JP5601496B2 - Method for producing silica sol for coating, coating composition, coating, resin laminate having coating on surface, and method for producing the same - Google Patents

Description

  The present invention relates to a method for producing a silica sol for coating, a composition for coating, a coating, a resin laminate having a coating on the surface, and a method for producing the same.

  Transparent resins such as acrylic resins and polycarbonate resins are widely used as various materials such as industrial materials and building materials. Particularly in recent years, acrylic resins and polycarbonate resins have been used as front plates for various displays such as CRTs, liquid crystal televisions, plasma displays and the like from the viewpoint of transparency and impact resistance.

  In recent years, various functions have been required for the front plate. One of the required functions is an antireflection function.

  The antireflection function is a function for reducing the reflected light of an indoor fluorescent lamp or the like reflected on the front plate and displaying the image more clearly. Examples of the method for imparting the antireflection function include a method of forming an antireflection layer on the surface of the front plate.

  The antireflection layer has a single layer structure in which a low refractive index layer is provided on the display surface, or one or more intermediate to high refractive index layers are provided on the display surface in order to improve the antireflection performance. There is a multilayer structure in which a low refractive index layer is provided thereon.

  Examples of the compound having a low refractive index function include a compound containing a fluorine atom. However, in order to reduce the refractive index, there is a problem that when added in a large amount, the hardness and strength of the coating film are lowered.

  As another method for reducing the refractive index, reducing the refractive index of the entire coating film by making air having a refractive index of 1 smaller than the wavelength of visible light and including it in the coating film. Are known. For example, a low refractive index layer obtained by curing a composition comprising fine particles such as hollow silica having a cavity inside and a compound having an ionizing radiation low refractive index group is disclosed (Patent Document 1). Furthermore, it is disclosed that the mechanical strength of the coating film is improved by treating the surface of the fine particles with a silane coupling agent. However, when the fine particles obtained by performing the surface treatment by the method described therein were used, the mechanical strength was improved as compared with the untreated one, but the performance was insufficient. Furthermore, chemical resistance was insufficient.

  Further, it is disclosed that a coating film excellent in abrasion resistance and durability, and also in weather resistance can be obtained by reacting a hydrolyzate of a silane compound with silica fine particles in a nonpolar solvent. (Patent Document 2). However, if an attempt is made to modify the surface of the hollow silica by the disclosed method, local aggregation (gelation) occurs when a nonpolar solvent is additionally added, making it difficult to form a coating.

JP 2005-99778 A JP 07-109355 A

  An object of the present invention is to provide a method for producing a silica sol for coating that does not cause local aggregation (gelation) and has excellent dispersion stability.

  Another object of the present invention is to provide a composition capable of forming a low refractive index (cured) film having good surface hardness (abrasion resistance) and chemical resistance.

  Furthermore, it is providing the coating film formed by hardening | curing the said composition, the resin laminated body, and its manufacturing method.

  The present invention includes (a-1) 40 to 90% by mass of hollow silica fine particles, (a-2) the following general formula (1)

(In the formula, X is CH ₂ ═CH—COO— group, CH ₂ ═C (CH ₃ ) —COO— group, or CH ₂ ═CH— group, R ₁ is an alkylene group having 1 to 8 carbon atoms, R ₂ , R ₃ is an alkyl group having 1 to 8 carbon atoms or hydrogen, a is a positive integer of 1 to 3, b is a positive integer of 0 to 2, and a + b is an integer of 1 to 3. A first step of heating a mixture containing 60 to 10% by mass and a polar solvent, a nonpolar solvent having a boiling point higher than the boiling point of the polar solvent in the mixture in which the solid content concentration of the mixture is 35% by mass or less A second step of adding, a third step of heating to volatilize the polar solvent and setting the solid content concentration to 30% by mass to 80% by mass, and a fourth step of performing a condensation reaction in the mixture This is a method for producing a silica sol.

  The present invention also provides a coating composition containing the silica sol obtained by the above method and a compound having at least two (meth) acryloyloxy groups in the molecule.

  Moreover, this invention is a film formed by hardening | curing the said composition.

  Moreover, this invention is a resin laminated body which has the said film in a surface layer.

Moreover, this invention is a manufacturing method of the resin laminated body which has the process as described in the following (1)-(5).
(1) Coating film forming step of coating the composition on the surface of the transparent substrate film to form a coating film (2) Cured coating film forming step of curing the coating film to form a cured coating film (3) The cured coating film A resin base laminate forming step of forming a resin base laminate by laminating a resin base via a thermoplastic resin coating layer on the surface of the resin (4) Pressurizing and heating the resin base laminate Thermoplastic resin coating layer-containing transfer film laminate forming step of forming a thermoplastic resin coating layer-containing transfer film laminate by integrating the resin substrate laminate by at least one treatment selected from the treatments (5) Resin laminate forming process for obtaining a resin laminate by peeling a transparent substrate film from a thermoplastic resin coating layer-containing transfer film laminate

Furthermore, this invention is a manufacturing method of the resin laminated body which has the process as described in the following (1)-(5).
(1) Coating film forming step of coating the composition on the surface of the transparent substrate film to form a coating film (2) Cured coating film forming step of curing the coating film to form a cured coating film (3) The cured coating film An active energy ray-curable resin substrate in which an active energy ray-curable resin substrate laminate is formed by laminating a resin substrate via a layer of a curable coating film containing the active energy ray-curable composition on the surface of Laminate Forming Step (4) Curable Coating Cured Layer-Containing Transfer Film Laminate Forming Step (Forming a Cured Layer of a Curable Coating Film by Irradiating the Active Energy Ray Curable Resin Base Laminate with Active Energy Rays ( 5) A resin laminate forming step of obtaining a resin laminate by peeling the transparent substrate film from the curable coating film cured layer-containing transfer film laminate.

  According to the present invention, it is possible to obtain a silica sol for coating excellent in dispersion stability in which local aggregation (gelation) does not occur in the surface treatment process of inorganic fine particles. Further, a composition capable of forming a low refractive index (cured) film having good surface hardness (abrasion resistance) and chemical resistance can be obtained. Furthermore, the coating film which consists of the said composition, and the resin laminated body which has the said coating film in a surface layer can be obtained.

  The silica sol for coating of the present invention can be produced by the following first to fourth steps, that is, by surface treatment of hollow silica fine particles.

  (A-1) 40 to 90% by mass of hollow silica fine particles, and (a-2) the following general formula (1)

(In the formula, X is CH ₂ ═CH—COO— group, CH ₂ ═C (CH ₃ ) —COO— group, or CH ₂ ═CH— group, R ₁ is an alkylene group having 1 to 8 carbon atoms, R ₂ , R ₃ is an alkyl group having 1 to 8 carbon atoms or hydrogen, a is a positive integer of 1 to 3, b is a positive integer of 0 to 2, and a + b is an integer of 1 to 3. The 1st process of heating the mixture containing 60-10 mass% and a polar solvent.

  A second step of adding a nonpolar solvent having a boiling point higher than that of the polar solvent to the mixture having a solid content concentration of 35% by mass or less.

  A third step of heating to volatilize the polar solvent and adjusting the solid content concentration to 30% by mass to 80% by mass.

  A fourth step of performing a condensation reaction in the mixture;

  First, each component used for the surface treatment of the hollow silica fine particles will be described.

  The hollow silica fine particles (a-1) used in the present invention are usually in a dispersion medium, and the average particle diameter is preferably 5 nm or more, and more preferably 30 nm or more. Moreover, it is preferable that it is 100 nm or less, and it is more preferable that it is 60 nm or less. The average particle diameter of the silica fine particles is appropriately selected according to the thickness of the coating film to be formed, and is preferably in the range of 2/3 to 1/10 of the thickness of the coating film.

  The thickness of the outer shell layer of the hollow silica fine particles is preferably in the range of 1 to 30 nm, preferably 2 to 20 nm. If the thickness of the outer shell layer is too small, the particles may not be completely coated, and binder components and the like will enter the fine particles, reducing the internal cavities and porous structure, resulting in a low refractive index effect. May not be sufficiently obtained. On the other hand, if the thickness of the outer shell layer is too large, the porosity of the fine particles may be reduced, and the low refractive index effect may not be sufficiently obtained.

