JP4715993B2 - Photocurable coating liquid, curable resin composition, and method for producing laminate using the same - Google Patents

Description

  The present invention relates to a photocurable coating liquid and a curable resin composition as a specific embodiment thereof. More specifically, even when a relatively thin coating is applied to the surface of a substrate having a surface made of a material having a low surface tension, for example, a silicone resin, a fluorine resin, or glass, Photo-curing coating liquid capable of providing uniform and thin (for example, about 0.01 to 10 μm thickness) coating film without occurrence of repellency and pinholes and curable resin composition which is a specific embodiment thereof About. Moreover, this invention relates to manufacture of the laminated body using this photocurable coating liquid or curable resin composition.

  The principle of the antireflection function exhibited by a general antireflection film is that a low refractive index layer is provided on the surface of a high refractive index layer, and the light reflected by the high refractive index layer and the light reflected by the low refractive index layer are those. The reflected light is reduced by interfering with each other using the optical path difference. Image display devices such as liquid crystal display devices and plasma display devices in recent years are not only strongly required to have such an antireflection function, but also have a hard coat function. In such a case, the antireflection film is cured after a coating solution for forming a high refractive index layer is formed on the base material that has been subjected to a hard coating treatment by a dip method or a roll coating method, and further, In addition, a low refractive index layer-forming coating solution is similarly formed and then cured.

  By the way, polyorganosilane is widely used for such hard coat treatment, but since polyorganosilane does not have sufficient wettability to the coating solution, the surface of the polyorganosilane layer formed on the substrate When a coating liquid for forming a high refractive index layer or a coating liquid for forming a low refractive index layer is applied to the film, there is a problem that repelling or pinholes frequently occur. The same problem occurs when applying a photocurable resin coating solution on a plastic substrate or glass substrate that has been surface-treated with a fluororesin or olefin resin with a relatively low surface tension among the resins. Also occurred.

  For this problem, it is conceivable to increase the viscosity of the photocurable resin coating solution, but it becomes difficult to obtain a uniform thin film because the coating becomes difficult. Therefore, a polymerizable compound having an epoxy group and a fluoropolymer are used in combination as a main component of the photocurable resin coating liquid (Patent Document 1), and a fluorosurfactant is added to the photocurable resin coating liquid. It has been proposed to add (Patent Document 2) and to blend a metal alkoxide or a decomposition product thereof into the photo-curable resin coating liquid (Patent Document 3).

JP-A-6-25590 JP-A-11-323255 JP 61-130382 A

  However, in the case of the technique of Patent Document 1, since a fluoropolymer is used, the manufacturing cost of the coating liquid is high, and the epoxy group of the polymerizable compound easily reacts with water. There has been a problem that the storage stability of the coating solution may be greatly reduced. In the case of the technique of Patent Document 2, there is an advantage that the production cost of the coating liquid is low because the amount of the fluorine-containing component added is smaller than that of the technique of Patent Document 1, but the alkoxysilane part is included in the coating liquid. Since the hydrolyzate is contained, as in Patent Document 1, if water is mixed in the coating liquid, the hydrolysis reaction is promoted, so that the storage stability of the coating liquid may be reduced, and There is a concern that the manufacturing cost of the cured resin layer increases because it takes time to thermally cure the coating film of the coating liquid. In the case of the technique of Patent Document 3, a coating solution having relatively good wettability is obtained, and the curing time can be shortened as compared with the thermosetting resin coating solution. As in the case of the technique of Patent Document 2, since hydrolysis of alkoxysilane is necessary, there is a possibility that a problem may occur in the storage stability of the coating liquid.

  In the present invention, a photocurable coating solution or a curable resin composition is made relatively thin with respect to a material that generally repels a coating solution, for example, a substrate having a surface layer made of polyorganosiloxane, polyvinylidene fluoride, or the like. An object of the present invention is to make it possible to form a uniform and thin (for example, about 0.01 to 10 μm thick) coating film without occurrence of repelling or pinholes in the coating film obtained when applied.

  The present inventors can achieve the above-mentioned object by dispersing fine particles of a solid polymerizable material in the photocurable coating solution, instead of making the photocurable coating solution a uniform liquid. The present invention was completed.

