JP6557966B2 - Laminate and optical film - Google Patents

Description

  The present invention provides an aqueous resin composition containing silica as a primer for improving adhesion between a substrate and the cured coating film when a cured coating film of an active energy ray-curable composition is formed on the substrate surface. It is related with the laminated body and optical film which were used.

  In recent years, a display device such as a liquid crystal display is usually configured by laminating a large number of optical films having various functions in order to display a clear image. Specific examples of the optical film and sheet include an antireflection film, a retardation film, and a prism lens sheet.

  As the base material of the optical film, a polyester film, especially a polyethylene terephthalate (PET) film is used because of its excellent optical properties, mechanical strength, and durability. For optical applications, the active energy ray-curable composition is applied to the surface of the polyester film and cured to form a hard coat layer or a layer in which the active energy ray-curable composition is cast. The polyester film may be a prism sheet, but the polyester film has a problem of low adhesion to the cured coating film of the active energy ray-curable composition due to its high crystallinity.

  Therefore, as a method for improving the adhesion between the polyester film and the cured coating film of the active energy ray-curable composition, an acrylic resin is interposed between the polyester film as the substrate and the cured coating film of the active energy beam-curable composition. Providing a primer layer made of resin or urethane resin has been proposed (see, for example, Patent Document 1). At that time, there was a problem that blocking occurred at the time of film winding or film rewinding due to the smoothness of the coating surface and the stickiness of the resin used for the primer. One method for dealing with such problems is to apply a primer containing inorganic fine particles such as colloidal silica, and to prevent blocking by forming a fine uneven structure on the coating film surface ( For example, see Patent Document 2.) However, the primer containing inorganic fine particles often causes aggregation and precipitation, and the productivity is remarkably reduced.

  Therefore, the adhesion between the polyester film and the cured coating film of the active energy ray-curable composition can be made sufficient, and it can also be used as an optical film using a primer that does not block the coated film after coating. A possible laminate was sought.

JP 2010-215843 A JP 2014-048348 A

  The problem to be solved by the present invention is that even a difficult-to-adhere substrate such as a polyester film is water-based as a primer for improving the adhesion between the substrate and the cured coating film of the active energy ray-curable composition. It is providing the laminated body and optical film using a resin composition.

  As a result of diligent research to solve the above problems, the present inventors have used a water-based urethane resin having a sulfonic acid group and a water-based resin composition containing silica as a primer, which makes it difficult to adhere like a polyester film. Even if it was a base material, it discovered that the laminated body which improved the adhesiveness of the base material and the cured coating film of an active energy ray curable composition significantly was obtained, and completed this invention.

  That is, the present invention has a primer layer formed on the surface of a base material using an aqueous resin composition containing an aqueous urethane resin (A) having a sulfonic acid group and silica (B), and the primer layer The present invention relates to a laminate and an optical film characterized by having a cured coating film formed using an active energy ray-curable composition on the surface.

  The laminate of the present invention uses an aqueous resin composition excellent in storage stability and coating transparency as a primer for improving the adhesion between the substrate and the cured coating film of the active energy ray-curable composition. Therefore, even if it is a hard-to-adhere substrate such as a polyester film, it can be a laminate in which a cured coating film of an active energy ray-curable composition is formed on the surface, and is suitably used as an optical film. be able to. Examples of such an optical film include an antireflection film, a retardation film, and a prism lens sheet. Further, these optical films can be applied to image display devices such as liquid crystal displays.

  The laminate of the present invention has a primer layer formed on the surface of a base material using an aqueous resin composition containing an aqueous urethane resin (A) having a sulfonic acid group and silica (B), and the primer It has a cured coating film formed using the active energy ray-curable composition on the surface of the layer.

  Examples of the aqueous urethane resin (A) having a sulfonic acid group include those obtained by reacting a polyol, a polyisocyanate, and, if necessary, a chain extender, and a part of the polyol. By using a polyol having a sulfonic acid group or a metal salt of a sulfonic acid group, the sulfonic acid group can be introduced into the urethane resin.

  Examples of the polyol having a sulfonic acid group include a polyester polyol obtained by reacting a dicarboxylic acid having a sulfonic acid group or a metal salt of a sulfonic acid group or a salt thereof with a low molecular weight polyol, 2-butene-1 And polyols having a sulfonic acid group obtained by sulfonating a polyol having an unsaturated group such as 1,4-diol.

  Examples of the dicarboxylic acid having a sulfonic acid group include 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and dialkyl esters thereof. . Moreover, what the sulfonic acid group which these compounds have is a metal salt can also be used. Among these, 5-sodium sulfoisophthalic acid and 5-sodium sulfoisophthalic acid dimethyl are preferable because long-term storage stability can be maintained and more excellent water resistance and solvent resistance can be imparted.

  The low molecular weight polyol preferably has a molecular weight in the range of 50 to 300. Specifically, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol Aliphatic polyols such as 1,3-butanediol; polyols having an alicyclic structure such as cyclohexanedimethanol; bisphenol compounds such as bisphenol A and bisphenol F; and polyols having an aromatic ring of an alkylene oxide adduct thereof. Can be mentioned.