  The hollow silica fine particles in the present invention have a cavity and a porous structure inside the hard outer shell layer of silica, so that the film strength when combined with a binder component is improved, for example, when a coating having an antireflection function is used. A refractive index of 1.45 or less required for the coating (low refractive index layer) can be easily achieved.

  The polar solvent, which is a dispersion medium used for the hollow silica fine particles, includes, in addition to water, monohydric alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, isobutanol and n-butanol, and many solvents such as ethylene glycol. Polyhydric alcohol derivatives such as monohydric alcohol solvents, ethyl cellosolve, butyl cellosolve, ketone solvents such as methyl ethyl ketone, methyl-isobutyl ketone, diacetone alcohol, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, etc. Although there are monomers, an alcohol solvent having 3 or less carbon atoms is particularly preferable in the reaction step with the compound (a-2). These hollow silica fine particles are produced by a known method as colloidal silica and are commercially available.

  The hollow silica fine particles contain a gas such as air having a refractive index of 1, so that the refractive index of the coating itself is relatively low, and the refractive index of the coating can be lowered. Good antireflection performance. Furthermore, by treating the surface with a compound (silane coupling agent) such as (a-2), the bonding strength with the binder resin is strengthened, and the strength of the coating (low refractive index layer) is improved.

  The hydrolyzate of the compound (a-2) represented by the general formula (1) is at least two in the molecule, which are the hollow silica fine particles (a-1) and the component (B) of the coating composition described later. It is a component which improves compatibility with the compound which has a (meth) acryloyloxy group. Chemical bond formation with the polyfunctional (meth) acrylate of the component (B) is possible by using a silane compound having a polymerization activity by ultraviolet irradiation (a-2), that is, an acryloyl group, a methacryloyl group or a vinyl group. Yes, toughness can be imparted to the low refractive index coating. Furthermore, by using together with the hollow silica fine particles, the wear resistance of the low refractive index coating can be further improved, and in particular, the effect of improving the wear resistance against metal fibers such as steel wool is great.

  Specific examples of (a-2) include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacrylic. Roxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-acryloxyethyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane Vinyltrimethoxysilane and vinyltriethoxysilane. One of these may be used alone, or two or more may be used in combination.

  Next, a method for obtaining a silica sol for coating by surface treatment of hollow silica fine particles will be described.

In the first step, (a-1) hollow silica fine particles (solid content) of 40 to 90% by mass, (a-2) compound (solid content) represented by the general formula (1) 60 to 10% by mass and polarity The mixture containing the solvent is heated.
The content of the polar solvent can be appropriately selected. This step is a step of hydrolyzing the silane compound (a-2). The hydrolysis of the silane compound in this step is
(1) A hydrolysis catalyst such as 0.5 to 6 moles of 0.001 to 0.1 N hydrochloric acid or an aqueous acetic acid solution in the presence or absence of an organic solvent such as an alcohol solvent with respect to 1 mole of a silane compound. In addition, a method of adding hollow silica fine particles after hydrolysis by stirring at room temperature or under heating.

  (2) It can be obtained by a known method such as adding a hydrolysis catalyst to the hollow silica fine particles (a-1) and the silane compound (a-2) and stirring at normal temperature or under reflux. The heating temperature is preferably 60 ° C. or higher, more preferably 75 ° C. or higher, although it depends on the dilution solvent. The heating time is preferably 2 hours or more. Hydrolysis proceeds sufficiently under these reaction conditions.

  When the ratio of the compound (a-2) is 60 to 10% by mass, the hardness of the film is improved and the chemical resistance is also improved. Furthermore, the affinity for the binder is good and the dispersion stability is excellent.

  Next, in the second step, a nonpolar solvent having a boiling point higher than that of the polar solvent is added to the mixture having a solid content concentration of 35% by mass or less. When the solid content concentration exceeds 35% by mass, it can be diluted with a polar solvent to 35% by mass or less. When a nonpolar solvent is added to the mixture having a solid content concentration higher than 35% by mass, local aggregation (gelation) occurs.

  The nonpolar solvent used in the present invention is selected on the basis of dielectric constant, dipole efficiency or hydrogen bonding parameter, and in a broad sense, a solvent having medium polarity is also included in the present invention. . For example, a nonpolar solvent having a dielectric constant of 2 to 10 at 20 ° C. is a particularly preferable solvent in the present invention.

  Specific examples of the nonpolar solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, saturated hydrocarbons such as cyclohexane, and halogenated hydrocarbons such as trichloroethylene and tetrachloroethylene. . Among these nonpolar solvents, aromatic hydrocarbons are preferable, and toluene can be mentioned as a particularly preferable nonpolar solvent.

  Next, heating is performed in the third step to volatilize the polar solvent, so that the solid content concentration is 30% by mass to 80% by mass. In this step, the proportion of the nonpolar solvent in the total amount of the solvent is preferably 80% by mass or more.

  In order to volatilize the polar solvent from the mixture, the boiling point of the polar solvent is lower than the boiling point of the nonpolar solvent. A combination of solvents in which the polar solvent is methanol and isopropanol and the nonpolar solvent is toluene and xylene is preferable. Further, when the polar solvent is volatilized, the solvent may be volatilized by reducing the pressure.

  When volatilizing the polar solvent, polar solvent such as alcohol used for dispersion of the hollow silica fine particles, alcohol generated by hydrolysis of silane compound (a-2), alcohol such as ethanol, etc., produced by condensation reaction The reaction of (a-1) and (a-2) is promoted by volatilizing water or the like. Furthermore, it becomes a reaction system with a large proportion of nonpolar solvents, and an environment in which the reaction proceeds more easily. By allowing the condensation reaction to proceed in a nonpolar solvent, a silica sol for coating that can form a coating with good surface hardness (abrasion resistance) and chemical resistance can be obtained.

  By concentrating the solid content concentration to 30% by mass to 80% by mass, local aggregation (gelation) does not occur, the dispersion stability is excellent, the condensation reaction proceeds sufficiently, and the hardness of the coating becomes good. Good chemical resistance.

  Finally, as a fourth step, a condensation reaction is performed in the mixture. For example, the condensation reaction can be carried out by stirring at a temperature of 60 ° C. to 150 ° C., preferably 80 ° C. to 130 ° C. for 3 to 10 hours.

  Here, the proportion of the nonpolar solvent is preferably 80% by mass or more continuously from the third step.

  In this condensation reaction, a catalyst such as an acid, a base or a salt may be added for the purpose of accelerating the reaction, if necessary.

  Furthermore, in this condensation reaction, a compound capable of reacting with the residual silanol group generated by hydrolysis of (a-2) may be added for the purpose of preventing further condensation reaction from proceeding as necessary. Examples of this compound include an epoxy group-containing compound, an oxetane skeleton-containing compound, an isocyanate group-containing compound, hexamethyldisiloxane, and trimethylsilyl chloride.

  By performing the reaction under the above condensation reaction conditions, local aggregation (gelation) does not occur, the dispersion stability is excellent, the condensation reaction proceeds sufficiently, the film hardness is improved, and the chemical resistance is also improved. It becomes good.

  Furthermore, by using the silica sol for coating produced by the above production method, the antifouling property (water repellency and oil repellency) of the laminate surface layer produced by the transfer method described later is improved.

  Next, the coating composition of the present invention will be described.

  The coating composition includes the above-described silica sol for coating (hereinafter referred to as “component (A)”) and a compound having at least two (meth) acryloyloxy groups in the molecule described below (hereinafter referred to as “component (B)”. ) ”)). Moreover, you may contain the antifouling compound (henceforth "component (C)") mentioned later as needed.

  First, the component (A) will be described.

  Component (A) is a silica sol for coating obtained through the above steps, and component (A) has the effect of improving the hardness and chemical resistance of the coating, and lowering the refractive index and reducing the reflectance.

