36 (manufactured by UCB Corporation). ); Esacure KIP150, KIP100F, ONE (manufactured by Lamberti), etc.

[(D) ingredient]

In the energy ray-curable resin composition of the present invention, a photopolymerization initiation aid is preferably added as the component (D). By adding a photopolymerization initiation aid, it is prevented by irradiation of energy rays When the energy ray-curable resin composition of the present invention is cured, oxygen barrier is generated on the surface of the cured product, so that a cured product having a higher hardness can be obtained. Examples of such a photopolymerization initiation aid include an amine compound, a carboxylic acid compound, and a polyfunctional thiol compound. These photopolymerization start-up aids may be used singly or in combination of two or more. The polyfunctional thiol compound may further increase the efficiency of the radical polymerization reaction, and therefore it is preferred to use a polyfunctional thiol compound. .

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; for example, methyl 4-dimethylaminobenzoate and ethyl 4-dimethylaminobenzoate Ester, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-di Aromatic such as methyl-p-toluidine, 4,4'-bis(dimethylamino)diphenyl ketone (commonly known as mickleone), 4,4'-bis(diethylamino)diphenyl ketone Amine compound.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxybenzenesulfide. Acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine An aromatic heteroacetic acid such as naphthyloxyacetic acid.

Examples of the polyfunctional thiol compound include hexanedithiol, decanedithiol, 1,4-dimethylnonylbenzene, butanediol dithiopropionate, and butanediol bis-mercaptoacetate. Ethylene glycol bis-mercaptoacetate, trimethylolpropane tridecyl acetate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane tridecyl B Acid ester, neopentyl alcohol tetrathiopropionate, neopentyl alcohol tetradecyl acetate, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, trishydroxyethyltrithiopropionate, pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3- Mercaptobutoxy)butane. Among these, it is a 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-three of a secondary thiol compound. -2,4,6(1H,3H,5H)-trione is preferred in terms of excellent storage stability.

The content of the component (D) in the energy ray-curable resin composition of the present invention is preferably 0.1 part by mass or less, and the upper limit is preferably 5 parts by mass based on 100 parts by mass of the energy ray-curable resin solid content component. Hereinafter, it is more preferably 3 parts by mass or less.

Further, the energy ray-curable resin composition of the present invention may be added with other resins, solvents, or leveling agents, antifoaming agents, ultraviolet absorbers, and light stabilizers as needed within the range not impairing the effects of the present invention. , antioxidants, polymerization inhibitors, crosslinking agents, pigments, antifouling agents, lubricants, fluorescent whitening agents, antistatic agents, flame retardants, antibacterial agents, antifungal agents, plasticizers, fluidity regulators Additives such as dispersants and release agents give the functionality of each target.

The solvent is not particularly limited as long as it does not contain a functional group reactive with the above components (A), (B) and (E). Preferred examples of the solvent include aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, and methoxypropyl acetate; acetone and methyl groups; a ketone solvent such as ethyl ketone, methyl isobutyl ketone or cyclohexanone; diethyl ether, dibutyl ether, tetrahydrofuran, 1,3-dioxane, 1,4-two An ether solvent such as an alkane, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether or diethylene glycol ethyl methyl ether; and other known organic solvents. The type of the organic solvent to be used is determined in consideration of the solubility of the obtained resin and the polymerization temperature, and is preferably methyl ethyl ketone or methyl isobutyl ketone in terms of the extent to which the residual solvent does not easily remain during drying. An organic solvent having a boiling point of 120 ° C or lower, such as tetrahydrofuran. These may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited, and it is preferably adjusted so that the viscosity of the composition becomes a viscosity suitable for the coating method to be employed. The amount of use is preferably from 5 to 90% by mass, more preferably from 10 to 85% by mass, even more preferably from 20 to 80% by mass, based on the total of the energy ray-curable resin composition.