  The polyol having a sulfonic acid group is preferably used in the range of 50 to 90% by mass in the total amount of the aqueous urethane resin (A) because good water dispersibility can be imparted.

  Moreover, as a polyol used for manufacture of the said water-based urethane resin (A), in addition to the said polyol which has a sulfonic acid group, another polyol can be used as needed.

  Examples of the other polyols include polycarbonate polyols, polyether polyols, and polyolefin polyols. These polyols can be used alone or in combination of two or more.

  Examples of the polycarbonate polyol include those obtained by reacting a carbonate with a polyol, and those obtained by reacting phosgene with bisphenol A and the like.

  Examples of the carbonate ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, and the like.

  Examples of the polyol that can react with the carbonate ester include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5. -Diols having a molecular weight of 50 to 2,000, such as pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol; polyester polyols such as polyethylene glycol, polypropylene glycol, polyhexamethylene adipate, etc. It is done.

  Examples of the polyether polyol include those obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator.

  Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, bisphenol A, glycerin, Examples include trimethylolethane and trimethylolpropane.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

  Examples of the polyolefin polyol include polyethylene polyol, polypropylene polyol, polyisobutene polyol, hydrogenated (hydrogenated) polybutadiene polyol, and hydrogenated (hydrogenated) polyisoprene polyol.

  Moreover, as said other polyol, in addition to said polyol, for example, ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,3-propanediol, 2-ethyl-2-butyl-1, Comparison of 3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol, etc. A low molecular weight polyol may be used in combination.

  Examples of the polyisocyanate used as a raw material for the aqueous urethane resin (A) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, It has an alicyclic structure such as aromatic polyisocyanate such as naphthalene diisocyanate, aliphatic polyisocyanate such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate. Polyisocyanate etc. And the like. These polyisocyanates can be used alone or in combination of two or more.

  Among the polyisocyanates, aromatic polyisocyanates or polyisocyanates having an alicyclic structure are preferable among the above polyisocyanates because the coating film properties of the aqueous resin composition used in the present invention can be further improved. Since the light resistance of a coating film can be improved more, the polyisocyanate which has an alicyclic structure is more preferable.

  The aqueous urethane resin (A) is produced, for example, by reacting the polyol and the polyisocyanate in the absence of a solvent or in the presence of an organic solvent, and then making the urethane resin hydrophilic. When there is a group, when neutralizing a part or all of the hydrophilic group, if necessary, in an aqueous medium and mixing with an aqueous medium, if necessary, mixed with a chain extender, It can be produced by reacting.

  The reaction between the polyol and the polyisocyanate is carried out, for example, in an equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group possessed by the polyisocyanate to the hydroxyl group possessed by the polyol in the range of 0.8 to 2.5. Preferably, it is more preferably carried out in the range of 0.9 to 1.5.

  Examples of the organic solvent that can be used in producing the aqueous urethane resin (A) include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetate solvents such as ethyl acetate and butyl acetate. Nitrile solvents such as acetonitrile; amide solvents such as dimethylformamide and N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more.

  Examples of the chain extender include ethylenediamine, 1,3-propanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, and 3-amino. Methyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), 4,4′-dicyclohexylmethanediamine, 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis ( Diamine compounds such as aminomethyl) bicyclo [2.2.1] heptane, 1,3-bis (aminomethyl) cyclohexane, hydrazine, o-tolylenediamine, m-tolylenediamine, p-tolylenediamine; Triamine compounds, triethylenetetramine, tetraethylenepentamine, etc. Polyamine compounds having amino groups 4 or more, and the like. These chain extenders can be used alone or in combination of two or more.

  Since the urethane resin obtained using the chain extender has a urea bond in the molecule, it is preferable because a coating film having excellent wear resistance can be formed. On the other hand, since the urethane resin tends to lower the alcohol resistance due to the influence of the urea bond, a chain extender is not used as the urethane resin when forming a coating film excellent in solvent resistance. And the urethane resin obtained by limiting the amount of use to a minimum, specifically, the urethane bond content contained in the urethane resin is 10% by mass or less. It is preferable.

  The weight-average molecular weight of the water-based urethane resin (A) obtained by the above method is 3,000 to 200,000 because the adhesion between the substrate and the cured coating film of the active energy ray-curable composition is further improved. Is preferably in the range of 5,000 to 100,000, more preferably in the range of 10,000 to 80,000.

  The sulfonic acid group concentration in the aqueous urethane resin (A) having a sulfonic acid group improves dispersibility in the aqueous resin composition used as a primer in the present invention of silica (B) described later, and the aqueous resin Since the storage stability of a composition can be improved more, the range of 0.5-2 mol / kg is preferable and the range of 0.8-1.5 mol / kg is more preferable. The sulfonic acid group concentration in the present invention is calculated from the amount of raw material used.