The present invention is a photocurable resin composition for coating on a repellent coating liquid base material having a silicone-based hard coat layer surface exhibiting a surface tension of 40 dyn / cm or less at 20 ° C. Components (A) to (C):
(A) A solid photopolymerizable metal salt composed of (meth) acrylic acid and any one of divalent or trivalent metals of calcium, zinc, magnesium and aluminum and having a particle size of 5 nm to 1 μm;
(B) a photopolymerizable ethylenically unsaturated compound containing a polyfunctional monomer; and (C) a photopolymerization initiator, the amount (parts by mass) of component (A) being (Awt), and component (B) providing the amount (parts by mass) to (BWT) and the time in the following formula (1a) and (2a) at least one layer having laminate a photocurable resin composition or Ranaru cured layer satisfying.

Furthermore, the present invention is a method for producing a laminate in which a cured resin layer is laminated on a repellent coating liquid-repellent substrate having a surface of a silicone-based hard coat layer exhibiting a surface tension of 40 dyn / cm or less at 20 ° C. The following steps (a ′) and (b ′):
(A ′) a step of forming a photocurable resin layer comprising the above-mentioned photocurable resin composition on a coating material that is repellent coating; and (b ′) active energy rays on the resulting photocurable resin layer. The method for producing the above-mentioned laminate including the step of curing the photocurable resin layer by irradiating and forming a cured resin layer is also provided.

  According to the photocurable coating solution of the present invention, a uniform and thin film (for example, a thickness of about 0.01 to 10 μm) is formed on the surface of the coating liquid-repellent or low wettability without causing repelling or pinholes. ) A thin film can be formed. Therefore, it can be advantageously used for articles such as a laminate foil, an image display screen protection plate, and a helmet shield.

  The photocurable coating liquid of the present invention is obtained by dispersing fine particles of a solid photopolymerizable substance in a liquid photopolymerizable composition. Here, the meaning of “solid” in the solid photopolymerizable substance means that it exists as a solid in the photocurable coating liquid, and therefore, the solvent type used in the photocurable coating liquid. Depending on the curing conditions, the same photopolymerizable substance may become solid or liquid, but in general, solid photopolymerizable substances are lower alcohols, esters It means a photopolymerizable substance that does not dissolve in a general-purpose solvent such as a liquid and does not exhibit a melting point or a melting point of 150 ° C. or higher. In addition, the “photocurability” of the photocurable coating liquid means a property that is cured by irradiation with active energy rays such as ultraviolet rays, visible rays, electron beams, X-rays, and the like. The “photopolymerization” of a substance means the property of being polymerized by irradiation with active energy rays as described above.

  The photocurable liquid of the present invention having such a structure is generally capable of repelling or pinholes in the obtained coating film even when applied relatively thinly to a substrate having a surface layer made of a material that easily repels the coating liquid. Thus, a coating film that is uniform and thin (for example, about 0.01 to 10 μm thick) can be provided. The reason for this is not clear but is considered as follows.

  That is, when the photocurable coating solution of the present invention is applied to the surface of a substrate having a high repellent coating property, fine particles of a solid photopolymerizable substance are dispersed on the surface. Then, it becomes possible to hold the liquid photopolymerizable composition between the fine particles of the solid photopolymerizable substance or at the boundary between the fine particles and the substrate surface, that is, the fine particles exhibit a coating liquid holding function. This is considered to be because a uniform thin film without repelling or pinholes can be formed.

  In addition, the solid polymerizable substance reacts with the polymerizable component in the liquid photopolymerizable composition surrounding the solid polymerizable substance, so that it is not a mere filler but a component integrated with the cured layer. Therefore, after the polymerization, the boundary between the solid polymer fine particles and the liquid polymerizable composition substantially disappears, and as a result, the hardness becomes higher than the method of adding a simple filler, and the visible light of the cured layer is visible. It can be expected that the optical isotropic properties of

  In the present invention, if the particle size of the solid polymerizable substance is too small, repelling occurs, and if it is too large, the optical isotropy cannot be ensured, so 1 nm to 10 μm, more preferably 5 nm to 1 μm. is there.

