Low-reflection coatings, coating kits, cured products and laminates

Abstract

To provide a low-reflection coating agent, a coating agent kit, a cured product, and a laminate. [Solution] The present disclosure provides a low-reflection coating agent comprising an acidic group-containing poly(meth)acrylate, hollow inorganic particles, and solid alumina particles, the solid alumina particles being present in an amount of 2 to 15 mass% of the solid content. The present disclosure also provides a coating agent kit comprising a low-reflection coating agent containing 2 to 15 mass% of solid alumina particles of the solid content, and an anchoring agent containing solid alumina particles.

Description

[Technical Field]

[0001] The present disclosure relates to a low-reflection coating agent, a coating agent kit, a cured product, and a laminate. [Background technology]

[0002] In recent years, liquid crystal display devices have been used as display devices for televisions, personal computers, etc. In such liquid crystal display devices, the use of an anti-reflection film including a low refractive index layer has been proposed to prevent reflection of external light and improve image quality (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-085383 Summary of the Invention [Problem to be solved by the invention]

[0004] Hollow particles are sometimes used to give coatings low reflectivity (low refractive index), but in this case, the hollow particles have the problem of lower scratch resistance.

[0005] By further blending solid alumina particles into a coating agent containing hollow particles, it is possible to prevent a decrease in scratch resistance. However, it was found that the coexistence of hollow particles and solid alumina particles in the same system poses stability problems.

[0006] Therefore, one of the problems to be solved by the present invention is to provide a low-reflection coating agent with good stability.

[0007] One of the problems that the invention aims to solve is to provide a coating agent kit that can produce a laminate that has good scratch resistance while maintaining low reflectivity. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have found that the above problems can be solved by using a specific component.

[0009] The present disclosure provides the following: (Item 1) an acidic group-containing poly(meth)acrylate; hollow inorganic particles and Contains solid alumina particles, The content of the solid alumina particles is 2 to 15 mass% of the solid content. Low-reflection coating agent. (Item 2) The low-reflection coating agent according to the above item, which contains a (meth)acryloyl group-containing perfluoropolyether. (Item 3) A low-reflection coating agent containing 2 to 15 mass% of solid alumina particles in the solid content, and A coating agent kit comprising an anchoring agent comprising solid alumina particles. (Item 4) A cured product of the low-reflection coating agent according to any one of the above items and / or the coating agent kit according to the above items. (Item 5) A laminate comprising the cured product described in the above item.

[0010] In the present disclosure, one or more of the above-described features may be provided in further combinations in addition to the combinations explicitly stated. [Effects of the Invention]

[0011] The low-reflection coating agent according to this embodiment has good stability.

[0012] By using the coating agent kit according to this embodiment, a laminate having low reflectivity and excellent scratch resistance can be produced. DETAILED DESCRIPTION OF THE INVENTION

[0013] Throughout this disclosure, the range of the values ​​of the physical properties, contents, etc. can be set as appropriate (for example, by selecting from the upper and lower limit values ​​described in each item below). Specifically, when A3, A2, A1 (where A3 > A2 > A1) are exemplified as the upper and lower limits of the value α, the range of the value α can be exemplified as A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more but A2 or less), A1 to A3, A2 to A3, A1 or more but less than A3, A1 or more but less than A2, A2 or more but less than A3, greater than A1 but less than A3, greater than A1 but less than A2, greater than A2 but less than A3, greater than A1 ...

[0014] [Low-reflection coating agent: also called coating agent] The present disclosure relates to an acidic group-containing poly(meth)acrylate, hollow inorganic particles and Contains solid alumina particles, The content of the solid alumina particles is 2 to 15 mass% of the solid content. To provide a low-reflection coating agent.

[0015] <Poly(meth)acrylate containing acidic groups> The acidic group-containing poly(meth)acrylates may be used alone or in combination of two or more.

[0016] In the present disclosure, "acidic group-containing poly(meth)acrylate" means a compound having one or more acidic groups and two or more (meth)acryloyl groups.

[0017] In the present disclosure, an "acidic group" refers to a group in which one or more hydrogen atoms dissociate to generate a base.

[0018] Examples of the acidic group include a hydroxyl group, a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

[0019] In this disclosure, "(meth)acrylic" means "at least one selected from the group consisting of acrylic and methacrylic." Similarly, "(meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate." Furthermore, "(meth)acryloyl" means "at least one selected from the group consisting of acryloyl and methacryloyl."

[0020] It is believed that the use of an acidic group-containing poly(meth)acrylate can improve the stability of the low-reflectivity coating agent. This is believed to be because the acidic group-containing poly(meth)acrylate acts as a dispersant for the solid alumina particles, preventing the solid alumina particles from aggregating and settling. Note that the above is merely one theory, and it is not intended that the present invention be limited to this theory.

[0021] Examples of the acidic group-containing poly(meth)acrylate include hydroxyl group-containing poly(meth)acrylate and carboxyl group-containing poly(meth)acrylate.

[0022] (Hydroxyl group-containing poly(meth)acrylate) Examples of hydroxyl group-containing poly(meth)acrylates include hydroxyl group-containing (poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, hydroxyl group-containing (poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, and hydroxyl group-containing (poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate.

[0023] Hydroxyl group-containing (poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate (Poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (A') or the like. [ka] [wherein n is an integer of 0 to 2, and R b1’ ~R b6 ’ are each independently a hydrogen atom, [ka] wherein each q is independently an integer of 0 to 16; 1’ ~R 3’ are each independently a hydrogen atom or an alkyl group, and R 1’ may have different groups in each unit. and R b4’ , and R b5’ may be different groups for each structural unit, Formula (A ’ ) in R b1’ ~R b6 ’ Two or more of [ka] wherein q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, and R 1’ may have different groups in each unit. and R b1’ ~R b6 ’ At least one of the atoms is a hydrogen atom.

[0024] In the present disclosure, the phrase "the groups may be different for each structural unit" means, for example, when n is 2 in formula (A'), [ka] R b4A and R b4B and R b5A and R b5B This means that the group may be a group different from

[0025] In the present disclosure, "hydroxyl group-containing (poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of hydroxyl group-containing pentaerythritol poly(meth)acrylate, hydroxyl group-containing pentaerythritol polyalkylene oxide-modified (meth)acrylate, hydroxyl group-containing pentaerythritol polyepoxy-modified (meth)acrylate, hydroxyl group-containing polypentaerythritol poly(meth)acrylate, hydroxyl group-containing polypentaerythritol polyalkylene oxide-modified (meth)acrylate, and hydroxyl group-containing polypentaerythritol polyepoxy-modified (meth)acrylate."