  As said silica (B), since the transparency of the coating film of the aqueous resin composition used as a primer by this invention can be improved more, the thing of a nanometer order size is preferable and colloidal silica is preferable. The specific average particle diameter of the silica (B) is preferably in the range of 5 to 100 nm, more preferably in the range of 10 to 50 nm, and still more preferably in the range of 10 to 20 nm. In addition, an average particle diameter is calculated | required from the result measured by the dynamic light scattering method.

  The content of the silica (B) can further improve the transparency of the coating film of the aqueous resin composition used as a primer in the present invention, and can further prevent blocking, so that the aqueous urethane resin having the sulfonic acid group (A ) The range of 0.1 to 20 parts by mass is preferable with respect to 100 parts by mass, the range of 0.2 to 10 parts by mass is more preferable, and the range of 0.4 to 5 parts by mass is more preferable.

  Moreover, since content of the water-based urethane resin (A) having the sulfonic acid group can further improve the storage stability of the water-based resin composition used as a primer in the present invention, it is based on 100 parts by mass of the silica (B). The range of 20 to 400 parts by mass is preferable, the range of 50 to 300 parts by mass is more preferable, and the range of 100 to 250 parts by mass is more preferable.

  The aqueous resin composition used in the present invention includes a film-forming aid, a curing agent, a crosslinking agent, a plasticizer, an antistatic agent, a wax, a light stabilizer, a flow regulator, a dye, a leveling agent, and a rheology as necessary. Additives such as control agents, ultraviolet absorbers, antioxidants, photocatalytic compounds, inorganic pigments, organic pigments and extender pigments; other resins such as polyester resins, urethane resins and acrylic resins can be blended.

  Examples of the crosslinking agent include melamine compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and isocyanate compounds. Examples of the melamine compound include alkylated methylol melamine resins. The alkylated methylol melamine resin is obtained, for example, by reacting a methylolated melamine resin with a lower alcohol (alcohol having 1 to 6 carbon atoms) such as methyl alcohol or butyl alcohol. Examples of the methylolated melamine resins include methylol melamine resins having amino groups obtained by condensing melamine and formaldehyde, methylol melamine resins having imino groups, trimethoxymethylol melamine resins, hexamethoxymethylol melamine resins, and the like. It is done. Among these, trimethoxymethylol melamine resin and hexamethoxymethylol melamine resin are preferable. Examples of the alkylated methylol melamine resin include an alkylated methylol melamine resin having an imino group and an alkylated methylol melamine resin having an amino group.

  The laminate of the present invention has a primer layer formed using the aqueous resin composition used in the present invention described above, and a cured coating formed using an active energy ray-curable composition on the surface of the primer layer. It has a film.

  The active energy ray-curable composition preferably contains a resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group. The type of the monomer having a polymerizable unsaturated group is preferably appropriately selected according to the properties required for the cured coating film of the active energy ray-curable composition.

  Examples of the resin having a polymerizable unsaturated group include urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, acrylic (meth) acrylate resin, and resin having maleimide group. Etc. These resins having a polymerizable unsaturated group can be used alone or in combination of two or more.

  In the present invention, “(meth) acrylate” refers to one or both of acrylate and methacrylate, and “(meth) acryloyl group” refers to one or both of acryloyl group and methacryloyl group.

  Examples of the urethane (meth) acrylate resin include a urethane bond and a (meth) acryloyl group obtained by urethanization reaction of an aliphatic polyisocyanate or an aromatic polyisocyanate with a (meth) acrylate having a hydroxyl group. Examples thereof include resins.

  Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, and 3-methyl-1. , 5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, Hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate Cyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, and the like. Examples of the aromatic polyisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and the like.

  Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1 , 5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, hydroxypivalate neopentyl glycol mono (meth) acrylate, etc. (Meth) acrylate; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate Mono- or di (meth) acrylates of trivalent alcohols such as relate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or hydroxyl groups obtained by modifying some of these alcoholic hydroxyl groups with ε-caprolactone Mono- and di (meth) acrylates having a monofunctional hydroxyl group and tri- or more functional (meth) acryloyl such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. A compound having a group, or a polyfunctional (meth) acrylate having a hydroxyl group obtained by modifying the compound with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, poly (Meth) acrylate compounds having an oxyalkylene chain such as propylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) (Meth) acrylate compounds having a block structure oxyalkylene chain such as acrylate; random structures such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate And (meth) acrylate compounds having an oxyalkylene chain.

  The unsaturated polyester resin is a curable resin obtained by polycondensation of an α, β-unsaturated dibasic acid or acid anhydride thereof, an aromatic saturated dibasic acid or acid anhydride thereof, and glycol. Examples of the α, β-unsaturated dibasic acid or acid anhydride thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. Examples of the aromatic saturated dibasic acid or acid anhydride thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride, and the like. And the like. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. Examples of the glycol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, Examples include tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, and others. In addition, oxides such as ethylene oxide and propylene oxide can be used in the same manner.

  As the epoxy (meth) acrylate resin, (meth) acrylic acid is reacted with an epoxy group of an epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, or the like. What is obtained is mentioned.

  As said polyester (meth) acrylate resin, what is obtained by making (meth) acrylic acid react with the hydroxyl group of polyester polyol is mentioned, for example.