  The solid photopolymerizable substance is a substance that exists as a solid without being dissolved in the photocurable coating liquid and is polymerizable with the polymerizable substance dissolved in the coating liquid. For example, a metal salt of a polymerizable substance (polymerizable monomer, oligomer or polymer), preferably a metal salt of an organic carboxylic acid having an unsaturated bond. Here, as the number of unsaturated bonds in the metal salt of the organic carboxylic acid, it is preferable that at least two unsaturated bonds exist in the metal salt from the viewpoint of improving the mechanical strength of the cured layer. Therefore, when there are a plurality of unsaturated bonds in the organic carboxylic acid, a monovalent metal (sodium, potassium, etc.) can be used, but regardless of the number of unsaturated bonds in the organic carboxylic acid, Use of a polyvalent metal is preferable because the range of selection of the organic carboxylic acid having an unsaturated bond is widened. However, if the valence of the metal becomes too large, the metal salt tends to become liquid, and the steric hindrance of the entire metal salt increases, so that unsaturated groups (for example, double bonds) cannot be used effectively, and in the hardened layer In some cases, an unsaturated group may remain. In such a case, the weather resistance of the cured layer may be lowered. Therefore, the valence of the polyvalent metal is preferably divalent or trivalent.

  As the organic carboxylic acid having an unsaturated bond, those capable of forming a solid metal salt by forming a salt with a polyvalent metal or polyvalent metal compound can be used. For example, acrylic acid, methacrylic acid (Hereinafter, acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid. Also, acryloyl group and methacryloyl group are collectively referred to as (meth) acryloyl group.), Crotonic acid, oleic acid, undecenoic acid, 9,12-octadienoic acid, 9,12,15-octatrienoyl acid, etc. are mentioned. Among these, (meth) acrylic acid is particularly preferable in order to form a film having high hardness because a polymer having high reactivity during polymerization is more preferable.

  Specific examples of the divalent metal include beryllium, magnesium, calcium, barium, zinc, and cadmium. Examples of the trivalent metal include cobalt, nickel, and aluminum. These may be single or plural. Among these, calcium, zinc, magnesium, and aluminum are preferable from the viewpoint of safety and availability, and zinc is particularly preferable.

  Preferable specific examples of the solid photopolymerizable substance include calcium (meth) acrylate, zinc (meth) acrylate, magnesium (meth) acrylate, aluminum (meth) acrylate and the like. Of these, zinc (meth) acrylate, particularly zinc acrylate is preferred from the viewpoint of dispersibility in the coating solution.

  On the other hand, the liquid photopolymerizable composition contains a photopolymerizable ethylenically unsaturated compound. Here, the “photopolymerizable” of the photopolymerizable ethylenically unsaturated compound means a property capable of being polymerized by irradiation with active energy rays. Specific examples of such photopolymerizable ethylenically unsaturated compounds include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t -Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenoxy Ethyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl ( ) Acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl ( (Meth) acrylate, biphenoxyethyl (meth) acrylate, biphenoxyethoxyethyl (meth) acrylate, norbornyl (meth) acrylate, phenylepoxy (meth) acrylate, (meth) acryloylmorpholine, diacetone acrylamide, N- [2- ( (Meth) acryloylethyl] -1,2-cyclohexanedicarboximide, N- [2- (meth) acryloylethyl] -1,2-cyclohexanedicarbomido-1-ene, N- Monofunctional (meth) acrylate monomers such as 2- (meth) acryloylethyl] -1,2-cyclohexanedicarbomido-4-ene; N-vinylpyrrolidone, N-vinylimidazole, N-vinylcaprolactam, styrene, Vinyl monomers such as α-methylstyrene, vinyl toluene, allyl acetate, vinyl acetate, vinyl propionate, vinyl benzoate; 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol pivalic acid ester di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tri Tylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol-A-diglycidyl ether di (meth) acrylate, 1,4-cyclohexanedimethanol ethylene oxide modified diacrylate, ethylene oxide modified tetrabromobisphenol- A bifunctional (meth) acrylate such as A-di (meth) acrylate; trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate , Pentaerythritol hexa (meth) acrylate, tri (meth) acrylate of ethylene oxide-added trimethylolpropane, ethylene Side addition ditrimethylolpropane tetra (meth) acrylate, propylene oxide addition trimethylolpropane tri (meth) acrylate, ethylene oxide modified isocyanuric acid tri (meth) acrylate, propylene oxide addition ditrimethylolpropane tetra (meth) acrylate, Tetra (meth) acrylate of ethylene oxide-added pentaerythritol, tetra (meth) acrylate of propylene oxide-added pentaerythritol, penta (meth) acrylate of ethylene oxide-added dipentaerythritol, penta (meth) acrylate of propylene oxide-added dipentaerythritol, Ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide Polyfunctional monomers such as hexa (meth) acrylates of id-added dipentaerythritol, triallyl cyanurate, triallyl isocyanurate, triallyl formal, 1,3,5-triacryloylhexahydro-s-hydrazine; urethane acrylate, Examples include oligomeric acrylates such as ester acrylates. These may be used alone or in combination. Of these, bifunctional or higher functional monomers are preferably used.