Examples of the leveling agent include a fluorine-based compound, a polyfluorene-based compound, and an acrylic compound. Examples of the antioxidant include a phenol compound and the like. Examples of the polymerization inhibitor include hydroquinone monomethyl ether, methyl hydroquinone, and hydroquinone, and examples of the crosslinking agent include polyisocyanates and melamine compounds. Examples of the pigment include inorganic fine particles such as cerium oxide and calcium carbonate, and organic fine particles such as polymethyl methacrylate or polystyrene. The antifouling agent may, for example, be a fluorine-based compound, an anthraquinone-based compound or a mixture thereof, and is preferably a fluorine-based compound in terms of antifouling properties.

The energy ray-curable resin composition of the present invention may be added in any order (A), (B), and (C), and optionally (D), (E), solvent, and Obtained from additives.

<hardened matter>

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 ray-curable resin composition of the present invention to a desired coating target and hardening it. The object to be coated is a substrate which is expected to have scratch resistance. The aspect of the substrate which can be used in the embodiment is not particularly limited, and may be any thickness such as a film, a sheet or a plate. Further, the surface of the substrate may be, for example, a convex-concave shape, or may have a three-dimensional shape having a three-dimensional curved surface.

The material of the substrate is not particularly limited, and may be a hard substrate such as a glass plate. However, in the present embodiment, a flexible resin substrate is preferable. The type of the resin constituting the resin substrate is not particularly limited. Examples of the resin in the case of forming a resin substrate in the form of a film or a sheet include, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, and polypropylene. , cellophane, diacetyl cellulose, triethylene sulfonate, Ethyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polyfluorene, polyether Ether ketone, polyether oxime, polyether oximine, polyimine, fluororesin, nylon, acrylic, cyclic olefin, and the like. In addition, examples of the resin in the case where the resin substrate is formed in a plate shape include, for example, acrylic, polycarbonate, polyvinyl chloride, and the like.

Further, it is also possible to improve the adhesion to the energy ray-curable resin composition, and to perform surface unevenness treatment such as blasting or solvent treatment, or corona discharge treatment, chromic acid treatment, flame treatment, hot air. Surface treatment such as treatment, plasma treatment, ozone-ultraviolet irradiation treatment, formation of an undercoat easy layer, and the like. On the substrate, an adhesive layer may be formed in advance on one or both sides before application of the energy ray-curable resin composition or to impart design printing or coating.

In addition, the base material may contain an additive similar to the additive which can be contained in the energy ray-curable resin composition of the present embodiment, which is represented by a pigment or an ultraviolet absorber, insofar as it does not impair the effects of the present invention.

The energy ray-curable resin composition may be applied to the substrate by a known method such as a gravure coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, or a die coating method. Method, spin coating method, shower coating method, dip coating method, spray coating method, screen printing method, brush coating, and the like.

When the energy ray-curable resin composition contains a solvent, it is necessary to dry it after coating. The drying temperature may be determined in consideration of the length of the drying line, the line speed, the amount of coating, the amount of residual solvent, the type of the substrate, and the like. If the substrate is a polyethylene terephthalate film, the usual drying temperature is 50 to 150 °C. There are multiple dryers in one line In the shape, each dryer can be set to different temperatures and wind speeds. In order to obtain a coating film having a good coating appearance, it is preferred to set the drying conditions on the inlet side to mild conditions. The coating thickness is not particularly limited, and the film thickness after drying is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 2 μm or more, and the upper limit is 20 μm or less, more preferably 15 μm or less, and still more preferably 10 μm. the following.

Examples of the active energy ray that hardens the energy ray-curable resin composition of the present invention include ultraviolet rays, electron beams, and the like. In the case of curing by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high pressure mercury lamp, a metal halide lamp or the like as a light source is used, and the amount of light, the arrangement of the light source, and the like are adjusted as needed. In the case of using a high-pressure mercury lamp, it is preferred to cure at a transport speed of 5 to 60 m/min per lamp of a lamp having an energy of 80 to 160 W/cm ² . In the case of hardening by an electron beam, it is preferred to use an electron beam accelerating device having an energy of 100 to 500 eV.