[0026] Examples of the hydroxyl group-containing pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate and pentaerythritol tri(meth)acrylate.

[0027] Examples of the hydroxyl group-containing pentaerythritol polyalkylene oxide-modified (meth)acrylate include pentaerythritol di(ethylene oxide-modified (meth)acrylate), pentaerythritol tri(ethylene oxide-modified (meth)acrylate), pentaerythritol di(propylene oxide-modified (meth)acrylate), and pentaerythritol tri(propylene oxide-modified (meth)acrylate).

[0028] Examples of the hydroxyl group-containing pentaerythritol polyepoxy-modified (meth)acrylate include pentaerythritol diepoxy (meth)acrylate and pentaerythritol triepoxy (meth)acrylate.

[0029] Examples of hydroxyl group-containing polypentaerythritol poly(meth)acrylates include dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, and tripentaerythritol hepta(meth)acrylate.

[0030] Hydroxyl group-containing polypentaerythritol polyalkylene oxide-modified (meth)acrylates include dipentaerythritol di(ethylene oxide-modified (meth)acrylate), dipentaerythritol tri(ethylene oxide-modified (meth)acrylate), dipentaerythritol tetra(ethylene oxide-modified (meth)acrylate), dipentaerythritol penta(ethylene oxide-modified (meth)acrylate), dipentaerythritol hexa(ethylene oxide-modified (meth)acrylate), acrylate), dipentaerythritol di(propylene oxide modified (meth)acrylate), dipentaerythritol tri(propylene oxide modified (meth)acrylate), dipentaerythritol tetra(propylene oxide modified (meth)acrylate), dipentaerythritol penta(propylene oxide modified (meth)acrylate), tripentaerythritol di(ethylene oxide modified (meth)acrylate), tripentaerythritol tri(ethylene oxide modified (meth)acrylate) Tripentaerythritol tetra(ethylene oxide modified (meth)acrylate), tripentaerythritol penta(ethylene oxide modified (meth)acrylate), tripentaerythritol hexa(ethylene oxide modified (meth)acrylate), tripentaerythritol hepta(ethylene oxide modified (meth)acrylate), tripentaerythritol octa(ethylene oxide modified (meth)acrylate), tripentaerythritol di(propylene

[0033] Examples of the acrylate include tripentaerythritol tri(propylene oxide-modified (meth)acrylate), tripentaerythritol tetra(propylene oxide-modified (meth)acrylate), tripentaerythritol penta(propylene oxide-modified (meth)acrylate), tripentaerythritol hexa(propylene oxide-modified (meth)acrylate), and tripentaerythritol hepta(propylene oxide-modified (meth)acrylate).

[0031] Examples of hydroxyl group-containing polypentaerythritol polyepoxy-modified (meth)acrylates include dipentaerythritol diepoxy(meth)acrylate, dipentaerythritol triepoxy(meth)acrylate, dipentaerythritol tetraepoxy(meth)acrylate, dipentaerythritol pentaepoxy(meth)acrylate, tripentaerythritol diepoxy(meth)acrylate, tripentaerythritol triepoxy(meth)acrylate, tripentaerythritol tetraepoxy(meth)acrylate, tripentaerythritol pentaepoxy(meth)acrylate, tripentaerythritol hexaepoxy(meth)acrylate, and tripentaerythritol heptaepoxy(meth)acrylate.

[0032] Hydroxyl group-containing (poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate The hydroxyl group-containing (poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (B') or the like. [ka] [In the formula, m is an integer of 0 to 2, and R b7’ ~R b10 ’ are each independently a hydrogen atom, [ka] wherein each q is independently an integer of 0 to 16; 1’ ~R 3’ are each independently a hydrogen atom or an alkyl group, and R 1’ may have different groups in each unit. and R b9’ may be different groups for each structural unit, Formula (B ’ ) in R b7’ ~R b10 ’ Two or more of [ka] wherein q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, and R 1’ may have different groups in each unit. and R b7’ ~R b10 ’ At least one of the atoms is a hydrogen atom.

[0033] In the present disclosure, "hydroxyl group-containing (poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of hydroxyl group-containing trimethylolpropane poly(meth)acrylate, hydroxyl group-containing trimethylolpropane polyalkylene oxide-modified (meth)acrylate, hydroxyl group-containing trimethylolpropane polyepoxy-modified (meth)acrylate, hydroxyl group-containing polytrimethylolpropane poly(meth)acrylate, hydroxyl group-containing polytrimethylolpropane polyalkylene oxide-modified (meth)acrylate, and hydroxyl group-containing polytrimethylolpropane polyepoxy-modified (meth)acrylate."

[0034] Examples of the hydroxyl group-containing trimethylolpropane poly(meth)acrylate include trimethylolpropane di(meth)acrylate.

[0035] Examples of the hydroxyl group-containing trimethylolpropane polyalkylene oxide-modified (meth)acrylate include trimethylolpropane di(ethylene oxide-modified (meth)acrylate) and trimethylolpropane di(propylene oxide-modified (meth)acrylate).

[0036] Examples of the hydroxyl group-containing trimethylolpropane polyepoxy-modified (meth)acrylate include trimethylolpropane diepoxy (meth)acrylate.

[0037] Examples of the hydroxyl group-containing polytrimethylolpropane poly(meth)acrylate include ditrimethylolpropane di(meth)acrylate and ditrimethylolpropane tri(meth)acrylate.

[0038] Examples of the hydroxyl group-containing polytrimethylolpropane polyalkylene oxide-modified (meth)acrylate include ditrimethylolpropane di(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane tri(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane di(propylene oxide-modified (meth)acrylate), and ditrimethylolpropane tri(propylene oxide-modified (meth)acrylate).

[0039] Examples of the hydroxyl group-containing polytrimethylolpropane polyepoxy-modified (meth)acrylate include ditrimethylolpropane diepoxy (meth)acrylate and ditrimethylolpropane triepoxy (meth)acrylate.