  For example, when obtaining a high refractive index cured layer having a refractive index of 1.60 or more, 9,9-bis (acryloyloxyphenyl) fluorene, 9,9- Fluorene-based (meth) acrylates such as bis (EO-modified acryloyloxyphenyl) fluorene and 9,9-bis (epoxy-modified acryloyloxyphenyl) fluorene, bis (4- (meth) acryloyloxythiophenyl sulfide), bis (4- Sulfur-containing compounds such as vinylthiophenyl) sulfide, titanium (meth) acrylate triisopropoxide, titanium (meth) acryloyloxyethyl acetoacetate triisopropoxide, (2- (meth) acryloyloxyethoxy) triisopropoxy titanate, etc. Titanium coupling Agent, it is preferable to use a high refractive polymerizable compound such.

  In addition to the photopolymerizable ethylenically unsaturated compound, the liquid photopolymerizable composition can contain a photopolymerizable vinyl ether compound, epoxy compound or oxetane compound, if necessary.

  Examples of vinyl ether compounds include ethylene oxide modified bisphenol-A-divinyl ether, ethylene oxide modified bisphenol-F-divinyl ether, ethylene oxide modified catechol divinyl ether, ethylene oxide modified resorcinol divinyl ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide modified -1,3,5, benzenetriol trivinyl ether, epoxy compounds include 1,2-epoxycyclohexane, 1,4-butanediol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxy Cyclohexanecarboxylate, trimethylolpropane diglycidyl ether, bis (3,4-epoxy-6-methylcyclohexyl) Methyl) adipate, phenol novolak glycidyl ether, bisphenol A diglycidyl ether, oxetane compounds such as 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, di [1-ethyl (3- Oxetanyl)] methyl ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane and the like.

  Moreover, in order to superpose | polymerize by irradiation of an active energy ray, a photoinitiator is usually contained. In addition, it is preferable to contain one or more photocatalytic compounds such as a photosensitizer and a photo accelerator. As a photocatalyst compound, it can select from a well-known photocatalyst compound suitably, and can be used.

  As a photoinitiator, it can select suitably according to the kind (an ultraviolet ray, visible light, an electron beam, etc.) of the active energy ray which is a hardening means.

  Specific examples of the photopolymerization initiator include 2,2-dimethoxy-2-phenylacetone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4-diaminobenzophenone, Benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-thioxanthone, camphorquinone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one and the like. Further, a photopolymerization initiator having at least one (meth) acryloyl group in the molecule such as N-acryloyloxyethylmaleimide can also be used.

  The blending amount of the photopolymerization initiator is preferably based on 100 parts by mass of the solid content of the photocurable coating liquid excluding the diluent described later (total of components already solid before curing and solid components after curing). Is 0.1 to 10 parts by mass, more preferably 3 to 5 parts by mass.

  Specific examples of photosensitizers that can be used together with a photopolymerization initiator to promote photopolymerization include 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like. Specific examples of the photo-accelerating agent that can be used together with the photo-polymerization initiator for promoting photo-polymerization include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid 2-n. -Butoxyethyl, 2-dimethylaminoethyl benzoate and the like can be mentioned.

  In addition, a diluent can be added to the photocurable coating liquid in order to improve the coating property. The addition amount of the diluent can be appropriately determined according to the thickness of the cured layer to be formed. For example, when the thickness of the cured layer is about 0.1 μm, it is preferable that the coating is applied at a wet film thickness of 1.9 μm with a diluent of 94.75% by mass with respect to a solid content of 5.25% by mass.