  As said acrylic (meth) acrylate resin, after polymerizing (meth) acrylate monomers, such as glycidyl methacrylate and alkyl (meth) acrylate as needed, for example, after obtaining the acrylic resin which has an epoxy group And those obtained by reacting the epoxy group with (meth) acrylic acid.

  As the resin having a maleimide group, a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethylmaleimide and isophorone diisocyanate, a bifunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol, Examples thereof include a tetrafunctional maleimide ester compound obtained by esterification of maleimidocaproic acid and a tetraethylene oxide adduct of pentaerythritol, a polyfunctional maleimide ester compound obtained by esterification of maleimide acetic acid and a polyhydric alcohol compound, and the like.

  Examples of the monomer having a polymerizable unsaturated group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and a number average molecular weight in the range of 150 to 1,000. Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (number average molecular weight in the range of 150 to 1000) (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (me ) Acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tetra (meth) acrylate, Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate Rate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, aliphatic alkyl (meth) acrylate such as isostearyl (meth) acrylate, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethyl Amino) ethyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropy Glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycolicol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, Polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acrylate Isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N -Octylmaleimide, N-dodecylmaleimide, N-stearylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-propyl carbonate, N-ethyl- (2-maleimidoethyl) Carbamate, N, N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidopropyl) ether, bis (2-maleimidoethyl) carbonate, 1,4-dimale And maleimide compounds such as midcyclohexane. These monomers having a polymerizable unsaturated group can be used alone or in combination of two or more.

  The said active energy ray-curable composition can be made into a cured coating film by irradiating an active energy ray after apply | coating to a base material etc. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When the active energy ray-curable composition is used as a cured coating by irradiating ultraviolet rays as active energy rays, a photopolymerization initiator is added to the active energy ray-curable composition to improve curability. It is preferable to do. Further, if necessary, a photosensitizer can be further added to improve curability. On the other hand, when irradiating an active energy ray with electron beam, α ray, β ray or γ ray to make the active energy ray curable composition as a cured coating film, a photopolymerization initiator or a photosensitizer is used. Since it cures quickly even if it is not used, it is not necessary to add a photopolymerization initiator or a photosensitizer.

  Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) -phenyl] -2. -Hydroxy-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

  Examples of the photosensitizer include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, sulfur such as sodium diethyldithiophosphate, s-benzylisothiuronium-p-toluenesulfonate, and the like. Compound etc. are mentioned.

  As a base material used for the laminated body of this invention, a metal base material, a plastic base material, a glass base material, a paper base material, a wood base material, a fiber base material etc. are mentioned, for example. Among these base materials, in order to improve the adhesion between the cured coating film of the active energy ray-curable composition and the base material, when the aqueous resin composition used in the present invention is used as a primer, a plastic base material is used. Is preferred.

  Materials for the plastic substrate include polyester, acrylic resin (polymethyl methacrylate, etc.), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), composite resin of ABS resin and polycarbonate, polystyrene, polyurethane, epoxy resin , Polyvinyl chloride, polyamide, polyolefin (polyethylene, polypropylene, polycycloolefin (COP), etc.), triacetyl cellulose (TAC), and the like.

  The aqueous resin composition used in the present invention is very useful as a primer for a polyester base material among the above plastic base materials. Specific examples of the polyester include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).

  Examples of the plastic substrate include plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, and office automation equipment. Moreover, the film base material which used the plastic as a raw material is also mentioned. When the film substrate is used as the substrate of the laminate of the present invention, it can be used for optical films such as antireflection films, retardation films, and prism lens sheets; and high-performance films such as food packaging such as aluminum vapor deposition films. it can.

  Further, when the laminate of the present invention is used as an optical film such as an antireflection film, a retardation film, or a prism lens sheet, various kinds of liquid crystal display (LCD), organic EL display (OLED), plasma display (PDP), etc. It can be used as a member of a screen display device.

  The aqueous resin composition used in the present invention can form a coating film on the surface of the substrate by, for example, directly applying to the surface of the substrate and then drying and curing. The method of drying and curing the aqueous resin composition used in the present invention may be a method of curing for about 1 to 10 days at room temperature. However, since curing can proceed rapidly, 100 ° C. A method of heating at about 150 ° C. for about 1 to 600 seconds is preferable. Moreover, when using the plastic base material which is easy to deform | transform and discolor at comparatively high temperature, it is preferable to heat at comparatively low temperature about 70 to 100 degreeC.

  Examples of a method for applying the aqueous resin composition used in the present invention to the surface of the substrate include, for example, a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, flow coater, Examples of the coating method include spin coater, dipping, screen printing, spraying, brush coating, applicator, and bar coater.

  Although the film thickness of the coating film formed using the aqueous resin composition used by this invention can be suitably adjusted according to the use used, Usually, it is preferable that it is the range of 0.01-20 micrometers.