[0040] Hydroxyl group-containing (poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate The hydroxyl group-containing (poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (C') or the like. [ka] [wherein p is an integer of 0 to 7, and R b11’ ~R b14 ’ are each independently a hydrogen atom, [ka] wherein q is an integer of 0 to 16, and R 1’ ~R 3’ are each independently a hydrogen atom or an alkyl group, and R 1’ may have different groups in each unit. and R b13’may be different groups for each structural unit, Formula (C ’ ) in R b11’ ~R b14 ’ Two or more of [ka] wherein q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, and R 1’ may have different groups in each unit. and R b11’ ~R b14 ’ At least one of the is a hydrogen atom.

[0041] In the present disclosure, "hydroxyl group-containing (poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of hydroxyl group-containing glycerin poly(meth)acrylate, hydroxyl group-containing glycerin polyalkylene oxide-modified (meth)acrylate, hydroxyl group-containing glycerin polyepoxy-modified (meth)acrylate, hydroxyl group-containing polyglycerin poly(meth)acrylate, hydroxyl group-containing polyglycerin polyalkylene oxide-modified (meth)acrylate, and hydroxyl group-containing polyglycerin polyepoxy-modified (meth)acrylate."

[0042] Examples of the hydroxyl group-containing glycerin poly(meth)acrylate include glycerin di(meth)acrylate.

[0043] Examples of the hydroxyl group-containing glycerin polyalkylene oxide-modified (meth)acrylate include glycerin di(ethylene oxide-modified (meth)acrylate) and glycerin di(propylene oxide-modified (meth)acrylate).

[0044] Examples of the hydroxyl group-containing glycerin polyepoxy-modified (meth)acrylate include glycerin diepoxy (meth)acrylate.

[0045] Examples of the hydroxyl group-containing polyglycerol poly(meth)acrylate include diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, triglycerol di(meth)acrylate, triglycerol tri(meth)acrylate, and triglycerol tetra(meth)acrylate.

[0046] Examples of hydroxyl group-containing polyglycerol polyalkylene oxide-modified (meth)acrylates include diglycerol di(ethylene oxide-modified (meth)acrylate), diglycerol tri(ethylene oxide-modified (meth)acrylate), triglycerol di(ethylene oxide-modified (meth)acrylate), triglycerol tri(ethylene oxide-modified (meth)acrylate), triglycerol tetra(ethylene oxide-modified (meth)acrylate), diglycerol di(propylene oxide-modified (meth)acrylate), diglycerol tri(propylene oxide-modified (meth)acrylate), triglycerol di(propylene oxide-modified (meth)acrylate), triglycerol tri(propylene oxide-modified (meth)acrylate), triglycerol tetra(propylene oxide-modified (meth)acrylate), and the like.

[0047] Examples of hydroxyl group-containing polyglycerol polyepoxy-modified (meth)acrylates include diglycerol diepoxy (meth)acrylate, diglycerol triepoxy (meth)acrylate, triglycerol diepoxy (meth)acrylate, triglycerol triepoxy (meth)acrylate, and triglycerol tetraepoxy (meth)acrylate.

[0048] (Carboxyl group-containing poly(meth)acrylate) Examples of the carboxyl group-containing poly(meth)acrylate include a reaction product of a hydroxyl group-containing poly(meth)acrylate with a carboxylic acid anhydride.

[0049] Examples of carboxylic acid anhydrides include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, maleic anhydride, itaconic anhydride, and succinic anhydride.

[0050] Examples of carboxyl group-containing poly(meth)acrylate products include Aronix M510 (acid value: 80 to 120 mgKOH / g, manufactured by Toagosei Co., Ltd.) and Aronix M520 (acid value: 20 to 40 mgKOH / g, manufactured by Toagosei Co., Ltd.).

[0051] In one embodiment, from the viewpoint of achieving good scratch resistance in a cured product, the acidic group-containing poly(meth)acrylate is preferably a carboxyl group-containing poly(meth)acrylate, more preferably a reaction product of pentaerythritol tri(meth)acrylate or dipentaerythritol penta(meth)acrylate with a carboxylic acid anhydride, still more preferably a reaction product of pentaerythritol tri(meth)acrylate with a carboxylic acid anhydride, and particularly preferably a reaction product of pentaerythritol tri(meth)acrylate with succinic anhydride.

[0052] Examples of upper and lower limits of the molecular weight of the acidic group-containing poly(meth)acrylate include 50,000, 40,000, 30,000, 20,000, 10,000, 5,000, 4,000, 2,000, 1,000, 900, 800, 700, 600, 500, 450, 400, 300, 250, 100, and 50. In one embodiment, the molecular weight is preferably 50 to 50,000.

[0053] In this disclosure, when simply referring to "molecular weight," it means either formula weight or number average molecular weight. When the structure of a compound can be unequivocally expressed by a specific chemical formula (i.e., the molecular weight distribution is 1), the molecular weight refers to the formula weight. On the other hand, when the structure of a compound cannot be unequivocally expressed by a specific chemical formula (i.e., the molecular weight distribution is greater than 1), the molecular weight refers to the number average molecular weight.

[0054] Examples of upper and lower limits of the acid value of the acidic group-containing poly(meth)acrylate are 300, 290, 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, and 10 mgKOH / g. In one embodiment, the acid value is preferably 10 to 300 mgKOH / g.

[0055] Examples of upper and lower limits of the hydroxyl value of the acidic group-containing poly(meth)acrylate include 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, and 0 mgKOH / g. In one embodiment, the hydroxyl value is preferably 0 to 280 mgKOH / g, and more preferably 10 to 280 mgKOH / g.

[0056] The upper and lower limits of the number of (meth)acryloyl groups in the acidic group-containing poly(meth)acrylate are, for example, 30, 28, 26, 24, 22, 20, 18, 16, 14, 12, 10, 9, 8, 7, 6, 5, 4, 3, and 2. In one embodiment, the number is preferably about 2 to 30.

[0057] The upper and lower limits of the number of acidic groups in the acidic group-containing poly(meth)acrylate are, for example, 10, 9, 8, 7, 6, 5, 4, 3, 2, and 1. In one embodiment, the number is preferably 1 to 10.