  As the diluent, a diluent used in a general resin coating solution can be used. Specifically, for example, ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone; methyl acetate, ethyl acetate, acetic acid Ester compounds such as butyl, ethyl lactate and methoxyethyl acetate; ether compounds such as diethyl ether, ethylene glycol dimethyl ether, ethyl cellosolve, butyl cellosolve, phenyl cellosolve and dioxane; aromatic compounds such as toluene and xylene; pentane and hexane Aliphatic compounds; halogen-based hydrocarbons such as methylene chloride, chlorobenzene and chloroform; alcohol compounds such as methanol, ethanol, normal propanol and isopropanol. As the diluent, water and lower alcohols (for example, methanol, ethanol, propanol, etc.) having high affinity with the solid photopolymerizable substance can be preferably used.

  If necessary, the liquid photopolymerizable composition may further include an inorganic filler, a polymerization inhibitor, a color pigment, a dye, an antifoaming agent, a leveling agent, a dispersant, a light diffusing agent, a plasticizer, an antistatic agent, an interface. An activator, a non-reactive polymer, a near-infrared absorber, etc. can be added in the range which does not impair the effect of this invention.

  The photocurable coating liquid of the present invention is a solid photopolymerizable substance described above dispersed in a liquid photopolymerizable composition, but the solid photopolymerizable material in the photocurable coating liquid. When the compounding amount of the substance is too small, the wettability of the coating liquid to the substrate is lowered, and when it is too large, the solid photopolymerizable substance is easily precipitated. Therefore, the blending amount of the solid photopolymerizable substance in the photocurable coating liquid is preferably 5 to 40 mass in the total resin solid content (including not only the solid resin but also the liquid resin content that becomes solid after curing). %, More preferably 10 to 30% by mass.

  In particular, when the solid photopolymerizable substance is a divalent or trivalent metal salt of an organic carboxylic acid having an unsaturated bond, and the liquid photopolymerizable composition contains a photopolymerizable ethylenically unsaturated compound, When the blending amount (parts by mass) of the divalent or trivalent metal salt of the organic carboxylic acid having a saturated bond is (Awt) and the blending amount (parts by mass) of the photopolymerizable ethylenically unsaturated compound is (Bwt) Moreover, it is preferable that the photocurable coating liquid of the present invention satisfies the following formulas (1) and (2). The reason for this is that when the value of “(Awt) / {(Awt) + (Bwt)}” is less than 0.05, the wettability to the substrate is lowered, and if it is 0.4 or more, the component (A) And the content of the component (A) increases relatively when the value of “(Bwt) / {(Awt) + (Bwt)}” is less than 0.6, and the component (A) This is because precipitation tends to occur, and when it is 0.95 or more, the content of (A) is relatively lowered, and thus wettability is lowered.

  In addition, from the viewpoint of the refractive index of the cured layer and the wettability of the coating liquid to the substrate, the photocurable coating liquid of the present invention further satisfies the relationship of the following formulas (1a) and (2a): Is preferred.

  The photocurable coating liquid of the present invention can be produced by uniformly mixing the above-described solid photopolymerizable substance and liquid photopolymerizable composition according to a conventional method.

  In addition, when obtaining the hardened | cured layer of refractive index 1.62, as an example of a specific compounding example of a photocurable coating liquid, ethylene oxide modified bisphenol A diacrylate 30 mass%, bis (4- (meth) acryloyloxythio) Examples thereof include 40% by mass of phenyl) sulfide, 10% by mass of ethylene oxide-modified isocyanuric acid triacrylate, and 20% by mass of zinc acrylate.

  Since the photocurable coating liquid of the present invention contains photopolymerizable substance particles that are polymerizable and do not dissolve in the coating liquid and are present in a particulate form, A uniform and thin film can be formed without causing repelling or pinholes, and the film becomes a cured layer having a high refractive index (for example, 1.60 or more). Therefore, a laminate in which such a thin cured layer, preferably a cured layer having a thickness of 0.01 to 10 μm, is provided on a substrate is advantageous for articles such as a laminated foil, an image display screen protection plate, and a helmet shield. Can be used.