<Laminated body>

The laminated system of the present invention has a hard coat layer composed of the above-mentioned cured product on at least one side of the substrate. Thus, the laminate of the present invention is subjected to a steel wool resistant test using a #0000 steel wool, applying a load of 500 g/3 cm ^{2 to} one surface of the hard coat layer, and performing 100 round-trip friction at a speed of 200 mm/sec. Among them, the haze difference (ΔH) before and after the steel wool resistance test was 0.5% or less. As described above, in the laminate of the present invention, the hard coat layer is extremely excellent in scratch resistance.

Further, in the case where the hard coat layer is formed of a polyethylene terephthalate film of 50 μm to 188 μm as a test piece, the laminate according to the present invention is a cylinder according to JIS K5600-5-1:1999. The value of the bending resistance test measured by the mandrel method is 16 mm or less. Thus, in the laminate of the present invention, the hard coat layer has high scratch resistance properties, and It is soft.

The thickness of the hard coat layer is not particularly limited, and in view of the above-mentioned scratch resistance and flexibility, the lower limit is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 2 μm or more, and the upper limit is 20 μm or less, and more preferably It is 15 μm or less, and more preferably 10 μm or less.

Further, in the laminate of the present invention, the wetting tension of the hard coat layer measured according to JIS K6768 is 27 mN/m or more and 45 mN/m or less. In particular, when the energy ray-curable resin composition of the present invention contains a polyfunctional (meth) acrylate monomer having a hydrophilic group as the component (E), the wetting tension measured in accordance with JIS K6768 can be made 30 mN/m or more and 40 mN/m or less can be formed to have superior fingerprint erasability. The reason why the fingerprint wiping property can be improved by the wetting tension within the above range is not clear, but it is considered that it is possible to make the aqueous component in the fingerprint easy to be hard-coated by making the wetting tension 27 mN/m or more. The surface is moderately affinityd, and the oil component does not easily remain on the surface of the hard coat layer when the fingerprint component is wiped off, so that the fingerprint erasability is improved. In addition, it is considered that it is possible that the water-repellent component in the fingerprint does not become too easy to be affinityd by the wetting tension of 40 mN/m or less, so that the aqueous component does not easily remain on the surface of the hard coat layer when the fingerprint component is wiped off, and thus the fingerprint The eraseability is improved.

Further, the laminate of the present invention has at least one layer including a metal deposition layer, a printing layer, and an adhesive layer on at least one side of the substrate. In other words, as a configuration of the laminate of the present invention, for example, a metal deposition layer, a printing layer, and an adhesive layer are laminated on a substrate having a surface opposite to the surface having the hard coat layer. Any one of the layers or any two or more of the layers; having a hard coat layer on both sides of the substrate and stacking one of the metal evaporated layer, the printed layer and the subsequent layer on one of the hard coat layers or a structure of any two or more layers, and a metal deposition layer or a printing layer on one surface of the substrate, and a hard coat layer on the upper layer, and further The upper layer has a structure of an adhesive layer; however, the laminated body of the present invention is not limited to the above configuration.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. In the examples, the parts represent the parts by mass unless otherwise specified.

(hardness)

The pencil scratch value of the surface of the hard coat layer of the laminate of the present invention was measured by the method according to JIS K5400.

(scratch resistance)

As a steel wool resistance test, #0000 steel wool was wrapped on a 3 cm ² cylindrical jig and placed on the hard coat layer of the present invention at a speed of 200 mm/sec under a load of 500 g. Go back and forth 100 times and observe the state of the hard coat. The result of the total flawlessness was evaluated as ○, the number of scars was evaluated as Δ, and the tens of scars were evaluated as ×.