[0058] The upper and lower limits of the content of the acidic group-containing poly(meth)acrylate in 100% by mass of the solid content of the coating agent are 70, 65, 60, 57, 55, 54, 53, 52, 51, 50, 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, 35, 30, 25, 20% by mass, etc. In one embodiment, the content is preferably 20 to 70% by mass.

[0059] <Hollow inorganic particles> The hollow inorganic particles may be used alone or in combination of two or more kinds.

[0060] The hollow particles can be any shape, such as spherical, rod-like, plate-like, fibrous, or irregular, as long as they have voids inside.

[0061] Examples of hollow inorganic particles include hollow silica particles, hollow aluminosilicate particles, hollow alumina particles, hollow mullite particles, hollow titanium oxide particles, hollow magnesium fluoride particles, and fly ash balloons.

[0062] In one embodiment, the hollow inorganic particles are preferably surface-modified hollow inorganic particles. Examples of the modified hollow inorganic particles include (meth)acrylic-modified hollow inorganic particles and silicone-modified hollow inorganic particles.

[0063] The upper and lower limits of the content of the modified moiety relative to 100% by mass of the modified hollow inorganic particles are, for example, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0.1, 0.01% by mass, etc. In one embodiment, from the viewpoint of improving the dispersibility of the particles and the scratch resistance of the cured product, the content is preferably about 0.01 to 40% by mass, more preferably 0.1 to 30% by mass, and even more preferably 1 to 20% by mass.

[0064] Examples of hollow inorganic particle products include Sururia 5320, Sururia 4320, Sururia 4110, Sururia 2320, Sururia 1110, JX1008SIV, JX1009SIV (manufactured by JGC Catalysts and Chemicals Industries, Ltd.), and Silinax (manufactured by Nittetsu Mining Co., Ltd.).

[0065] The upper and lower limits of the particle diameter of the hollow inorganic particles are, for example, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, and 40 nm. In one embodiment, the particle diameter is preferably 40 to 100 nm.

[0066] The particle size of the hollow inorganic particles is measured using a scanning electron microscope (for example, JSM-7800F Prime (manufactured by JEOL Ltd.)) and a STEM detector (manufactured by DEBEN UK Ltd.). Specifically, the measurement is performed according to the following procedure. First, the particle sample was diluted with methyl isobutyl ketone to 0.2% active ingredient and thoroughly stirred. Next, a drop of the dispersion was placed on a microgrid with a support film for STEM (Hi-Res Carbon HRC-C10 STEM Cu100P grid (manufactured by Stem Corporation)) and dried to prepare the measurement sample. Next, images are taken using a scanning electron microscope at an accelerating voltage of 30 kV at a magnification (e.g., 300k times) that allows the particles in the field of view to be measured sufficiently, and the particle diameters of 50 randomly selected particles are measured to determine the particle diameter on a number basis. The particle diameter measurement can be done manually or using a measuring tool.

[0067] The upper and lower limits of the refractive index of the hollow inorganic particles are exemplified as 1.5, 1.4, 1.3, 1.2, 1.1, etc. In one embodiment, the refractive index of the hollow inorganic particles is preferably 1.1 to 1.5.

[0068] The refractive index of the hollow inorganic particles is calculated by forming a film of a composition containing the object to be measured at a solid ratio of 1 mass %, 10 mass %, or 20 mass % in an active energy ray-curable resin (for example, dipentaerythritol polyacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.: product name NK Ester A-9550W), measuring the refractive index at the wavelength of the sodium D line using an Abbe refractometer (product name "NAR-1T SOLID" manufactured by Atago Co., Ltd.) in accordance with JIS K7142:2014, and extrapolating the result to a solid ratio of 100 mass %.

[0069] The upper and lower limits of the content of hollow inorganic particles in 100% by mass of the solid content of the coating agent are 65, 60, 55, 50, 45, 44, 43, 42, 41, 40, 39, 38, 37, 35, 30, 25, 20% by mass, etc. In one embodiment, the content is preferably 20 to 65% by mass.

[0070] <Solid alumina particles> The solid alumina particles may be used alone or in combination of two or more types.

[0071] Solid particles are particles that do not have any internal voids.

[0072] Alumina refers to aluminum oxide represented by Al2O3, and is known to have various forms such as α-type, γ-type, σ-type, and mixtures thereof.

[0073] The solid alumina particles may be spherical, rod-like, plate-like, fibrous, or irregular in shape.

[0074] In one embodiment, the solid alumina particles are preferably surface-modified solid alumina particles, such as (meth)acrylic-modified solid alumina particles and silicone-modified solid alumina particles.

[0075] Examples of solid alumina particle products include Alumisol F-3000 (Kawaken Fine Chemicals Co., Ltd.), Bylar AL-7 (Taki Chemical Co., Ltd.), NANOBYK-3610 (BYK Chemie), and Optisol LAA530U (RANCO).

[0076] The upper and lower limits of the primary particle diameter of the solid alumina particles are, for example, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10, 7, 3 nm, etc. In one embodiment, the primary particle diameter is preferably 3 to 110 nm.

[0077] The primary particle size of the solid alumina particles can be measured by the same method as the method for measuring the particle size of the hollow inorganic particles.

[0078] The upper and lower limits of the secondary particle diameter of the solid alumina particles are, for example, 110, 100, 90, 80, 70, 60, 55, 50, 45, 40, 35, 30, 25 nm, etc. In one embodiment, the secondary particle diameter is preferably 25 to 110 nm.

[0079] The secondary particle size of the solid alumina particles is measured by the following procedure. First, the particle sample is diluted with methyl isobutyl ketone to 1% active ingredient to prepare a sample solution. Next, the prepared sample solution is measured using a nanoparticle size measurement device (product name "Nanotrac UPA-EX150 (Microtrac Bell Co., Ltd.)") using dynamic light scattering. The particle size obtained by this measurement method is the volume average particle size, and the median diameter value is used as the particle size.

[0080] The upper and lower limits of the content of the solid alumina particles in 100% by mass of the solid content of the coating agent are exemplified as 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2% by mass, etc. In one embodiment, the content is preferably 2 to 15% by mass, more preferably 6 to 15% by mass.

[0081] <(Meth)acryloyl group-containing perfluoropolyether> In one embodiment, the coating agent may contain a (meth)acryloyl group-containing perfluoropolyether. The (meth)acryloyl group-containing perfluoropolyether may be used alone or in combination of two or more kinds.