  In the step, a part of the compound (a-2) (silane coupling agent) may not be introduced on the surface of the silica fine particles but may be present alone or as a condensate in the silica sol solution for coating. The component (A) which is a silica sol includes hollow silica fine particles, a silane coupling agent introduced on the surface of the fine particles, and a silane cup which is not introduced on the surface of the fine particles alone or as a condensate in the silica sol solution for coating. This means that all ring agents are integrated.

  The content of the component (A) in the coating composition is preferably 30% by mass or more, and more preferably 40% by mass or more in the total solid components of the coating composition. Moreover, 80 mass% or less is preferable, and 75 mass% or less is more preferable.

  Next, the component (B) will be described.

  Component (B) is a compound having at least two (meth) acryloyloxy groups in the molecule.

  As content of a component (B), 5 mass% or more is preferable in all the solid components of the composition for a film, and 10 mass% or more is more preferable. Moreover, 30 mass% or less is preferable, and 20 mass% or less is more preferable.

  Examples of the component (B) include esterified products obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or a derivative thereof, polycarboxylic acid or anhydride thereof, polyhydric alcohol (meta) ) An esterified product obtained from acrylic acid or a derivative thereof.

  Specific examples of the esterified product obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or a derivative thereof include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol. Polyethylene glycol di (meth) acrylate such as di (meth) acrylate; 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate Alkyl diol di (meth) acrylates such as; and trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate Pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate and other trifunctional or higher functional polyol poly (meth) acrylates It is done.

  In an esterified product obtained from a polyvalent carboxylic acid or its anhydride, a polyhydric alcohol, and (meth) acrylic acid or a derivative thereof, a combination of a polyvalent carboxylic acid or its anhydride, a polyhydric alcohol and (meth) acrylic acid ( Examples of polycarboxylic acid or anhydride / polyhydric alcohol / (meth) acrylic acid) include, for example, malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylolpropane / (meth) acrylic acid, Malonic acid / glycerin / (meth) acrylic acid, malonic acid / pentaerythritol / (meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid / trimethylolpropane / (meth) acrylic acid, succinic acid Acid / glycerin / (meth) acrylic acid, succinic acid / pentaerythritol / (meth) acrylic Acid, adipic acid / trimethylolethane / (meth) acrylic acid, adipic acid / trimethylolpropane / (meth) acrylic acid, adipic acid / glycerin / (meth) acrylic acid, adipic acid / pentaerythritol / (meth) acrylic acid Glutaric acid / trimethylolethane / (meth) acrylic acid, glutaric acid / trimethylolpropane / (meth) acrylic acid, glutaric acid / glycerin / (meth) acrylic acid, glutaric acid / pentaerythritol / (meth) acrylic acid, Sebacic acid / trimethylolethane / (meth) acrylic acid, sebacic acid / trimethylolpropane / (meth) acrylic acid, sebacic acid / glycerin / (meth) acrylic acid, sebacic acid / pentaerythritol / (meth) acrylic acid, fumar Acid / Trimethylolethane / (Me ) Acrylic acid, fumaric acid / trimethylolpropane / (meth) acrylic acid, fumaric acid / glycerin / (meth) acrylic acid, fumaric acid / pentaerythritol / (meth) acrylic acid, itaconic acid / trimethylolethane / (meth) Acrylic acid, itaconic acid / trimethylolpropane / (meth) acrylic acid, itaconic acid / glycerin / (meth) acrylic acid, itaconic acid / pentaerythritol / (meth) acrylic acid, maleic anhydride / trimethylolethane / (meth) Acrylic acid, maleic anhydride / trimethylolpropane / (meth) acrylic acid, maleic anhydride / glycerin / (meth) acrylic acid and maleic anhydride / pentaerythritol / (meth) acrylic acid.

  Other examples of compounds having at least two (meth) acryloyloxy groups in the molecule include trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 4,4'-methylenebis. (Cyclohexyl isocyanate), isophorone diisocyanate, trimethylhexamethylene diisocyanate and other diisocyanates trimerized to give 1 mol of polyisocyanate 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy- 3-methoxypropyl (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylic 3 or more moles of an acrylic monomer having active hydrogen such as imide, 15,3-propanetriol-1,3-di (meth) acrylate, 3-acryloyloxy-2-hydroxypropyl (meth) acrylate Urethane (meth) acrylate obtained; poly [(meth) acryloyloxyethylene] isocyanurate such as di (meth) acrylate or tri (meth) acrylate of tris (2-hydroxyethyl) isocyanuric acid; epoxy poly (meth) acrylate; And urethane poly (meth) acrylate.

  A component (B) can be used individually or in combination of 2 or more types.

  When the coating composition is an active energy ray curable composition, a photoinitiator described later can be blended in the coating composition.

  Next, the component (C) will be described. Component (C) is an antifouling compound and can be added to impart antifouling properties (water repellency and oil repellency) to the coating.

  As a specific example of component (C), first, triisocyanate (I) obtained by trimerizing diisocyanate (hereinafter referred to as “triisocyanate (I)”) and active hydrogen-containing compound (II) are reacted. And fluorine group-containing polyether compound (III) (hereinafter referred to as “compound (III)”).

  Examples of the diisocyanate used to obtain the triisocyanate (I) include an isocyanate group bonded to an aliphatic skeleton, such as hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and dicyclohexylmethane diisocyanate. Examples thereof include diisocyanates in which an isocyanate group is bonded to an aromatic skeleton, such as diisocyanate and tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate.

  Examples of the active hydrogen-containing compound (II) include compounds containing active hydrogen such as hydroxyl groups.

  Specific examples of the active hydrogen-containing compound (II) include perfluoropolyether (II-1) having one active hydrogen (hereinafter referred to as “polyether (II-1)”) and active hydrogen and carbon-carbon two. And a monomer (II-2) having a heavy bond (hereinafter referred to as “monomer (II-2)”).

  Examples of the polyether (II-1) include compounds having a perfluoropolyether group and one hydroxyl group at one molecular end.

  Specific examples of the polyether (II-1) include a compound represented by the following formula (2).

(2)
Wherein X is a fluorine atom, Y and Z are each a fluorine atom or a trifluoromethyl group, a is an integer of 1 to 16, c is an integer of 0 to 5, b, d, e, f and g are 0 to 0. 200 is an integer, and h is an integer of 0 to 16.)

  In the formula (2), if the numerical values of a to h are not too large, the molecular weight does not become too large and the solubility tends to be good. On the other hand, if the numerical value is not too small, water repellency and oil repellency tend to be good.

  Examples of the monomer (II-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.

  In the present invention, “(meth) acryl” means “acryl” or “methacryl”.

  As a synthesis method of component (C), for example, polyether (II-1) is reacted with one isocyanate group of triisocyanate (I), and monomer (II-2) is reacted with the remaining two isocyanate groups. It can be obtained by reacting.

  In the above reaction, triisocyanate (I) may be reacted with polyether (II-1) and monomer (II-2) at the same time or sequentially.

  Specific examples of component (C) include compound (III) represented by the following formula (3).

(3)

(In the formula, W represents a perfluoropolyether group.)

  Other examples of the component (C) include a compound having one isocyanate group, one or two (meth) acryloyloxy groups in the same compound, and a component having at least one active hydrogen at the molecular end. Examples thereof include compounds obtained by reacting with fluoropolyether. Examples of the compound having one isocyanate group and one or two (meth) acryloyloxy groups in the same compound include, for example, Showa Denko Co., Ltd., product names: Karenz BEI, Karenz AOI, Karenz MOI, etc. Is mentioned. Examples of the perfluoropolyether having at least one active hydrogen at the molecular end include product names: FLUOROLINK D10H, FLUOROLINK D, and FLUOROLINK D4000 manufactured by Solvay Solexis.

  As content of the component (C) contained in this film composition, 10 mass% is preferable in solid content of a film composition, and 12 mass% is more preferable. Moreover, 50 mass% or less is preferable, and 30 mass% is more preferable. By making content of a component (C) into the said range, it exists in the tendency which can make favorable the water repellency, oil repellency, and abrasion resistance of the surface of the laminated body obtained by this invention. A component (C) can be used individually by 1 type or in combination of 2 or more types. Here, the “solid content” means a component excluding the solvent.