  The base material of the sheet-like, film-like or plate-like laminate provided with such a cured layer is preferably one whose surface material exhibits an affinity with the photocurable coating liquid of the present invention. Thus, the photocurable coating liquid of this invention is applicable also to the base-material surface which shows repellent coating liquid property. Specifically, a substrate made of a material having a surface exhibiting a surface tension of at least 40 dyn / cm or less at 20 ° C. can be used. Examples of such surface materials include polyolefins such as polyethylene and polypropylene, polyvinylidene fluoride, polyvinyl fluoride, polyhexafluoropropylene, polyheptafluoroisopropyl (meth) acrylate, and other fluorine atom-containing polymers, polyoxydimethylsilylene, Examples include silicon-containing polymers such as polyoxymethylsilylene, polyoxydimethylsilylene-α, ω-dibutanoic acid, and polyoxyvinylsilylene. Moreover, although these may constitute a base material itself, these are made of an inorganic base material such as a metal such as iron or aluminum, glass or ceramic, an organic base material such as an acrylic resin, a polyester resin, or a polycarbonate, When used for optical applications, an acrylic resin base material and a polyester resin base material are more preferable.

  The laminate of the present invention has a thermoplastic resin layer, a thermosetting resin layer, a photocurable resin layer, etc. in addition to at least one cured layer formed from the photocurable coating liquid of the present invention. be able to.

  The laminated body of this invention can be manufactured according to the manufacturing method which consists of a process (a) and a process (b) so that it may demonstrate below.

Step (a)
The photocurable coating liquid of the present invention is applied on a substrate to form a photocurable film. About a base material and a photocurable coating liquid, it is as having already demonstrated. As a coating method of the photocurable coating liquid, a known coating method such as a dipping method, a relief printing method, a lithographic printing method, an intaglio printing method, a spray method, a curtain flow method, a roll coating method can be employed. . When a diluent is contained in the photocurable coating solution, the coating film is preferably heated and dried in a heating furnace, a far infrared furnace, or a super far infrared furnace.

Step (b)
When the photocurable film obtained in the step (a) is irradiated with active energy rays such as ultraviolet rays, visible rays, lasers, electron beams, and X-rays as described above, the photocurable film is cured to be a cured layer. It becomes. Thereby, the laminated body which has a hardened layer which consists of a photocurable coating liquid of this invention is obtained. In addition, as a light source when using an ultraviolet-ray, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp etc. are mentioned.

  The laminate obtained in this way is not limited to a two-layer structure of a base material and a cured layer, and a layer of thermoplastic, thermosetting, or photocurable material may be provided in advance, or a cured layer is formed. It may be provided again later.

  As mentioned above, although the photocurable coating liquid of this invention, the laminated body which has a hardened layer which consists of it, and its manufacturing method were demonstrated, of these preferable examples of a photocurable coating liquid, a laminated body, and a manufacturing method of these photocurable coating liquids. An example is shown below. In addition, the meaning of the term in them is as having already demonstrated.

Preferred specific embodiments of the photocurable coating liquid of the present invention include the following components (A) to (C):
(A) a solid photopolymerizable metal salt comprising an organic carboxylic acid having an unsaturated bond and a divalent or trivalent metal;
(B) a photopolymerizable ethylenically unsaturated compound; and (C) a photopolymerization initiator, the blending amount (parts by mass) of component (A) is (Awt), and the blending amount (parts by mass) of component (B) ) Is (Bwt), and a photocurable resin composition satisfying the following formulas (1) and (2) is exemplified. In this case, the component (A) is a polyvalent metal salt of (meth) acrylic acid having any one metal atom of Ca, Zn, Mg, and Al. In particular, the component (A) is preferably zinc acrylate.

Moreover, as a preferable specific aspect of the laminated body of this invention, what formed the photocurable resin layer from the above-mentioned photocurable resin composition on the base material is mentioned. In this case, the laminate is made up of the following steps (a ′) and (b ′):
(A ′) a step of forming a photocurable resin layer comprising the photocurable resin composition according to any one of claims 11 to 13 on a substrate; and (b ′) the obtained photocurable resin layer. Can be produced by a method for producing a laminate comprising a step of irradiating an active energy ray to cure the photocurable resin layer to form a cured resin layer.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to this.