[0082] In the present disclosure, the (meth)acryloyl group-containing perfluoropolyether refers to a compound in which one or more (meth)acryloyl groups are bonded to a perfluoropolyether. The perfluoropolyether refers to a compound having a perfluoroalkylene ether as a repeating unit.

[0083] Examples of the (meth)acryloyl group-containing perfluoropolyether include perfluoropolyethers containing (meth)acryloyl groups at both ends, and perfluoropolyethers containing a (meth)acryloyl group at one end.

[0084] Examples of (meth)acryloyl group-containing perfluoropolyether products include KY-1203 and KY-1207 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0085] In one embodiment, silicon atom- and (meth)acryloyl group-containing perfluoropolyethers are preferred from the viewpoint of imparting water and oil repellency, slipperiness, and fingerprint resistance to the surface of the cured product. Commercially available silicon atom- and (meth)acryloyl group-containing perfluoropolyethers include KY-1203.

[0086] The upper and lower limits of the content of the (meth)acryloyl group-containing perfluoropolyether in 100% by mass of the solid content of the coating agent are, for example, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0% by mass, etc. In one embodiment, the content is preferably 0 to 10% by mass.

[0087] <Photopolymerization initiator> In one embodiment, the coating agent may contain a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more kinds.

[0088] Examples of the photopolymerization initiator include a radical photopolymerization initiator, a cationic photopolymerization initiator, and an anionic photopolymerization initiator.

[0089] Examples of the radical photopolymerization initiator include alkylphenone-type photopolymerization initiators, acylphosphine oxide-type photopolymerization initiators, hydrogen abstraction-type photopolymerization initiators, and oxime ester-type photopolymerization initiators.

[0090] Examples of alkylphenone-type photopolymerization initiators include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one, α-hydroxyalkylphenones such as 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, and α-aminoalkylphenones such as 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0091] Examples of the acylphosphine oxide type photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like.

[0092] Examples of hydrogen abstraction type photopolymerization initiators include phenylglyoxylic acid methyl ester.

[0093] Examples of oxime ester type photopolymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and the like.

[0094] Examples of cationic photopolymerization initiators include a mixture of iodonium, (4-methylphenyl)]4-(2-methylpropyl)phenyl]-hexafluorophosphate(1-) and propylene carbonate, triarylsulfonium hexafluorophosphate, and triarylsulfonium tetrakis-(pentafluorophenyl)borate.

[0095] Examples of the anionic photopolymerization initiator include cobalt amine complexes, o-nitrobenzyl alcohol carbamic acid esters, and oxime esters.

[0096] The upper and lower limits of the content of the photopolymerization initiator in 100% by mass of the solid content of the coating agent are 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0% by mass, etc. In one embodiment, the content is preferably 0 to 10% by mass.

[0097] <Organic solvents> In one embodiment, the coating agent may contain an organic solvent. The organic solvent may be used alone or in combination of two or more kinds.

[0098] Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum-based solvents, haloalkane solvents, and amide solvents.

[0099] Examples of the ketone solvent include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.

[0100] Examples of aromatic solvents include toluene and xylene.

[0101] Examples of alcohol solvents include methanol, ethanol, n-propanol, isopropanol, and butanol.

[0102] Examples of glycol solvents include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol.

[0103] Examples of glycol ether solvents include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, and ethylene glycol mono-t-butyl ether.

[0104] Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

[0105] Examples of petroleum-based solvents include Solvesso #100 (manufactured by Exxon Corporation) and Solvesso #150 (manufactured by Exxon Corporation).

[0106] The haloalkane solvent is exemplified by chloroform.

[0107] The amide solvent is exemplified by dimethylformamide.

[0108] The upper and lower limits of the content of the organic solvent in 100% by mass of the coating agent are 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, 0% by mass, etc. In one embodiment, the content is preferably 0 to 99% by mass.

[0109] The upper and lower limits of the mass ratio of the acidic group-containing poly(meth)acrylate to the hollow inorganic particles in the coating agent (mass of acidic group-containing poly(meth)acrylate / mass of hollow inorganic particles) are exemplified as 3.5, 3.3, 3, 2.7, 2.5, 2.3, 2, 1.7, 1.5, 1.3, 1, 0.7, 0.5, 0.3, etc. In one embodiment, the mass ratio is preferably 0.3 to 3.5.

[0110] The upper and lower limits of the mass ratio of the acidic group-containing poly(meth)acrylate to the solid alumina particles in the coating agent (mass of acidic group-containing poly(meth)acrylate / mass of solid alumina particles) are 11.7, 11.5, 11.3, 11, 10.7, 10.5, 10.3, 10, 9.7, 9.5, 9.3, 9, 8.7, 8.5, 8.3, 8, 7.7, 7.5, 7.3, 7, 6.7, 6.5, 6.3, 6, 5.7, 5.5, 5.3, 5, 4.7, 4.5, 4, 3.7, 3.5, 3.3, 3, 2.7, 2.5, 2.3, 2, 1.7, 1.5, 1.3, etc. In one embodiment, the mass ratio is preferably 1.3 to 11.7.

[0111] The upper and lower limits of the mass ratio of hollow inorganic particles to solid alumina particles in the coating agent (mass of hollow inorganic particles / mass of solid alumina particles) are exemplified as 10.8, 10.5, 10.3, 10, 9.7, 9.5, 9.3, 9, 8.7, 8.5, 8.3, 8, 7.7, 7.5, 7.3, 7, 6.7, 6.5, 6.3, 6, 5.7, 5.5, 5.3, 5, 4.7, 4.5, 4, 3.7, 3.5, 3.3, 3, 2.7, 2.5, 2.3, 2, 1.7, 1.5, 1.3, etc. In one embodiment, the mass ratio is preferably 1.3 to 10.8.

[0112] <Additives> The coating agent may contain, as an additive, an agent that does not fall into any of the following categories: acidic group-containing poly(meth)acrylate, hollow inorganic particles, solid alumina particles, (meth)acryloyl group-containing perfluoropolyether, photopolymerization initiator, and organic solvent.

[0113] Examples of additives include binder resins (acrylic resins, urethane resins, polyester resins, epoxy resins, alkyd resins, etc.), antislip agents, slip agents, preservatives, rust inhibitors, pH adjusters, pigments, dyes, lubricants, leveling agents, catalysts, antifoaming agents, and photosensitizers (amines, quinones, etc.).