  The coating composition is cured by a polymerization reaction. The polymerization is not particularly limited, and may be active energy ray polymerization or thermal polymerization.

  When the coating composition is curable with active energy rays (hereinafter also referred to as “light” for convenience), examples of the photoinitiator added to the composition include benzoin, benzoin methyl ether, and benzoin ethyl ether. , Benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethyl Carbonyl compounds such as phenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one; Sulfur compounds such as lamethylthiuram monosulfide and tetramethylthiuram disulfide; and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzoyldiethoxyphos Phosphorus compounds such as fin oxide are listed.

  The addition amount of the photoinitiator is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the solid content of the low refractive index composition in terms of low refractive index due to ultraviolet irradiation of the low refractive index cured coating, More preferably 5 parts by mass or more, and still more preferably 1 part by mass or more. Further, the addition amount of the photoinitiator is preferably 10 parts by mass or less, and more preferably 7 parts by mass or less from the viewpoint of improving the color tone of the low refractive index cured film and improving the antifouling property.

  When this film composition is a thermosetting composition, a thermosetting agent can be mix | blended in this composition.

  Examples of the thermosetting agent include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2, Azo polymerization initiators such as 4-dimethylvaleronitrile); and lauroyl peroxide, diisopropyl peroxydicarbonate, benzoyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyneodeca And organic peroxide polymerization initiators such as noate and t-hexylperoxypivalate. These can be used alone or in combination of two or more.

  If necessary, various additives such as a slip improver, a leveling agent, a UV absorber, and a light stabilizer such as HALS can be blended in the present composition.

  As a compounding quantity of an additive, 10 mass parts or less are preferable with respect to 100 mass parts of solid content of this composition at the transparency point of a film.

  In this invention, in order to adjust the solid content density | concentration of this composition, a dilution solvent can be contained in this composition.

  Examples of the dilution solvent include methyl ethyl ketone, methyl isobutyl ketone, isopropanol, ethanol, 1-methoxy-2-propanol, and 2,2,3,3-tetrafluoro-1-propanol.

  As solid content concentration of this composition, 0.1-20 mass% is preferable. By setting the solid content concentration of the present composition within the above range, the storage stability of the present composition can be improved, and the desired film thickness tends to be easily controlled.

  The method of laminating the coating of the present invention on the substrate is not particularly limited. For example, a method of directly applying the composition to the substrate and curing it, forming a coating on a transparent substrate film, and once producing a transfer film Thereafter, a method of transferring the coating film to the substrate side through an adhesive layer can be mentioned, but the latter method (hereinafter also referred to as “transfer system”) is preferable from the viewpoint of improving productivity and suppressing foreign matter defects.

  Hereinafter, a method for forming a laminate by a transfer method will be described in detail, but the present invention is not limited thereto.

Transparent substrate film The transparent substrate film used in the present invention is removed by laminating a transfer film, which will be described later, on the surface of the resin substrate and then removed, for example, using an active energy ray transmissive film. be able to.

  Specific examples of the transparent substrate film include a polyethylene terephthalate film (hereinafter referred to as “PET film”), a synthetic resin film such as a polycarbonate film, a polyamide film, and a polyamideimide film, and a composite film or a composite sheet thereof. And those having a release layer laminated thereon.

  Although there is no restriction | limiting in particular as thickness of a transparent base film, 4 micrometers or more are preferable at the point of the ease of manufacture of a transfer film without a wrinkle, a crack, etc., 12 micrometers or more are more preferable, and 30 micrometers or more are still more preferable. Moreover, as thickness of a transparent base film, 500 micrometers or less are preferable, 150 micrometers or less are more preferable, and 120 micrometers or less are still more preferable.

  As a release layer forming material for forming a release layer on the surface of the transparent substrate film, a polymer, wax, or the like that forms a known release layer can be appropriately selected and used.

Coating Film The main coating film is a film formed by applying the coating composition to a substrate.

Coating film forming step The coating film forming step is a step of forming a coating film. Examples of the method for forming the coating film include the following methods.

  The coating composition is applied to the surface of the transparent substrate film. When the diluent solvent is contained, it is preferable to remove the diluent solvent by drying or the like.

  Examples of the method for applying the composition to the surface of the transparent substrate film include casting, roller coating, bar coating, spray coating, air knife coating, spin coating, flow coating, and curtain coating. Method, film cover method and dipping method.

Volatile compound The present volatile compound can obtain a laminate exhibiting good water repellency and oil repellency by the present transfer method by volatilizing the volatile compound applied to the surface of the coating film. The content of component (C) can be reduced.

  Examples of the volatile compound include at least one solvent selected from alcohol compounds, ketone compounds, ether compounds, and ester compounds.

  Examples of alcohol compounds include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pen. Tanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n- Nonyl alcohol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohex Nord, benzyl alcohol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and 1-methoxy-2-propanol. Among these, ethanol, isopropanol, and 1-methoxy-2-propanol are preferable, and isopropanol is more preferable among them in terms of water repellency and oil repellency on the surface of the obtained laminate.

  Examples of ketone compounds include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-isobutyl ketone, methyl-n-pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, and di-isobutyl. Examples include ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and γ-butyrolactone. Among these, methyl-isobutyl ketone is preferable in terms of water repellency and oil repellency on the surface of the obtained laminate.

  Examples of ether compounds include ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, and ethylene. Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol dibutyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl Ether, diethylene glycol diethyl ether, diethylene glycol Mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran and 2-methyltetrahydrofuran. Among these, ethylene glycol mono-n-butyl ether (hereinafter also referred to as “buticello”) is preferable in terms of water repellency and oil repellency on the surface of the obtained laminate.

Examples of ester compounds include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, and 3-methoxybutyl acetate. , Methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, nonyl acetate, γ-butyrolactone, γ-valerolactone, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol acetate Monomethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-propionate Butyl, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, methyl (meth) acrylate, (meth), ethyl acrylate, ( Examples include n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. Among these, methyl methacrylate is preferable from the viewpoint of water repellency and oil repellency on the surface of the obtained laminate.
These volatile compounds can be used alone or in combination of two or more.

  In the present invention, the boiling point of the volatile compound is preferably 200 ° C. or less.

  In volatile compounds, slip stabilizers, leveling agents, UV absorbers, light stabilizers such as HALS, photoinitiators, thermal initiators, amines, inorganic fine particles, organic fine particles, binders, etc. Various additives can be added.

Volatile compound coating step In the volatile compound coating step, a volatile compound is coated on the surface of the coating film formed on the transparent substrate film to form a coating film of the volatile compound.

  As a method for applying a volatile compound to the surface of the coating film, for example, casting method, roller coating method, bar coating method, spray coating method, air knife coating method, spin coating method, flow coating method, curtain coating method, Examples thereof include a film cover method and a dipping method. Among these, the vacuum slot die coating method, the spray coating method, the air knife coating method, the spin coating method, the flow coating method, the curtain coating method, and the dipping method are preferable in terms of suppressing damage to the coating film.

Volatilization step In the volatilization step, the volatile compound applied to the surface of the coating film formed on the transparent substrate film is volatilized.

  Examples of the method for volatilizing a volatile compound include a method of volatilizing at a temperature equal to or higher than room temperature under normal pressure or reduced pressure.

Film The film in the present invention is a film formed by curing the film composition. When the coating is a “low refractive index layer” having a refractive index lower than that of the lower layer (a layer in contact with the coating), antireflection performance is obtained.

  The film thickness of the coating is preferably 10 nm or more, more preferably 60 nm or more, from the viewpoint of the water repellency, oil repellency, scratch resistance and optical properties of the surface of the laminate obtained in the present invention. Moreover, 1.3 micrometers or less are preferable, 300 nm or less are more preferable, and 110 nm or less are still more preferable.

Film Forming Process The film forming process is a process of curing the film composition constituting the coating film after volatilizing the volatile compound in the volatilization process.

  Examples of the method for curing the composition include a thermal curing method and an active energy ray curing method.