Examples 1-6, Comparative Examples 1-5
Silicone hard coat layer forming coating solution comprising 3 parts by weight of fine silica powder (average particle size 20 nm), 3 parts by weight of methyltriethoxysilane, 0.2 parts by weight of acetic acid, 54 parts by weight of isopropyl alcohol and 40 parts by weight of ethanol Was coated on a 2 mm thick acrylic resin substrate with a bar coater so that the solid content dry film thickness was 5 μm, and dried at 80 ° C. for 30 minutes to form a hard coat layer. On this layer, the photocurable resin composition shown in Table 1 was applied with a bar coater so that the dry thickness of the solid content was 0.1 μm, dried at 140 ° C. for 30 seconds, and then 80 W high-pressure mercury lamp (USHIO Inc.) Using a belt conveyor (manufactured by company) (conveyor speed 1 m / min, distance between light source and irradiated object 10 cm), ultraviolet rays were irradiated once and cured. As a result, a laminate comprising an acrylic resin substrate / hard coat layer / high refractive index cured resin layer was obtained.

(Evaluation methods)
Hajiki :
The laminates obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were divided so as to have a mass of 100, the covering area of the curable resin layer was measured, and the obtained results are shown in Tables 1 and 2. In Tables 1 and 2, “Coating area (%)” was expressed as a percentage by counting the number of squares completely covered with the photocurable resin in which no occurrence of repellency or pinholes was observed.

Refractive index:
The laminated bodies obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were measured for 5 ° reflectance (400 to 700 nm), the refractive index of the high refractive index layer was calculated from the lowest reflectance, and the obtained results Are shown in Tables 1 and 2.

Reflectivity:
After coating OPSTA-JN1214 (manufactured by JSR Corporation) as a low refractive index layer on the laminates obtained in Examples 1 to 6 and Comparative Examples 1 to 5 to a solid content film thickness of 0.1 μm, 80 ° C. For 30 minutes, 5 ° reflectance was measured (400 to 700 nm), and the obtained minimum values in the measurement wavelength range are shown in Tables 1 and 2.

Table 1 and Table 2 * 1: After replacing the nitrogen in the 50 ml three-necked flask, 30 g of ethanol was added, then 4.1 g of zinc chloride (Mw. 136.29 30 mmol), 6.8 g of sodium p-styrenesulfonate (Mw .206.20 35 mmol) was added, and the resulting precipitate was stirred for 3 hours at room temperature, filtered, dried in a vacuum dryer for 24 hours, and then used in the composition.
* 2: APTMS: γ-acryloyloxypropyltrimethoxysilane (trade name KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 3: ATIT: (2-acryloyloxy) triisopropoxytitanate After replacing the 50 ml 3-neck flask with nitrogen, 10.0 g of tetraisopropoxytitanate (Mw. 284.25 35.2 mmol) was added and acrylic acid was used at room temperature. After adding a mixed solution of 2.5 g (Mw. 72.06 35.2 mmol) and 8.3 g of isopropanol over 30 minutes, the mixture was stirred overnight at room temperature to obtain a 50% by mass solution of ATIT. It was.
* 4: Mw 100,000 (Brand name Parapet HR-L, manufactured by Kuraray Co., Ltd.)
* 5: Ethylene oxide modified bisphenol A diacrylate (Brand name Biscote # 540, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
* 6: Ethylene oxide modified isocyanuric acid triacrylate (trade name: M315, manufactured by Toagosei Co., Ltd.)
* 7: Bis (4- (meth) acryloyloxythiophenyl) sulfide (trade name: MPSMA manufactured by Sumitomo Seika Co., Ltd.)
* 8: 1-Hydroxy-cyclohexyl-phenyl ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals)
* 9: Cannot be applied because the solid content was separated. * 10: Since there was much repellency and the film could not be formed, it was applied directly on the acrylic plate as a reference value, and the refractive index value calculated from the reflectance is shown.
* 11: Since the film could not be formed due to many repelling, the reflectance calculated from the refractive index of the high refractive index layer is shown as a reference value.