[0114] In one embodiment, the content of the additive is, for example, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc., relative to 100 parts by mass of the coating agent. Further, for example, the content of the additive is, for example, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc., relative to 100 parts by mass of any of the acidic group-containing poly(meth)acrylate, hollow inorganic particles, solid alumina particles, (meth)acryloyl group-containing perfluoropolyether, photopolymerization initiator, and organic solvent.

[0115] The coating agent can be produced by dispersing and mixing the acidic group-containing poly(meth)acrylate, hollow inorganic particles, and solid alumina particles, as well as (meth)acryloyl group-containing perfluoropolyether, photopolymerization initiator, organic solvent, and additives as needed, by various known means. The order of addition of the components is not particularly limited. Various known devices (such as an emulsifying disperser or ultrasonic disperser) can be used as the dispersing and mixing means.

[0116] [Coating agent kit] The present disclosure provides a coating agent kit including a low-reflection coating agent containing 2 to 15 mass % of solid alumina particles in the solid content, and an anchor agent containing solid alumina particles.

[0117] The components and amounts contained in the low-reflection coating agent in the coating agent kit are exemplified by those mentioned above.

[0118] After preparing the coating kit, the coating kit can be used to prepare a laminate within a time period in which stability is not an issue. In this case, the desired laminate can be obtained even if the coating kit does not contain an acidic group-containing poly(meth)acrylate. Furthermore, low reflectivity can be achieved by using fluorine-based resins or the like, even without using hollow inorganic particles.

[0119] <Anchor agent> Examples of the solid alumina particles contained in the anchoring agent include those mentioned above. The solid alumina particles may be used alone or in combination of two or more kinds.

[0120] The upper and lower limits of the content of the solid alumina particles in 100% by mass of the anchor agent solid content are 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2% by mass, etc. In one embodiment, the content is preferably 2 to 18% by mass.

[0121] Poly(meth)acrylate In one embodiment, the anchoring agent may include poly(meth)acrylate. The poly(meth)acrylate may be used alone or in combination of two or more types.

[0122] Examples of poly(meth)acrylates include acidic group-containing poly(meth)acrylates and urethane poly(meth)acrylates.

[0123] Examples of the acidic group-containing poly(meth)acrylate include those mentioned above.

[0124] Examples of urethane poly(meth)acrylates include reaction products of compounds containing hydroxyl group-containing poly(meth)acrylates and polyisocyanates.

[0125] Examples of the hydroxyl group-containing poly(meth)acrylate that can be used as a raw material for the urethane poly(meth)acrylate include those mentioned above.

[0126] In this disclosure, a "polyisocyanate" is a compound having two or more isocyanate groups (-N=C=O).

[0127] Examples of polyisocyanates include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and their biurets, isocyanurates (nurates), allophanates, adducts, and the like.

[0128] Examples of the linear aliphatic polyisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate.

[0129] Examples of branched aliphatic polyisocyanates include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0130] Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanates, crosslinked cyclic alicyclic polyisocyanates, and condensed cyclic alicyclic polyisocyanates.

[0131] Examples of monocyclic alicyclic polyisocyanates include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, and dicyclohexylmethane diisocyanate.

[0132] Examples of the crosslinked alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0133] An example of the condensed ring alicyclic polyisocyanate is bicyclodecylene diisocyanate.

[0134] Examples of the aromatic group include a monocyclic aromatic group, a fused ring aromatic group, etc. Furthermore, one or more hydrogen atoms of the aromatic group may be substituted with a linear or branched alkyl group.

[0135] Examples of the monocyclic aromatic group include a phenyl group (phenylene group), a tolyl group (tolylene group), and a mesityl group (mesitylene group), and examples of the fused ring aromatic group include a naphthyl group (naphthylene group).

[0136] Examples of aromatic polyisocyanates include monocyclic aromatic polyisocyanates and condensed ring aromatic polyisocyanates.

[0137] Examples of monocyclic aromatic polyisocyanates include dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

[0138] An example of the condensed ring aromatic polyisocyanate is 1,5-naphthylene diisocyanate.

[0139] The biuret form of polyisocyanate is The following structural formula: [ka] [where n b is an integer equal to or greater than 1, and R bA ~R bE are each independently an alkylene group or an arylene group, and R bα ~R bβ are each independently an isocyanate group or [ka] (n b1 is an integer greater than or equal to 0, and R b1 ~R b5 are each independently an alkylene group or an arylene group, and R b '~R b '' each independently represent an isocyanate group or R bα ~R bβ It is a group of its own. R b4 ~R b5 , R b '' may be different groups for each structural unit. bD ~R bE , R bβmay be different groups for each structural unit.

[0140] Examples of biuret polyisocyanates include Duranate 24A-100, Duranate 22A-75P, and Duranate 21S-75E (all manufactured by Asahi Kasei Corporation), and Desmodur N3200A (a biuret of hexamethylene diisocyanate) (all manufactured by Sumika Covestro Urethane Co., Ltd.).

[0141] Isocyanurate of polyisocyanate The following structural formula: [ka] [where n i is an integer greater than or equal to 0, and R iA ~R iE are each independently an alkylene group or an arylene group, and R iα ~R iβ are each independently an isocyanate group or [ka] (n i1 is an integer greater than or equal to 0, and R i1 ~R i5 are each independently an alkylene group or an arylene group, and R i '~R i '' each independently represent an isocyanate group or R iα ~R iβ It is a group of its own. R i5 , R i '' may be different groups for each structural unit. iD ~R iE , R iβ may be different groups for each structural unit.

[0142] Commercially available isocyanurate polyisocyanates include Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, and Duranate MHG-80B (all manufactured by Asahi Kasei Corporation), Coronate HXR, Coronate HX, and Coronate HK (isocyanurate of hexamethylene diisocyanate), and Coronate 2037 (all manufactured by Tosoh Corporation), Takenate D-127N (isocyanurate of hydrogenated xylene diisocyanate), Takenate D-131N (isocyanurate of xylene diisocyanate), and Takenate D-204EA-1 (isocyanurate of tolylene diisocyanate) (all manufactured by Mitsui Chemicals, Inc.), and VESTANAT Examples include T1890 / 100 (isocyanurate of isophorone diisocyanate) (both manufactured by Evonik Japan Co., Ltd.).