  Examples of the active energy ray used in the active energy ray curing method include ultraviolet rays. Examples of the light source for irradiating with ultraviolet rays include a high-pressure mercury lamp, a metal halide lamp, and a fluorescent ultraviolet lamp.

Examples of the irradiation condition of the active energy ray include irradiation conditions of a peak illuminance of 1 to 500 mW / cm ² and an integrated light amount of 1 to 2000 mJ / cm ² .

  The active energy ray can be irradiated to at least one surface selected from the surface of the coating film and the surface of the transparent substrate film.

Transfer Film The transfer film used in the present invention is obtained by laminating a film that can be peeled off from the transparent substrate film on the surface of the transparent substrate film.

  The transfer film may be obtained by laminating an adhesive layer described later on the surface of the coating as necessary.

  Moreover, the said transfer film shall be what laminated | stacked the high refractive index layer mentioned later on the surface of a film as needed.

  Furthermore, the transfer film may be obtained by laminating an adhesive layer on the surface of the high refractive index layer as necessary.

  A known protective film can be laminated on the surface of the adhesive layer or the high refractive index layer of the transfer film as necessary.

Adhesive layer In the present invention, the adhesive layer is for adhering the transfer film obtained in the present invention to a resin substrate described later.

  The adhesive layer may be either laminated on the coating surface of the transfer film or laminated on the surface of the resin substrate on which the transfer film is laminated.

  Examples of the adhesive layer include a thermoplastic resin coating layer containing a thermoplastic resin and a curable coating layer containing an active energy ray curable composition.

Thermoplastic resin coating layer The thermoplastic resin for forming the thermoplastic resin coating layer is, for example, an acrylic resin, a chlorinated olefin resin, a vinyl chloride-vinyl acetate copolymer, a maleic acid resin, or a chlorinated rubber. Resin, cyclized rubber resin, polyamide resin, coumarone indene resin, ethylene-vinyl acetate copolymer, polyester resin, polyurethane resin, styrene resin, butyral resin, rosin resin, and epoxy resin Is mentioned.

Examples of the active energy ray-curable composition used for forming the layer of the curable coating film include those similar to the component (B) used in the coating composition. Can be mentioned.

Adhesive layer forming step In the adhesive layer forming step of the present invention, a thermoplastic film coating layer or a curable coating that is an adhesive layer on the surface of the transfer film or a high refractive index layer if it has a high refractive index layer. Membrane layers can be formed.

  As an adhesive layer forming material used for forming the thermoplastic resin coating layer, for example, a thermoplastic resin solution in which a thermoplastic resin is dissolved in a solvent can be used.

  Examples of the solvent that dissolves the thermoplastic resin include methyl ethyl ketone, methyl isobutyl ketone, isopropanol, ethanol, 1-methoxy-2-propanol, and toluene.

  As a method for forming the thermoplastic resin coating layer, for example, the above-mentioned thermoplastic resin solution is applied to the surface of the transfer film coating or the high refractive index layer if it has a high refractive index layer, and then the solvent is removed. The method of forming a thermoplastic resin coating layer by doing is mentioned.

  Examples of the method for forming the thermoplastic resin coating layer include a roll coating method, a bar coating method, and a slit die usage method.

  In the present invention, the thermoplastic resin coating layer can be formed on the surface of the resin substrate. In this case, the adhesive layer can be formed by applying the thermoplastic resin solution to the surface of the resin substrate and then removing the solvent.

  Moreover, when obtaining a resin base material, a thermoplastic resin layer can be laminated previously.

  When using an active energy ray-curable composition to form an adhesive layer, as a method of forming a layer of a curable coating film containing an active energy ray-curable composition, for example, a transfer film coating, Or when it has a high refractive index layer, the method of apply | coating said active energy ray curable composition on the surface of a high refractive index layer, and laminating | stacking the layer of a curable coating film is mentioned.

  Examples of the method for forming the curable coating film layer include the same method as the method for forming the thermoplastic resin coating layer described above.

  In the present invention, the curable coating layer can be formed on the surface of the resin substrate. In this case, the adhesive layer can be formed by applying the active energy ray-curable composition on the surface of the resin base material and laminating the curable coating layer.

High Refractive Index Layer The component forming the high refractive index layer preferably has a refractive index of about 1.6 to 2.0. Here, the high refractive index layer is a layer below the coating film (low refractive index layer) (a layer in contact with the coating film) and has a higher refractive index than the refractive index of the coating film.

  In the present invention, examples of the component for forming the high refractive index layer include those obtained by adding metal oxide fine particles having a higher refractive index to the component (B) in the coating composition. As metal oxide fine particles, tin oxide and antimony doped tin oxide (ATO), indium oxide and tin doped indium oxide (ITO), zinc oxide and aluminum doped zinc oxide, zinc antimonate, antimony pentoxide And metal oxide fine particles.

  Among these metal oxide fine particles, at least one of the metal oxide fine particles is used as a compound for forming a high refractive index layer (for example, the component (B)) in that the refractive index of the high refractive index layer can be further increased. It is preferable to mix. Moreover, since these metal oxide fine particles have antistatic properties, the antistatic function can be imparted to the laminate obtained by the present invention.

  When a compound containing an active energy ray-curable composition is used as the compound for forming a high refractive index layer, it can be cured by a known curing method.

  In this case, as the high refractive index metal oxide fine particles, it is preferable to use high refractive index metal oxide fine particles that have been surface-treated with a silane coupling agent.

  The film thickness of the high refractive index layer is preferably from 0.1 to 10 μm. When the film thickness is in this range, the surface of the laminate obtained in the present invention has a good surface hardness and the transparency of the laminate tends to be good. When the film thickness is within this range, even when an antistatic layer is provided in the laminate to provide an antistatic function, good antistatic performance tends to be provided.

Resin base material The resin base material used in the present invention includes, for example, polymethyl methacrylate, polycarbonate, a copolymer having a methyl methacrylate unit as a main component, a molded product of polystyrene and a styrene-methyl methacrylate copolymer. Can be mentioned. The molded product is preferably a plate-like product from the viewpoint of easy lamination.

  The thickness of the laminate is preferably 0.2 mm or more in terms of mechanical strength, and is preferably 10 mm or less in terms of productivity. The resin base material can contain additives such as a colorant and a light diffusing agent as necessary.

Resin Base Laminate In the present invention, a resin base laminate is obtained by sequentially laminating a thermoplastic resin coating layer (adhesive layer), a coating (low refractive index layer) and a transparent base film on the surface of a resin base. Alternatively, a thermoplastic resin coating layer (adhesive layer), a high refractive index layer, a coating (low refractive index layer), and a transparent substrate film are sequentially laminated on the surface of the resin substrate.

In the present invention, when a thermoplastic resin coating layer is used as the adhesive layer, the transfer film is passed through the surface of the thermoplastic resin coating layer in the resin substrate laminate forming step. A resin base laminate is obtained by laminating with a resin base.

  Examples of the method of laminating the resin base material and the transfer film include a method of pressure bonding with a rubber roll.

  In the pressure bonding, for example, the pressure bonding can be performed under a condition of 5 to 15 MPa. Moreover, it is preferable to heat the surface of the resin base material to laminate | stack at 40-125 degreeC at the point of adhesiveness with a transfer film.

Active energy ray-curable resin substrate laminate In the present invention, the active energy ray-curable resin substrate laminate is a layer of a curable coating film containing an active energy ray-curable composition (adhesion) on the surface of the resin substrate. Layer), a film (low refractive index layer) and a transparent substrate film sequentially laminated, or a layer of a curable coating film containing an active energy ray-curable composition (adhesion layer) on the surface of a resin substrate A high refractive index layer, a coating (low refractive index layer) and a transparent substrate film are sequentially laminated.

Active energy ray-curable resin substrate laminate formation process In the present invention, when using a layer of a curable coating film containing an active energy ray-curable composition as an adhesive layer, an active energy ray-curable resin group is used. In the material laminate forming step, the transfer film is laminated with the resin substrate through the surface of the curable coating layer to obtain an active energy ray-curable resin substrate laminate.