Further, according to JIS K7136, the haze of the laminate of the present invention before and after the steel wool resistance test was measured using a turbidimeter (Haze Meter NDH4000: manufactured by Nippon Denshoku Industries Co., Ltd.) to obtain a haze difference (?H). Further, in the measurement, light was incident from the surface having the hard coat layer.

(softness)

The value of the bending resistance test measured by the cylindrical mandrel method according to JIS K5600-5-1:1999 for the laminated body of the present invention was recorded.

(fingerprint eraser)

The wetting tension of the hard coat layer of the laminate of the present invention was measured by the method according to JIS-K6768. In addition, a fingerprint is attached to the surface of the hard coat layer of the laminate of the present invention, and the load is removed by applying a load of 500 g/cm ² using a soft cloth, and the number of times when the fingerprint cannot be visually confirmed is determined as follows. Fingerprint eraser. It is judged as ○ for three round trips, and × for four round trips or more.

(surface state of hard coating)

Regarding the surface state of the hard coat layer of the laminate of the present invention, the hard coat layer side was visually observed from an oblique direction under a three-wavelength fluorescent lamp. When the results were not confirmed to be undulating and completely formed into a mirror, the evaluation was ◎, and when the undulation was not confirmed, the surface was evaluated as ○, and when the undulation was confirmed, the flatness of the surface was evaluated as Δ.

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

(A1) component: Aliphatic amine ester acrylate oligomer (trade name: Art-Resin UN904, manufactured by Kokusai Industrial Co., Ltd., energy ray-curable functional group number: 10).

(A2) component: Aliphatic amine ester acrylate oligomer (trade name: Art-Resin UN-3320HS, manufactured by Kokusai Kogyo Co., Ltd., energy ray-curable functional group number: 15).

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

(B2) component: isomeric cyanuric acid ethylene oxide modified triacrylate monomer (trade name: Aronix M315, manufactured by East Asian Synthetic Chemical Co., Ltd., ring structure, number of ethylene oxide chains: 3).

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

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

(C2) component: 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).

(D) Component: 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-three -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, energy ray hardening functional group number: 3).

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

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

Leveling agent: polyether modified polydimethyl siloxane (trade name: BYK-331, manufactured by BYK-Chemie Japan)

Example 1

To 80 parts by mass of (A1), 20 parts by mass of (B1), 3 parts by mass of (C1), and 1 part by mass of (D), 75 parts by mass of methyl ethyl ketone (MEK) and propylene glycol monomethyl ether (PGM) 75 are added. The mass fraction was stirred and added to prepare an energy ray-curable resin composition of Example 1 having a solid content of 41%.

Next, the energy ray-curable resin composition was applied to the surface of a polyethylene terephthalate film (trade name: Cosmoshine A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 188 μm as a substrate by using a Baker-type applicator. After drying at ° C for 2 minutes, ultraviolet rays were irradiated at 300 mJ/cm ² to be hardened, whereby a hard coat layer having a film thickness of 6 μm was formed, and the laminate of Example 1 was obtained. The composition of the energy ray-curable resin composition and the evaluation results of the laminate are shown in Table 1.

Example 2~15

A layered product was produced in the same manner as in Example 1 using the energy ray-curable resin composition of the composition shown in Tables 1 to 3, respectively. Further, in Examples 11 to 13, the film thickness of the hard coat layer was set to 3 μm. Further, in the laminate of Example 14, the base material was a polyethylene terephthalate film (trade name: Cosmoshine A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm, and the film thickness of the hard coat layer was set to 10 μm. The evaluation results of the laminates are shown together in Tables 1 to 3.

Comparative Example 1~7

A layered product was produced in the same manner as in Example 1 using the energy ray-curable resin compositions of the compositions shown in Tables 3 and 4, respectively. The composition of the energy ray-curable resin composition and the evaluation results of the laminate are shown in Tables 3 and 4.