[0143] Allophanate forms of polyisocyanates are The following structural formula: [ka] [In the formula, n is an integer of 0 or more, and R A is an alkyl group or an aryl group, and R B ~R G are each independently an alkylene group or an arylene group, and R α ~R γ are each independently an isocyanate group or [ka] (n1 is an integer equal to or greater than 0, and R 1 ~R 6 are each independently an alkylene group or an arylene group, and R' to R''' are each independently an isocyanate group or R α ~R γ It is a group of its own. R 1 ~R 4 , R' to R'' may be different groups for each structural unit. B ~R E , R α ~R βmay be different groups for each structural unit.

[0144] Examples of commercially available allophanate polyisocyanate products include Coronate 2793 (manufactured by Tosoh Corporation) and Takenate D-178N (manufactured by Mitsui Chemicals, Inc.).

[0145] Polyisocyanate adducts are The following structural formula: [ka] [where n ad is an integer greater than or equal to 0, and R adA ~R adE are each independently an alkylene group or an arylene group, and R ad1 ~R ad2 are each independently [ka] (In the formula, n ad’ is an integer greater than or equal to 0, R ad’ ~R ad’’ are each independently an alkylene group or an arylene group, R ad’’’ is R ad1 ~R ad2 It is the foundation of oneself, R ad’ ~R ad’’’ may have different groups for each structural unit. and R adD ~R adE , R ad2 may be different groups for each structural unit.] an adduct of trimethylolpropane and polyisocyanate represented by The following structural formula [ka] [where n ad1 is an integer greater than or equal to 0, R adα ~R adεare each independently an alkylene group or an arylene group, R adA ~R adB are each independently [ka] (In the formula, n ad1’ is an integer greater than or equal to 0, R adδ’ ~R adε’ are each independently an alkylene group or an arylene group, R adB’ is R adA ~R adB It is the foundation of oneself, R adδ’ ~R adε’ , R adB’ may be different groups for each structural unit. R adδ ~R adε may be different groups for each structural unit.] Examples include an adduct of glycerin and polyisocyanate represented by the following formula:

[0146] Examples of polyisocyanate adducts include Duranate P301-75E (both manufactured by Asahi Kasei Corporation), Takenate D110N, Takenate D160N (both manufactured by Mitsui Chemicals, Inc.), Coronate L, Coronate HL (both manufactured by Tosoh Corporation), and the like.

[0147] The upper and lower limits of the NCO content (NCO%) of the polyisocyanate are, for example, 30, 25, 20, 15, 10%, etc. In one embodiment, the NCO content (NCO%) is preferably 10 to 30%.

[0148] The upper and lower limits of the isocyanate group equivalent of the polyisocyanate are, for example, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 meq / g, etc. In one embodiment, the isocyanate group equivalent is preferably 1 to 10 meq / g.

[0149] In the present disclosure, the isocyanate group equivalent weight means the amount of isocyanate groups present in 1 g of solid.

[0150] The group of compounds that serve as raw materials for the urethane poly(meth)acrylate may include alkylene polyols, polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, polyolefin polyols, and the like.

[0151] Alkylene polyol Examples of the alkylene polyol include a straight chain alkylene polyol and a branched alkylene polyol.

[0152] Examples of the linear alkylene polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol.

[0153] Examples of branched alkylene polyols include neopentyl glycol, 2,4-diethyl-1,5-pentanediol, 2,4-dibutyl-1,5-pentanediol, 1-methylethylene glycol, 1-ethylethylene glycol, trimethylolpropane, and pentaerythritol.

[0154] Examples of the cycloalkylene polyol include a monocyclic cycloalkylene polyol and a crosslinked cycloalkylene polyol.

[0155] Examples of monocyclic cycloalkylene polyols include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2,2'-bis(4-hydroxycyclohexyl)propane.

[0156] Examples of the bridged ring cycloalkylene polyol include tricyclodecane dimethanol.

[0157] Polyether polyol In the present disclosure, "polyether polyol" refers to a compound having two or more hydroxy groups and two or more repeating units containing an ether bond. Two or more types of polyether polyols may be used in combination. In one embodiment, the polyether polyol has the following structural formula: HO-(R 3’ -O-) n H (In the formula, R 3’ is an alkylene group or a cycloalkylene group, and n is an integer of 2 or more.

[0158] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

[0159] Polyester Polyol In the present disclosure, "polyester polyol" refers to a compound having two or more hydroxy groups and two or more repeating units containing an ester bond in the molecule. Two or more types of polyester polyols may be used in combination. In one embodiment, the polyester polyol has the following structural formula: HO-{R 4a’ -OC(O)-R 4b’ -C(O)O} m -R 4a’ -OH (In the formula, R 4a’ and R 4b’ are each independently an alkylene group or a cycloalkylene group, and m is an integer of 2 or more.

[0160] In this disclosure, a "polyester polyol" is the reaction product of a polycarboxylic acid or anhydride with a polyol.

[0161] Examples of polycarboxylic acids include dicarboxylic acids.

[0162] Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, trimesic acid, and cyclohexanedicarboxylic acid.

[0163] Examples of polycarboxylic acid anhydrides include acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, and trimellitic anhydride.

[0164] Examples of polyols include the above alkylene polyols and cycloalkylene polyols.

[0165] Polycarbonate Polyol In the present disclosure, "polycarbonate polyol" refers to, for example, a compound having two or more hydroxy groups and two or more repeating units containing carbonate bonds. The polycarbonate polyols may be used alone or in combination.

[0166] In one embodiment, the polycarbonate polyol has the following structural formula: HO-{R aCarbo -OC(=O)O} p -R bCarbo -OH (In the formula, R aCarbo , and R bCarbo are each independently an alkylene group or a cycloalkylene group, and p is an integer of 2 or more.

[0167] Examples of polycarbonate polyols include a reaction product of polyol and phosgene, and a ring-opening polymer of a cyclic carbonate (such as alkylene carbonate).

[0168] Examples of polyols include the alkylene polyols mentioned above.

[0169] Examples of alkylene carbonates include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate.

[0170] Acrylic Polyol The acrylic polyol is a polymer of a group of monomers including a hydroxyl group-containing monomer, which may also include a non-hydroxyl group-containing monomer.