  The laminate of the present invention is further obtained by applying the active energy ray-curable composition to the surface of the primer layer that is the coating film of the aqueous resin composition used in the present invention obtained as described above, By irradiating a line, it can be obtained by forming a cured coating film of the active energy ray-curable composition. In addition, the coating method of the said active energy ray curable composition can use the same method as the coating method of the aqueous resin composition used by said invention.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

(Synthesis Example 1: Synthesis of polyester polyol (1))
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 47.2 parts by mass of 1,6-hexanediol, 42.5 parts by mass of ε-caprolactone, 5-sodium sulfoisophthalic acid 10.7 parts by mass of dimethyl, 6.2 parts by mass of ethylene glycol, and 0.03 parts by mass of dibutyltin oxide were charged, and a polycondensation reaction was performed at 180 to 230 ° C. until the acid value became 1 or less. )

(Synthesis Example 2: Synthesis of polyester polyol (2))
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas inlet tube and a stirrer, 47.2 parts by weight of 1,6-hexanediol, 52.8 parts by weight of adipic acid, dimethyl 5-sodium sulfoisophthalate 10.6 parts by mass, 6.2 parts by mass of ethylene glycol, and 0.03 parts by mass of dibutyltin oxide were charged, a polycondensation reaction was performed at 180 to 230 ° C. until the acid value was 1 or less, and polyester polyol (2) Got.

(Synthesis Example 3: Synthesis of polyester polyol (3))
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 47.2 parts by mass of 1,6-hexanediol, 59.2 parts by mass of phthalic acid, dimethyl 5-sodium sulfoisophthalate 10.2 parts by mass, 6.2 parts by mass of ethylene glycol, and 0.03 parts by mass of dibutyltin oxide were charged, and a polycondensation reaction was carried out at 180 to 230 ° C. until the acid value became 1 or less. Got.

(Synthesis Example 4: Synthesis of polyester polyol (4))
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 27.6 parts by mass of isophthalic acid, 27.6 parts by mass of terephthalic acid, 11.7 parts by mass of ethylene glycol, 19. 9 parts by mass and 0.03 parts by mass of dibutyltin oxide were charged, and a polycondensation reaction was performed at 180 to 230 ° C. until the acid value became 1 or less, to obtain a polyester polyol (4).

(Production Example 1: Synthesis of aqueous urethane resin (I) having a sulfonic acid group)
In a reaction vessel, 100 parts by mass of the polyester polyol (1) obtained in Synthesis Example 1 was dehydrated at 100 ° C. under reduced pressure. After cooling to 80 ° C., 33.7 parts by mass of methyl ethyl ketone was added and stirred and mixed uniformly. Next, 6.1 parts by mass of 2-butyl-2-ethyl-1,3-propanediol was added, and then 23.1 parts by mass of isophorone diisocyanate was added and reacted at 80 ° C. for 12 hours to carry out a urethanization step. . After confirming that the isocyanate value became 0.1% or less, 3 parts by mass of n-butanol was added, and further reacted for 2 hours, then cooled to 50 ° C. and having a sulfonic acid group having a nonvolatile content of 80% by mass. Urethane resin (I) was obtained.

  Next, 391.5 parts by mass of ion-exchanged water was slowly added to 139.8 parts by mass of the urethane resin (I) obtained above. Next, an aqueous dispersion of an aqueous urethane resin (I) having a sulfonic acid group having a nonvolatile content of 25.0% by mass was obtained by removing methyl ethyl ketone at 30 ° C. to 50 ° C. under reduced pressure. The sulfonic acid group concentration in the aqueous urethane resin having a sulfonic acid group was 1.04 mol / kg.

(Production Example 2: Synthesis of aqueous urethane resin (II) having a sulfonic acid group)
In a reaction vessel, 100 parts by mass of the polyester polyol (2) obtained in Synthesis Example 2 was dehydrated at 100 ° C. under reduced pressure, and after cooling to 80 ° C., 33.7 parts by mass of methyl ethyl ketone was added and stirred to mix uniformly. Next, 23.1 parts by mass of hexamethylene diisocyanate was added and reacted at 80 ° C. for 12 hours to carry out a urethanization step. After confirming that the isocyanate value became 0.1% or less, 3 parts by mass of n-butanol was added, and further reacted for 2 hours, then cooled to 50 ° C. and having a sulfonic acid group having a nonvolatile content of 80% by mass. Urethane resin (II) was obtained.

  Next, 335.5 parts by mass of ion-exchanged water was slowly added to 139.8 parts by mass of the urethane resin (II) obtained above. Next, an aqueous dispersion of an aqueous urethane resin (II) having a sulfonic acid group having a nonvolatile content of 25.0% by mass was obtained by removing methyl ethyl ketone at 30 ° C. to 50 ° C. under reduced pressure. The sulfonic acid group concentration in the aqueous urethane resin having a sulfonic acid group was 1.04 mol / kg.