As is apparent from observations 1 to 3, any of Examples 1 to 15 was excellent in pencil hardness, scratch resistance, and flexibility. In particular, in Examples 11 to 13, the laminate of the hard coat layer was thinner than 3 μm, but it was a laminate having excellent scratch resistance. Further, in Example 14, it is understood that the thickness of the hard coat layer is 10 μm thicker than that of the other examples, but it is a laminate having excellent flexibility.

Further, it can be understood that in Examples 1 to 14, since the wetting tension was 27 mN/m or more and 45 mN/m or less, fingerprint erasing was compared with Example 15 in which the wetting tension was less than 22.6 mN/m. Excellent laminate.

As is apparent from observations 3 and 4, in Comparative Examples 1, 3, and 5, since the blending ratio of the component (A) was small, the scratch resistance was inferior. In Comparative Examples 2 and 6, since the blending ratio of the component (A) was large, the flexibility was poor. In Comparative Example 4, since a resin having a large number of oxyethylene chains was used, the flexibility was good, but the scratch resistance was inferior.

In addition, it can be understood that in Comparative Examples 2 to 7, since the component (A) or the component (B) is not contained, or the blending ratio is outside the range of 60:40 to 95:5 by mass ratio, the fingerprint is wiped. The sex is unsatisfactory. In Comparative Example 7, since the wetting tension of the hard coat layer was less than 22.6 mN/m, although not shown in the table, even if the fingerprint was wiped off 5 times or more, the fingerprint component only expanded and could not be erased. Compared with Examples 1 to 14 and Comparative Examples 2 to 6, the fingerprint erasability was very poor.

Claims (13)

An energy ray-curable resin composition comprising: (A) a urethane (meth) acrylate oligomer having an energy ray-curable functional group of 10 to 20; B) a (meth) acrylate monomer having an energy ray-curable functional group number of 2 to 6 and having a ring structure, a (meth) acrylate monomer having 3 to 15 ethylene oxide chains, and having At least one of a (meth) acrylate oligomer of a dendritic structure; and (C) a photopolymerization initiator; the energy ray-curable resin composition is characterized by: (A) component and (B) The blending ratio of the components is in the range of 60:40 to 95:5 by mass ratio. The energy ray-curable resin composition according to claim 1, wherein the component (C) comprises a photopolymerization initiator having a melting point of 70 ° C or higher. An energy ray-curable resin composition according to claim 1 which contains a photopolymerization initiation aid as the component (D). The energy ray-curable resin composition of claim 3, wherein the (D) photopolymerization initiation aid is a polyfunctional thiol compound. The energy ray-curable resin composition of the third aspect of the invention, wherein the content of the component (D) is 0.1 part by mass or more and 5 parts by mass or less based on 100 parts by mass of the resin solid content component. An energy ray-curable resin composition according to claim 1 which contains a polyfunctional (meth) acrylate monomer having a hydrophilic group as the component (E). A cured product obtained by hardening an energy ray-curable resin composition of the first application of the patent scope. A laminate having a hardening according to item 7 of the scope of the patent application on at least one side of the substrate A hard coating composed of matter. For example, in the layered body of claim 8, in which the load of 500 g/3 cm ² is applied to the surface of the hard coat layer by using #0000 steel wool, and 100 round trips are performed at a speed of 200 mm/sec. In the friction-resistant steel wool test, the haze difference (ΔH) before and after the steel wool resistance test was 0.5% or less. For example, in the case where the hard coat layer is formed of a polyethylene terephthalate film of 50 μm to 188 μm as a test piece, the use of the laminate according to JIS K5600- The value of the bending resistance test measured by the cylindrical mandrel method of 5-1:1999 is 16 mm or less. The laminate according to the eighth aspect of the invention, wherein the hard coat layer has a thickness of 0.5 μm or more and 20 μm or less. The laminate of the eighth aspect of the patent application, wherein the hard coat layer has a wetting tension of 27 mN/m or more and 45 mN/m or less as measured according to JIS K6768. The laminate according to claim 8, wherein at least one of the metal deposition layer, the printing layer and the adhesive layer is provided on at least one other side of the substrate.