  In order to prevent air entrainment when laminating the resin base material and the transfer film, it is possible to form a curable coating layer using raw materials for forming an excessive amount of the curable coating layer. preferable.

  Examples of the method for laminating the resin base material and the transfer film include the same method as in the case of using the thermoplastic resin coating layer as the adhesive layer.

Thermoplastic resin coating layer-containing transfer film laminate In the present invention, the thermoplastic resin coating layer-containing transfer film laminate is obtained by integrating the resin base laminate by the following treatment.

Thermoplastic resin coating layer-containing transfer film laminate forming step In the present invention, in the thermoplastic resin coating layer-containing transfer film laminate forming step, the resin is formed by at least one treatment selected from pressure treatment and heating treatment. Resin base material, thermoplastic resin coating layer (adhesive layer) and coating film (low refractive index layer) constituting the resin base material laminate obtained in the base material laminate forming step, or resin base material, thermoplastic resin coating The film layer (adhesive layer), the high refractive index layer, and the coating (low refractive index layer) can be integrated. Examples of the pressing method include a method of pressure bonding with a rubber roll. Examples of the pressurizing condition include 5 to 15 MPa.

  Examples of the heating treatment method include a method of heating a resin base material. As heating conditions, 40-125 degreeC is mentioned, for example. By making the heating conditions as described above, the adhesion between the transfer film and the resin base material can be improved, and there is no decrease in hardness due to excessive dissolution of the resin base material. There is also a tendency for less yellowing.

  The surface temperature of the resin base material when heating the resin base material can be adjusted by the set temperature of the heating unit, the heating time, and the like. Moreover, as a measuring method of the temperature of a resin base material, the method by a non-contact type surface thermometer is mentioned, for example.

  In the present invention, the thermoplastic resin coating layer-containing transfer film laminate may be formed simultaneously with the formation of the resin base laminate.

  In the present invention, if necessary, a cured low refractive index film can be obtained by promoting the curing of the low refractive index cured film during the heating treatment.

  In the present invention, if necessary, in addition to the above treatment, active energy rays may be irradiated to accelerate the curing of the coating, thereby obtaining a sufficiently cured coating.

Curable coating film cured layer containing transfer film laminate In the present invention, the curable coating film cured layer containing transfer film laminate is a cured layer of a curable coating film as a cured film of an adhesive layer on the surface of a resin base material. Low refractive index layer) and transparent substrate film laminated in sequence or on the surface of the resin substrate, as a cured film of the adhesive layer, a cured layer of a curable coating film, a high refractive index layer, a coating (low refractive index layer) ) And a transparent substrate film are sequentially laminated.

Cured layer of curable coating film The cured layer of the curable coating film is obtained by curing a layer of a curable coating film containing an active energy ray-curable composition used as an adhesive layer.

In the present invention, in the present invention, the activity obtained in the active energy ray-curable resin substrate laminate forming step in the curable coating film cured layer-containing transfer film laminate forming step. An energy ray curable resin substrate laminate can be irradiated with active energy rays to form a cured layer of a curable coating film.

  Irradiation of active energy rays to the active energy ray-curable resin substrate laminate can be carried out via a transfer film. Moreover, you may irradiate an active energy ray from the resin base material side as needed according to the shape of the resin base material.

  Examples of the active energy ray for forming the cured layer of the curable coating film include ultraviolet rays. Examples of the light source for irradiating with ultraviolet rays include a high-pressure mercury lamp, a metal halide lamp, and a fluorescent ultraviolet lamp.

Examples of the active energy ray irradiation conditions for forming a cured layer of the curable coating film include conditions with a peak illuminance of 100 mW / cm ² or more and an integrated light amount of 10 mJ / cm ² or more.

  In the present invention, when the cured layer of the curable coating film is formed, it is possible to obtain a sufficiently cured film by accelerating the curing of the film, if necessary.

Resin Laminate The resin laminate obtained in the present invention is a thermoplastic resin coating layer used as an adhesive layer or a cured layer of a curable coating film that is a cured film of an adhesive layer on the surface of a resin substrate ( A low-refractive index layer) is sequentially laminated. Further, other than the above may be laminated, but the resin laminate preferably has the coating film on the surface layer.

  In the present invention, a thermoplastic resin coating layer used as an adhesive layer or a cured film of a curable coating that is a cured film of the adhesive layer and a coating (low refractive index layer) as necessary. A high refractive index layer can be formed.

Resin Laminate Forming Process The resin laminate obtained in the present invention is obtained from the thermoplastic resin coating layer-containing transfer film laminate or the curable coating film cured layer-containing transfer film laminate in the laminate forming step. Obtained by peeling.

  When the transparent substrate film is peeled from the thermoplastic resin coating layer-containing transfer film laminate or the curable coating film cured layer-containing transfer film laminate, for example, the transparent substrate film is removed from the thermoplastic resin coating layer at room temperature. It can peel from a containing transfer film laminated body by a well-known method.

  The resin laminate obtained by the method of the present invention is suitable for various front plates.

Hereinafter, the present invention will be described by way of examples. In addition, the abbreviations of the compounds used in Examples and Comparative Examples are as follows. In the following, “part” and “%” represent “part by mass” and “% by mass”, respectively.
"TAS": Succinic acid / trimethylolethane / acrylic acid (molar ratio 1/2/4) condensation mixture (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
“C6DA”: 1,6-hexanediol diacrylate (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
“M305”: Pentaerythritol triacrylate (trade name, manufactured by Toagosei Co., Ltd.)
“M400”: Dipentaerythritol hexaacrylate (trade name, manufactured by Toagosei Co., Ltd.)
“OPTOOL DAC”: a solution of a fluorine group-containing polyether compound having a perfluoropolyether group and an active energy ray reactive group (produced by Daikin Industries, Ltd., solid concentration 20%, 2,2,3,3-tetra Fluoro-1-propanol solution, trade name)
“DAROCUR TPO”: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name, manufactured by Ciba Japan Co., Ltd.)
“IRGACURE819”: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name, manufactured by Ciba Japan Co., Ltd.)
“KBM503”: 3-methacryloxypropyltrimethoxysilane (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.)
“Thruria S”: Isopropyl alcohol (IPA) dispersion of hollow silica sol (solid content 20%) (trade name, manufactured by JGC Catalysts & Chemicals Co., Ltd.)
“PGM”: 1-methoxy-2-propanol (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
“IPA”: Isopropanol (Wako Pure Chemical Industries, Ltd.)
"Acrylite EX001": Methacrylic resin plate (trade name, manufactured by Mitsubishi Rayon Co., Ltd.)

The evaluation method implemented by this invention is shown below.
(1) Temperature of resin base material The surface temperature of the resin base material was measured using a non-contact type surface thermometer (manufactured by Chino Co., Ltd., handheld type radiation thermometer IR-TA (trade name)).

(2) Total light transmittance and haze value Based on the measurement method shown in JIS K7361-1, using Nippon Denshoku Industries Co., Ltd. HAZE METER NDH2000 (trade name), the total light transmittance of the resin laminate. The haze value was measured based on the measurement method shown in JIS K7136.

(3) Scratch resistance A circular pad with a diameter of 25.4 mm equipped with # 000 steel wool is placed on the surface of the low refractive index cured coating of the resin laminate, and a 20 mm distance is scratched 30 times under a load of 1 kg. Then, the haze value difference (Δhaze) before and after the scratch was determined from the following formula, and the number of scratches on the sample surface after the test was counted to evaluate the scratch resistance.
[Δhaze (%)] = [haze value after abrasion (%)] − [haze value before abrasion (%)]

(4) Anti-reflective property The surface on which the resin laminate film (low refractive index layer) is not laminated is roughened with sandpaper and then applied with a matte black spray. (Trade name: U-4000, manufactured by Hitachi, Ltd.), the reflectance of the surface of the coating film of the sample is measured according to the measurement method shown in JIS R3106 at an incident angle of 5 ° and a wavelength of 380 to 780 nm. Measurements were made to determine the lowest reflectance wavelength (bottom wavelength) and the reflectance at the bottom wavelength (bottom wavelength reflectance) of the resulting reflectance curve.