(Production Example 3: Synthesis of water-based urethane resin (III) having a sulfonic acid group)
In a reaction vessel, 100 parts by mass of the polyester polyol (3) obtained in Synthesis Example 3 was dehydrated at 100 ° C. under reduced pressure, and after cooling to 80 ° C., 33.7 parts by mass of methyl ethyl ketone was added and stirred to mix uniformly. Next, 11.5 parts by mass of hexamethylene diisocyanate and 11.5 parts by mass of isophorone diisocyanate were added and reacted at 80 ° C. for 12 hours to carry out a urethanization step. After confirming that the isocyanate value became 0.1% or less, 3 parts by mass of n-butanol was added, and further reacted for 2 hours, then cooled to 50 ° C. and having a sulfonic acid group having a nonvolatile content of 80% by mass. Urethane resin (III) was obtained.

  Next, 391.5 parts by mass of ion-exchanged water was slowly added to 139.8 parts by mass of the urethane resin (III) obtained above. Next, an aqueous dispersion of an aqueous urethane resin (III) having a sulfonic acid group having a nonvolatile content of 25.0% by mass was obtained by removing methyl ethyl ketone at 30 ° C. to 50 ° C. under reduced pressure. The sulfonic acid group concentration in the aqueous urethane resin having a sulfonic acid group was 1.04 mol / kg.

(Production Example 4: Synthesis of aqueous urethane resin (IV) having carboxyl group)
In a reaction vessel, 100 parts by mass of the polyester polyol (4) obtained in Synthesis Example 4 was dehydrated at 100 ° C. under reduced pressure, and after cooling to 80 ° C., 33.7 parts by mass of methyl ethyl ketone was added and stirred to mix uniformly. Next, 6.1 parts by mass of 2,2′-dimethylolpropionic acid was added, and then 23.1 parts by mass of isophorone diisocyanate was added and reacted at 80 ° C. for 12 hours to carry out a urethanization reaction. After confirming that the isocyanate value became 0.1% or less, 3 parts by mass of n-butanol was added, and further reacted for 2 hours, then cooled to 50 ° C. and urethane having a carboxyl group with a nonvolatile content of 80% by mass. Resin (IV) was obtained.

  Next, 3.7 parts by mass of triethylamine was added to 139.8 parts by mass of the urethane resin (IV) obtained above, and 385.2 parts by mass of ion-exchanged water was slowly added. Next, an aqueous dispersion of an aqueous urethane resin (IV) having a carboxyl group with a nonvolatile content of 22.5% by mass was obtained by removing methyl ethyl ketone at 30 ° C. to 50 ° C. under reduced pressure.

(Preparation Example 1: Preparation of aqueous resin composition (1))
400 parts by mass of an aqueous urethane resin (I) aqueous dispersion having a sulfonic acid group having a nonvolatile content of 25% by mass obtained in Production Example 1 (100 parts by mass as the aqueous urethane resin (I) having a sulfonic acid group) and colloidal silica An aqueous resin composition (1) was obtained by mixing 2 parts by mass (0.4 parts by mass as silica) (“Snowtex OL” manufactured by Nissan Chemical Industries, Ltd., dispersion having a nonvolatile content of 20% by mass).

(Preparation Example 2: Preparation of aqueous resin composition (2))
400 parts by mass of an aqueous urethane resin (II) aqueous dispersion having a sulfonic acid group having a nonvolatile content of 25% by mass obtained in Production Example 2 (100 parts by mass as the aqueous urethane resin (II) having a sulfonic acid group) and colloidal silica An aqueous resin composition (2) was obtained by mixing 2 parts by mass (0.4 parts by mass as silica) (“Snowtex OL” manufactured by Nissan Chemical Industries, Ltd., dispersion having a nonvolatile content of 20% by mass).

(Preparation Example 3: Preparation of aqueous resin composition (3))
400 parts by mass of an aqueous urethane resin (III) aqueous dispersion having a sulfonic acid group having a nonvolatile content of 25% by mass obtained in Production Example 3 (100 parts by mass as the aqueous urethane resin (III) having a sulfonic acid group) and colloidal silica An aqueous resin composition (3) was obtained by mixing 2 parts by mass (0.4 parts by mass as silica) (“Snowtex OL” manufactured by Nissan Chemical Industries, Ltd., non-volatile content 20% by mass dispersion).

(Preparation Example 4: Preparation of aqueous resin composition (4))
400 parts by mass of an aqueous urethane resin (I) aqueous dispersion having a sulfonic acid group having a nonvolatile content of 25% by mass obtained in Production Example 1 (100 parts by mass as the aqueous urethane resin (I) having a sulfonic acid group) and colloidal silica An aqueous resin composition (4) was obtained by mixing 4 parts by mass (0.8 parts by mass as silica) (“Snowtex OL” manufactured by Nissan Chemical Industries, Ltd., dispersion having a nonvolatile content of 20% by mass).

(Preparation Example 5: Preparation of aqueous resin composition (5))
400 parts by mass of an aqueous urethane resin (II) aqueous dispersion having a sulfonic acid group having a nonvolatile content of 25% by mass obtained in Production Example 2 (100 parts by mass as the aqueous urethane resin (II) having a sulfonic acid group) and colloidal silica An aqueous resin composition (5) was obtained by mixing 4 parts by mass (0.8 parts by mass as silica) (“Snowtex OL” manufactured by Nissan Chemical Industries, Ltd., dispersion having a nonvolatile content of 20% by mass).