  As shown in Table 1, from the results of Examples 1 to 6, when a polymerizable organic carboxylic acid metal salt was used, the coverage was 100%, and the cured resin layer was repelled and pinned on the substrate. It can be seen that the holes are uniformly formed without generating holes.

Example 7
Silicone hard coat layer forming coating solution comprising 3 parts by weight of fine silica powder (average particle size 20 nm), 3 parts by weight of methyltriethoxysilane, 0.2 parts by weight of acetic acid, 54 parts by weight of isopropyl alcohol and 40 parts by weight of ethanol Was coated on a 2 mm thick acrylic resin substrate with a bar coater to a solid film thickness of 5 μm, and dried at 80 ° C. for 30 minutes. On this hard coat layer, zinc acrylate 6% by mass, polyfunctional acrylate (trade name: Art Resin UN3320HC, manufactured by Negami Kogyo Co., Ltd.) 24% by mass, photopolymerization initiator (trade name, Irgacure 184, manufactured by Ciba Specialty Chemicals) ) A photocurable resin composition comprising 1.5% by mass, 20% by mass of methyl ethyl ketone, 28.5% by mass of isopropanol, and 20% by mass of methanol was applied to a solid content film thickness of 5 μm, and 30 ° C. at 30 ° C. After drying for a second, ultraviolet rays were irradiated once using a belt conveyor (conveyor speed: 1 m / min, distance between light source and irradiated object: 10 cm) equipped with an 80 W high-pressure mercury lamp (USHIO INC.) And cured. Thereby, the laminated body consisting of an acrylic resin substrate / hard coat layer / cured resin layer was obtained.

  The obtained laminate was divided so as to be 100 squares, and the covering area of the curable resin layer was measured. The evaluation method was the same as in Example 1, and the coverage area was 100%.

Since the photocurable coating liquid of the present invention can obtain a uniform thin film (for example, a film having a film thickness of 0.01 μm or more and 10 μm or less) on a surface having poor wettability, a laminate foil or an image display screen protection plate It can be advantageously used for articles such as helmet shields.

Claims (4)

A laminate in which at least one of the cured resin layers made of the photocurable resin composition is laminated on a coating- repellent liquid-repellent substrate having a silicone hard coat layer surface exhibiting a surface tension of 40 dyn / cm or less at 20 ° C. Body ,
The photocurable resin composition has the following components (A) to (C):
(A) A solid photopolymerizable metal salt composed of (meth) acrylic acid and any one of divalent or trivalent metals of calcium, zinc, magnesium and aluminum and having a particle size of 5 nm to 1 μm;
(B) a photopolymerizable ethylenically unsaturated compound containing a polyfunctional monomer; and
(C) Photopolymerization initiator
When the amount (parts by mass) of component (A) is (Awt) and the amount (parts by mass) of component (B) is (Bwt), the following formulas (1a) and (2a)

A laminate, which is a photocurable resin composition satisfying the requirements. The laminate according to claim 1, wherein the component (A) is zinc acrylate. The laminate according to claim 1 or 2 , wherein the refractive index of the cured resin layer is 1.60 or more. A method for producing a laminate in which a cured resin layer is laminated on a repellent coating liquid-repellent substrate having a silicone hard coat layer surface exhibiting a surface tension of 40 dyn / cm or less at 20 ° C, comprising the following steps (a ′) And (b ′):
(A ') Bachinuriko solution group step of forming a photocurable resin layer comprising a photocurable resin composition on material; and (b') the photocurable resin layer obtained an active energy ray to the A method for producing a laminate comprising a step of curing the photocurable resin layer to form a cured resin layer ,
The photocurable resin composition has the following components (A) to (C):
(A) A solid photopolymerizable metal salt comprising (meth) acrylic acid and any one of divalent or trivalent metals of calcium, zinc, magnesium and aluminum, and having a particle size of 5 nm to 1 μm;
(B) a photopolymerizable ethylenically unsaturated compound containing a polyfunctional monomer; and
(C) Photopolymerization initiator
When the amount (parts by mass) of component (A) is (Awt) and the amount (parts by mass) of component (B) is (Bwt), the following formulas (1a) and (2a)

The manufacturing method of the laminated body of any one of Claims 1-3 characterized by the above-mentioned.