In addition, the presence or absence of a change in reflected color when fingerprints were attached to the surface of the resin laminate film (low refractive index layer) was evaluated according to the following criteria.
○: No change in reflected color was observed.
X: Change in reflected color was observed.

(5) Antifouling property The antifouling property of the low refractive index cured film was evaluated by the following water contact angle, triolein contact angle and oil-based ink wiping property.
(A) In an environment where the water contact angle is 23 ° C. and the relative humidity is 50%, one drop of 0.2 μL of ion-exchanged water is dropped on the surface of the coating (low refractive index layer), and a portable contact angle meter (Fibro system ab The contact angle between water and the coating film was measured using a product name (trade name: PG-X), and the water contact angle was determined.
(B) Contact angle of triolein The contact angle of triolein was determined in the same manner as in the measurement of the water contact angle except that triolein was used instead of ion-exchanged water.
(C) Oil-based ink wiping property On the surface of the coating (low refractive index layer), write a line with “My Name” (trade name, manufactured by Sakura Crepas Co., Ltd.) as oil-based ink (black), and “Kim towel” after 3 minutes. (Nippon Paper Crecia Co., Ltd., trade name) was wiped off, and the wiping of the oil-based ink at that time was visually evaluated according to the following criteria.
A: Completely wiped off by wiping 5 times.
○: A trace of a line remains slightly after wiping 5 times.
X: Part or all of the oil-based ink remains adhered after wiping 5 times.

(6) Adhesiveness In accordance with JIS K5600-5-6, evaluation of peeling of 25 square grids was carried out at 4 locations, and the number of squares left without peeling in 100 squares was determined. The adhesion of the low refractive index cured film was evaluated.

(7) Film thickness of curable coating film A sample having a width of 100 nm was cut out with a microtome in the thickness direction of the curable coating film, and a resin laminate was obtained with a transmission electron microscope (JEM-1010 (trade name) manufactured by JEOL Ltd.). The film thickness of the curable coating film was measured.

(8) Chemical resistance test The resin laminate was cut to a size of 50 x 50 mm to obtain a sample for evaluation. Next, the absorbent cotton is cut into a size of 30 × 30 mm, placed on the sample for evaluation, using a syringe, and bleaching agent (Kao Co., Ltd., Kitchen Hiter (trade name)) is hung on the absorbent cotton to remove the absorbent cotton. Moistened. The sample was allowed to stand for 30 minutes in a constant temperature and humidity machine at a temperature of 20 ° C. and a relative humidity of 30%, taken out, the surface of the resin laminate was washed with water, and then the chemical resistance was evaluated by visual evaluation based on the following criteria.
○: No discoloration was observed.
X: Discoloration was recognized.

[Example 1] Manufacture of silica sol (1) subjected to hydrolysis treatment and condensation reaction treatment Into a four-necked flask reaction vessel equipped with a stirrer and a condenser tube, 400 g of sulria S as a dispersion of (a-1) was charged. Next, 51 g of KBM503 was added as (a-2). Thereafter, 28 g of 0.1N hydrochloric acid aqueous solution was added dropwise over 5 minutes with stirring. Thereafter, the temperature of the oil bath was set to 80 ° C. and heated to reflux for 2 hours. Next, 240 g of toluene was added dropwise over 10 minutes. The solid concentration before adding toluene was 27% by mass. Gelation due to the addition of toluene did not occur (Table 1).

  After adding toluene, the temperature of the oil bath was set to 120 ° C., and the cooling pipe was replaced with a Dean-Stark pipe. Thereafter, the solvent was distilled off from the Dean-Stark tube for 3 hours until the solid content was 60% by mass and concentrated.

  As a result of quantitative analysis of the toluene concentration in all the solvents in the reaction system by gas chromatography, the content of toluene as a nonpolar solvent was 90% by mass.

  Thereafter, the Dean-Stark tube was replaced with a cooling tube, and the oil bath was heated to reflux for 5 hours with the oil bath temperature set at 120 ° C. in a state where the solid content concentration was 60% by mass.

  The obtained silica sol (1) was a cloudy liquid, and the solid content concentration was 65% by mass. In addition, solid content concentration calculated | required by calculation from the weight difference before and behind drying by heating and drying silica sol (1) in an 80 degreeC environment for 3 days.

[Example 2] Production of silica sol (2) subjected to hydrolysis treatment and condensation reaction treatment 400 g of sulria S was charged into a four-necked flask reaction vessel equipped with a stirrer and a Dean-Stark tube, and then 51 g of KBM503 was added. Thereafter, 28 g of 0.1N hydrochloric acid aqueous solution was added dropwise over 5 minutes with stirring. Thereafter, the temperature of the oil bath was set to 80 ° C., and the solvent was distilled off from the Dean-Stark tube over 2 hours until the solid content concentration became 33% by mass and concentrated.

  Next, 240 g of toluene was added dropwise over 10 minutes. The solid concentration before adding toluene was 33% by mass. Gelation due to the addition of toluene did not occur (Table 1).

  After adding toluene, the temperature of the oil bath was set to 120 ° C., and the solvent was distilled off from the Dean Stark tube over 3 hours until the solid content concentration became 60% by mass, and concentrated.

  As a result of quantitative analysis of the toluene concentration in all the solvents in the reaction system by gas chromatography, the content of toluene as a nonpolar solvent was 93% by mass.

  Thereafter, the Dean-Stark tube was replaced with a cooling tube, and the oil bath was heated to reflux for 5 hours with the oil bath temperature set at 120 ° C. in a state where the solid content concentration was 60% by mass.

  The obtained silica sol (2) was a cloudy liquid, and the solid content concentration was 66% by mass. In addition, solid content concentration calculated | required by calculation from the weight difference before and behind drying by heating and drying silica sol (2) in an 80 degreeC environment for 3 days.

[Example 3] Production of silica sol (5) subjected to hydrolysis treatment and condensation reaction treatment Example 1 was the same as Example 1 except that the amount of KBM503 added was changed as described in Table 1. A silica sol (5) was prepared (Table 1). The solid content concentration of the silica sol (5) was 65% by mass.

[Example 4] Production of silica sol (6) subjected to hydrolysis treatment and condensation reaction treatment Example 1 was the same as Example 1 except that the amount of KBM503 added was changed as described in Table 1. A silica sol (6) was prepared (Table 1). The solid content concentration of the silica sol (6) was 64% by mass.

[Comparative Example 1] Production of silica sol (3) subjected to hydrolysis treatment and condensation reaction treatment Example 2 is the same as Example 2 except that the solid content concentration before adding toluene was 38% by mass. Surface treatment was performed. Since the solid content concentration was 35% by mass or more, gelation occurred due to the addition of toluene (Table 1).

Comparative Example 2 Production of Silica Sol (4) Treated with Hydrolysis and Condensation Reaction In Example 2, except that the solid content concentration before adding toluene was 45% by mass, it was the same as Example 2. Surface treatment was performed. Since the solid content concentration was 35% by mass or more, gelation occurred due to the addition of toluene (Table 1).

[Comparative Example 3] Production of silica sol (7) subjected to hydrolysis treatment and condensation reaction treatment 400 g of sulria S was charged into a four-necked flask reaction vessel equipped with a stirrer and a cooling tube, and then 51 g of KBM503 was added. Thereafter, 28 g of 0.1N hydrochloric acid aqueous solution was added dropwise over 5 minutes with stirring. Thereafter, the temperature of the oil bath was set to 80 ° C. and heated to reflux for 2 hours.

  Subsequently, the temperature of the oil bath was set to 100 ° C., and the cooling pipe was replaced with a Dean-Stark pipe. Thereafter, the solvent was distilled off from the Dean-Stark tube for 3 hours until the solid content was 60% by mass and concentrated. Toluene addition was not performed (Table 1).

  Thereafter, the Dean Stark tube was replaced with a cooling tube, and the oil bath was heated to reflux for 5 hours while the oil bath temperature was set at 100 ° C. in a state where the solid content concentration was 60% by mass.