(Preparation Example 6: Preparation of aqueous resin composition (6))
400 parts by mass of an aqueous urethane resin (II) aqueous dispersion having a sulfonic acid group having a nonvolatile content of 25% by mass obtained in Production Example 2 (100 parts by mass as an aqueous urethane resin (II) having a sulfonic acid group) and a production example 2 parts by mass of an aqueous urethane resin (III) aqueous dispersion having a sulfonic acid group having a nonvolatile content of 25% by mass obtained in 3 (0.5 part by mass as the aqueous urethane resin (III) having a sulfonic acid group) and colloidal silica An aqueous resin composition (6) was obtained by mixing 4 parts by mass (0.8 parts by mass as silica) (“Snowtex OL” manufactured by Nissan Chemical Industries, Ltd., dispersion having a nonvolatile content of 20% by mass).

(Comparative Preparation Example 1: Preparation of aqueous resin composition (C1))
444 parts by mass of an aqueous urethane resin (IV) aqueous dispersion having a carboxyl group with a nonvolatile content of 22.5% by mass obtained in Production Example 4 (100 parts by mass as the aqueous urethane resin (IV) having a carboxyl group) and colloidal silica (Nissan Chemical Co., Ltd. "Snowtex OL", non-volatile content 20% by weight dispersion) 2.2 parts by weight (0.44 parts by weight as silica) to obtain an aqueous resin composition (C1) It was.

(Comparative Preparation Example 2: Preparation of aqueous resin composition (C2))
444 parts by mass of an aqueous urethane resin (IV) aqueous dispersion having a carboxyl group with a nonvolatile content of 22.5% by mass obtained in Production Example 4 (100 parts by mass as the aqueous urethane resin (IV) having a carboxyl group) and colloidal silica (Nissan Chemical Industries Co., Ltd. "Snowtex OL", non-volatile content 20 mass% dispersion) 4.45 parts by mass (0.89 parts by mass as silica) to obtain an aqueous resin composition (C2) It was.

(Comparative Preparation Example 3: Preparation of aqueous resin composition (C3))
444 parts by mass of an aqueous urethane resin (IV) aqueous dispersion having a carboxyl group with a nonvolatile content of 22.5% by mass obtained in Production Example 4 (100 parts by mass as the aqueous urethane resin (IV) having a carboxyl group) and colloidal silica (Nissan Chemical Co., Ltd. "Snowtex OL", non-volatile content 20% by weight dispersion) 11.1 parts by weight (2.22 parts by weight as silica) to obtain an aqueous resin composition (C3) It was.

  Table 1 shows the compositions of the aqueous resin compositions (1) to (6) obtained in Preparation Examples 1 to 6 and the aqueous resin compositions (C1) to (C3) obtained in Comparative Preparation Examples 1 to 3. . In addition, the composition (blending amount) in Table 1 is expressed as a nonvolatile content.

(Preparation Example 7: Preparation of UV curable composition (UV-1))
An ultraviolet curable composition was obtained by mixing 50 parts by mass of urethane acrylate resin (“Unidic 17-824-9” manufactured by DIC Corporation) and 12.5 parts by mass of methyl ethyl ketone.

(Example 1: Production of laminate (1))
A primer (P-1) was obtained by mixing 100 parts by mass of the aqueous resin composition (1) obtained in Preparation Example 1 and 275 parts by mass of ion-exchanged water. Subsequently, the primer (P-) obtained as described above was formed on the surface of a film substrate (thickness: 125 μm) made of polyethylene terephthalate (hereinafter abbreviated as “PET”) so that the film thickness after drying was about 1 μm. The primer layer was formed on the surface of the substrate by applying 1) and heating at 150 ° C. for 5 minutes.

On the surface of the primer layer, the ultraviolet curable composition (UV-1) obtained in Preparation Example 7 was applied so as to have a film thickness of 15 μm, heated at 80 ° C. for 10 minutes, and then applied to the coated surface. By using a high-pressure mercury lamp as a light source and irradiating ultraviolet rays at an irradiation amount of 0.5 J / cm ² , the surface of the substrate has a primer layer, and the cured coating film of the ultraviolet curable composition on the surface of the primer layer A laminate (1) having (hereinafter abbreviated as “UV coating film”) was obtained.

(Examples 2 to 6: Production of laminates (2) to (6))
Instead of the aqueous resin composition (1) used in Example 1, the aqueous resin compositions (2) to (6) obtained in Preparation Examples 2 to 6 were used as primers (P-2) to (P- Except having prepared and used 6), it carried out like Example 1 and obtained laminated body (2)-(6).

(Comparative Example 1: Production of laminate (R1))
A primer (P′-1) was obtained by mixing 100 parts by mass of the aqueous resin composition (C1) obtained in Comparative Preparation Example 1 and 275 parts by mass of ion-exchanged water. Next, the primer (P′-1) obtained above was applied to the surface of a PET film substrate (thickness: 125 μm) so that the film thickness after drying was about 1 μm, and at 150 ° C. for 5 minutes. A primer layer was formed on the surface of the substrate by heating.

On the surface of the primer layer, the ultraviolet curable composition (UV-1) obtained in Preparation Example 7 was applied so as to have a film thickness of 15 μm, heated at 80 ° C. for 10 minutes, and then applied to the coated surface. A laminate (R1) having a primer layer on the surface of the substrate and a UV coating on the surface of the primer layer by irradiating ultraviolet rays at a dose of 0.5 J / cm ² using a high pressure mercury lamp as a light source )

(Comparative Examples 2 and 3: Production of laminates (R2) and (R3))
In place of the aqueous resin composition (C1) used in Comparative Example 1, primers (P′-2) and (P) were prepared using the aqueous resin compositions (C2) and (C3) obtained in Comparative Preparation Examples 2 to 5. Except having prepared and used P'-3), it carried out similarly to the comparative example 1, and obtained the laminated body (R2) and (R3).

  The following evaluation was performed using the aqueous resin compositions and laminates obtained in the above Examples and Comparative Examples.

[Evaluation of storage stability]
The aqueous resin compositions immediately after production obtained in Preparation Examples and Comparative Preparation Examples were stored for 7 days in a room temperature environment. The appearance of the aqueous resin composition was visually observed, and the storage stability was evaluated based on the following criteria.
(Double-circle): The aggregate was not seen at all and there was no change compared with the thing immediately after manufacture.
○: Some precipitates were confirmed, but at a practically usable level, and the precipitates could be redispersed by stirring again.
(Triangle | delta): The deposit was a little, and even if it stirred again, a part of deposit remained, and it could not fully re-disperse.
X: About 50% by mass or more of the total amount of the resin was precipitated, and could not be redispersed even by stirring again.

[Evaluation of substrate adhesion]
A 24 mm wide adhesive tape made by Nichiban Co., Ltd. was applied to the surface of the UV coating film of the laminate obtained above. Next, the adhesive tape is pulled in a direction perpendicular to the primer layer, and when the adhesive tape is peeled from the surface of the primer layer, the surface condition of the primer layer is evaluated according to the following evaluation criteria. did. It measured by the method based on the JIS test method (JIS K5600: 1999).
(Double-circle): UV coating film did not peel at all from the base-material surface.
○: Less than 10% of the total area of the UV coating film was peeled off from the substrate surface.
Δ: 10% or more and less than 50% of the total area of the UV coating film was peeled off from the substrate surface.
X: 50% or more of the total area of the UV coating film was peeled off from the substrate surface.

[Evaluation of film appearance (measurement of haze value)]
The haze value of the laminate obtained above was measured using a haze meter (manufactured by Suga Test Instruments Co., Ltd.). It measured by the method based on the JIS test method (JIS K7136: 2000). The haze value (H) was calculated from the following formula. Further, the haze value of only the PET substrate was also measured, and the haze value was 2.05%. Based on the obtained haze value, the film appearance was evaluated according to the following evaluation criteria.
H (%) = Td / Tt × 100
H: Haze (cloudiness value) (%)
Td: diffuse transmissivity (%)
Tt: Total light transmittance (%)
(Double-circle): The increase rate of the haze value was less than 10% with respect to the haze value of the PET base material alone, and no aggregate was observed.
A: The increase rate was 10% or more and less than 20% with respect to the haze value of the PET substrate alone, and no aggregate was observed.
(Triangle | delta): The raise rate was 20% or more and less than 50% with respect to the haze value only of PET base material, and the aggregate was seen a little.
X: The increase rate was 50% or more with respect to the haze value of the PET substrate alone, and many aggregates were observed.

  The evaluation results are shown in Table 2.

  From the evaluation results of Examples 1 to 6 shown in Table 2, the aqueous resin composition used in the laminate of the present invention is excellent in storage stability, and the coating film obtained using the aqueous resin composition It was confirmed that the film was excellent in transparency. Furthermore, it has also confirmed that the laminated body of this invention was excellent in adhesiveness with a base material.

  On the other hand, Comparative Examples 1 to 3 are examples using an aqueous resin composition containing an aqueous urethane resin having a carboxyl group. It was confirmed that the storage stability was remarkably worse than the aqueous resin composition used in the laminate of the present invention, and the transparency of the coating film obtained using the aqueous resin composition was low. Furthermore, it has confirmed that the laminated body obtained by Comparative Examples 1-3 was also insufficient in adhesiveness with a base material.

Claims (3)

It has a primer layer formed using an aqueous resin composition containing an aqueous urethane resin (A) having a sulfonic acid group (A) and silica (B) on the surface of the polyester substrate, and the surface of the primer layer is active. Having a cured coating film formed using an energy beam curable composition;
Sulfonic acid group concentration in the aqueous urethane resin (A) having a sulfonic acid group, it ranges der of 0.5 to 2 mol / kg,
Laminate the average particle size of the silica (B) is characterized by a range der Rukoto of 10 to 50 nm.   The laminate according to claim 1, wherein the content of the silica (B) is in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the aqueous urethane resin (A) having the sulfonic acid group.   An optical film comprising the laminate according to claim 1.