  The obtained silica sol (7) was a cloudy liquid, and the solid content concentration was 63% by mass. In addition, solid content concentration calculated | required by calculation from the weight difference before and behind drying by heat-drying silica sol (7) for 3 days in an 80 degreeC environment.

  Further, the ratio (%) of the inorganic fine particles in the silica sol was determined by the mass ratio of the inorganic fine particles to 100 parts in total of the hydrolyzable silane compound and the inorganic fine particles used.

[Production Example 1] Production of antifouling compound F In an eggplant flask equipped with a cooling pipe, 2.6 g of an isocyanate group-containing acrylate compound (manufactured by Showa Denko, product name: Karenz BEI) and polyether (II- 1) 8 g of perfluoropolyether compound (Solbe isorexis, product name: FLUOROLINK D 10 / H) and 0.005 g of dibutyltin dilaurate were added and stirred at 50 ° C. for 6 hours.
Methyl ethyl ketone was added to the resulting cloudy viscous liquid to dilute the solid content concentration to 20% by mass to obtain an antifouling compound F.

  Using this antifouling compound F as the component (C), a coating composition (5) having a low refractive index was prepared (Table 2).

[Example 5]
A low refractive index coating composition (1) is applied to the surface of a PET film having a thickness of 100 μm with an easy-adhesion layer (trade name: A4100, manufactured by Toyobo Co., Ltd.) on which the easy-adhesion layer is not formed. The coated film was formed by coating using a No. bar coater and drying at 80 ° C. for 15 minutes.

  The film thickness of the coating film was 93 nm as calculated from the solid content concentration, coating amount and coating area of the low refractive index composition (1) of the coating film.

  After applying IPA as a volatile compound on the coating film using the applicator (clearance; memory 5) to form a coating film of the volatile compound, it is heated at 80 ° C. for 15 minutes to volatilize the IPA. It was.

Next, the PET film on which the coating film is laminated is passed at a speed of 9 m / min under a 9.6 kW high-pressure mercury lamp (output setting 50%) at a position of 20 cm to cure the coating film. Thus, a laminated film having a coating (low refractive index) formed was obtained. The integrated light quantity at this time was 100 mJ / cm ² and the peak illuminance was 130 mW / cm ² .

  Next, an active energy ray-curable composition obtained by mixing 35 parts of TAS, 30 parts of C6DA, 10 parts of M305, 25 parts of M400 and 2 parts of DAROCUR TPO as an adhesive layer using a No. 10 bar coater Then, it was applied to the surface of the above-mentioned laminated film coating to form a curable coating layer to obtain a transfer film. In addition, when forming an adhesive layer on the surface of the coating, no repellency defects occurred.

  Acrylite EX001 having a plate thickness of 2 mm was used as the resin substrate, and the transfer film was superimposed on the surface of the resin substrate heated to 60 ° C. via an adhesive layer.

  Next, the active energy ray-curable composition constituting the adhesive layer is squeezed out using a rubber roll having a JIS hardness of 40 ° so that the adhesive layer has a thickness of 15 μm, and is compressed so as not to contain bubbles. A curable resin substrate laminate was obtained. The thickness of the adhesive layer was calculated from the supply amount and development area of the active energy ray-curable composition.

The above active energy ray-curable resin substrate laminate was allowed to pass through a PET film for 60 seconds while being heated to 60 ° C., and then the position 2 cm below the metal halide lamp with an output of 9.6 kW was passed through 2 points. Then, the adhesive layer was cured to form a cured layer of a curable coating film, and a curable coating film cured layer-containing transfer film laminate was obtained. As curing conditions for obtaining a curable coating film-cured layer-containing transfer film laminate, the integrated light amount was 570 mJ / cm ² and the peak illuminance was 220 mW / cm ² . Then, the PET film was peeled from the curable coating film cured layer-containing transfer film laminate to obtain a resin laminate. The film thickness of the cured layer of the curable coating film in the obtained resin laminate was 13 μm.
Table 2 shows the evaluation results of the resin laminate.

[Examples 6 to 9]
A laminate was obtained in the same manner as in Example 5 except that the coating composition was changed as shown in Table 2 in Example 5. The results are shown in Table 2.

[Comparative Example 4]
A laminate was obtained in the same manner as in Example 5 except that the coating composition was changed as shown in Table 2 in Example 5. The results are shown in Table 2. Since the surface treatment of the hollow silica fine particles was performed in a polar solvent, the chemical resistance was insufficient. Furthermore, the scratch resistance was insufficient. Moreover, water repellency and oil repellency could not be imparted to the surface of the laminate by the transfer method.

[Comparative Example 5]
A laminate was obtained in the same manner as in Example 5 except that the coating composition was changed as shown in Table 2 in Example 5. The results are shown in Table 2. Since the surface treatment of the hollow silica fine particles was not performed, the chemical resistance was insufficient. Furthermore, the scratch resistance was remarkably insufficient. Moreover, water repellency and oil repellency could not be imparted to the surface of the laminate by the transfer method.

  According to the present invention, it is possible to obtain a laminate having a coating having various functions such as scratch resistance, antireflection, and antifouling properties on a resin substrate, and can be widely applied to front plates of various displays. .

Claims (7)

(A-1) 40 to 90% by mass of hollow silica fine particles, and (a-2) the following general formula (1)

(In the formula, X is CH ₂ ═CH—COO— group, CH ₂ ═C (CH ₃ ) —COO— group, or CH ₂ ═CH— group, R ₁ is an alkylene group having 1 to 8 carbon atoms, R ₂ , R ₃ is an alkyl group having 1 to 8 carbon atoms or hydrogen, a is a positive integer of 1 to 3, b is a positive integer of 0 to 2, and a + b is an integer of 1 to 3. A first step of heating a mixture containing 60 to 10% by mass and a polar solvent, a nonpolar solvent having a boiling point higher than the boiling point of the polar solvent in the mixture in which the solid content concentration of the mixture is 35% by mass or less A second step of adding, a third step of heating to volatilize the polar solvent and setting the solid content concentration to 30% by mass to 80% by mass, and a fourth step of performing a condensation reaction in the mixture For producing silica sol for use.   A coating composition comprising a silica sol obtained by the method according to claim 1 and a compound having at least two (meth) acryloyloxy groups in the molecule.   The coating composition according to claim 2, further comprising an antifouling compound.   A film formed by curing the composition according to claim 2.   The resin laminated body which has the film of Claim 4 in a surface layer. The manufacturing method of the resin laminated body which has the process as described in the following (1)-(5).
(1) A coating film forming step of forming a coating film by applying the composition according to claim 2 on the surface of the transparent substrate film (2) A cured film forming step of curing the coating film to form a cured film ( 3) Resin substrate laminate forming step of forming a resin substrate laminate by laminating a resin substrate on the surface of the cured coating through a thermoplastic resin coating layer (4) Adding the resin substrate laminate Forming a thermoplastic resin coating layer-containing transfer film laminate by forming a thermoplastic resin coating layer-containing transfer film laminate by integrating the resin base laminate by at least one treatment selected from pressure treatment and heating treatment Step (5) A resin laminate forming step of obtaining a resin laminate by peeling a transparent substrate film from the thermoplastic resin coating layer-containing transfer film laminate The manufacturing method of the resin laminated body which has the process as described in the following (1)-(5).
(1) A coating film forming step of forming a coating film by applying the composition according to claim 2 on the surface of the transparent substrate film (2) A cured film forming step of curing the coating film to form a cured film ( 3) An active energy ray that forms an active energy ray-curable resin substrate laminate by laminating a resin substrate on the surface of the cured film via a layer of a curable coating film containing an active energy ray-curable composition. Curable Resin Base Laminate Formation Step (4) Curable Coating Cured Layer Containing Transfer Film Forming the Cured Layer of the Curable Coating Film by Irradiating the Active Energy Ray Curable Resin Base Laminate with Active Energy Rays Laminate formation step (5) Resin laminate formation step of obtaining a resin laminate by peeling the transparent substrate film from the curable coating film cured layer-containing transfer film laminate