[0171] Polyolefin polyol The polyolefin polyol is a polyolefin having two or more hydroxyl groups. Examples of the polyolefin polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, and chlorinated products thereof.

[0172] The upper and lower limits of the number of (meth)acryloyl groups in the poly(meth)acrylate contained in the anchor agent are, for example, 15, 14, 12, 13, 11, 10, 9, 8, 7, 6, 5, 4, 3, and 2. In one embodiment, the number is preferably 2 to 15, and more preferably 3 to 15.

[0173] Examples of upper and lower limits for the poly(meth)acrylate content in 100% by mass of the anchor agent solid content are 94, 90, 88, 85, 80, 75, 70, 66, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0% by mass, etc. In one embodiment, the content is preferably 0 to 94% by mass.

[0174] Photopolymerization initiator In one embodiment, the anchoring agent may include a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more types.

[0175] Examples of the photopolymerization initiator include those mentioned above.

[0176] The upper and lower limits of the content of the photopolymerization initiator in 100% by mass of the solid content of the anchor agent are 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0% by mass, etc. In one embodiment, the content is preferably 0 to 10% by mass.

[0177] Examples of upper and lower limits of the mass ratio of poly(meth)acrylate to solid alumina particles in the anchoring agent (mass of poly(meth)acrylate / mass of solid alumina particles) are 47, 45, 43, 41, 40, 39, 37, 35, 33, 31, 30, 29, 27, 25, 23, 21, 20, 19, 17, 15, 13, 11, 10, 9, 8, 7, 5, 4, 3, 2, 1, 0.5, 0.2, 0.1, and 0. In one embodiment, the mass ratio is preferably 0 to 47.

[0178] The upper and lower limits of the mass ratio of the photopolymerization initiator to the solid alumina particles in the anchor agent (mass of photopolymerization initiator / mass of solid alumina particles) are exemplified as 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.7, 0.5, 0.4, 0.3, 0.2, 0.1, 0, etc. In one embodiment, the mass ratio is preferably 0 to 5.

[0179] Organic solvents In one embodiment, the anchoring agent may contain an organic solvent. The organic solvent may be used alone or in combination of two or more kinds.

[0180] Examples of the organic solvent include those mentioned above.

[0181] The upper and lower limits of the content of the organic solvent relative to 100% by mass of the anchor agent solid content are 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, 0% by mass, etc. In one embodiment, the content is preferably 0 to 80% by mass.

[0182] Additives for anchoring agents The anchoring agent may contain an agent that does not fall into any of the categories of solid alumina particles, poly(meth)acrylate, photopolymerization initiator, and organic solvent as an anchoring agent additive.

[0183] Examples of the additive for the anchoring agent include those mentioned above.

[0184] In one embodiment, the content of the anchoring agent additive is, for example, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc., relative to 100 parts by mass of the anchoring agent. Furthermore, the content of the anchoring agent additive is, for example, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc., relative to 100 parts by mass of any of the solid alumina particles, poly(meth)acrylate, photopolymerization initiator, and organic solvent in the anchoring agent.

[0185] The anchoring agent can be produced by dispersing and mixing solid alumina particles, and optionally poly(meth)acrylate, a photopolymerization initiator, an organic solvent, and an anchoring agent additive, by any known means. The order in which the components are added is not particularly limited. Any known device (such as an emulsifying disperser or an ultrasonic dispersing device) can be used as the dispersing and mixing means.

[0186] [Cured product] The present disclosure provides a cured product of the low-reflective coating agent and / or the coating agent kit.

[0187] Examples of curing conditions include those described below.

[0188] [Laminate] The present disclosure provides a laminate comprising the above-described cured product.

[0189] In one embodiment, a cured material layer made of the low-reflection coating agent or the cured material of the coating agent kit is laminated on at least one surface of a substrate. In one embodiment, an anchor agent cured material layer made of the cured material of the anchor agent is laminated on at least one surface of a substrate, and a low-reflection coating agent cured material layer made of the cured material of the low-reflection coating agent is laminated on the anchor agent cured material layer.

[0190] The upper and lower limits of the thickness of the substrate are exemplified as 125, 120, 110, 100, 90, 75, 50, 25, 10, 9, 5, 1 μm, etc. In one embodiment, the thickness of the substrate is preferably 1 to 125 μm.

[0191] The upper and lower limits of the thickness of the cured product layer of the low-reflective coating agent are exemplified as 200, 175, 150, 125, 100, 90, 75, 60, 55 nm, etc. In one embodiment, the thickness of the cured product layer of the low-reflective coating agent is preferably 55 to 200 nm.

[0192] The upper and lower limits of the thickness of the anchor agent cured product layer are, for example, 6, 5, 4, 3, 2, 1 μm, etc. In one embodiment, the thickness of the anchor agent cured product layer is preferably 1 to 6 μm.

[0193] The laminate is produced by various known methods. In one embodiment, the method for producing the laminate includes a step of applying an anchor agent to at least one surface of a substrate (anchor agent application step), a step of applying a low-reflection coating agent on the anchor agent application layer (low-reflection coating agent application step), and a step of forming a cured product layer by irradiating with active energy rays (active energy ray curing step).

[0194] The anchor agent application process and low-reflection coating agent application process are collectively referred to as the application process.

[0195] (Coating process) Examples of coating methods include bar coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coat coating, offset printing, flexographic printing, and screen printing.

[0196] The coating amount is not particularly limited. The coating amount is 0.1 to 30 g / m2 in terms of the mass after drying. 2 is preferred.

[0197] (Active energy ray curing process) Examples of active energy rays used in the active energy ray curing reaction include ultraviolet rays and electron beams. Examples of ultraviolet light sources include ultraviolet irradiation devices having xenon lamps, high-pressure mercury lamps, and metal halide lamps. The light intensity, light source arrangement, transport speed, etc. can be adjusted as needed. When using a high-pressure mercury lamp, curing is preferably carried out at a transport speed of about 2 to 50 m / min using one lamp with a light intensity of about 80 to 160 W / cm. On the other hand, in the case of electron beams, curing is preferably carried out at a transport speed of about 5 to 50 m / min using an electron beam accelerator with an acceleration voltage of about 10 to 300 kV. [Example]

[0198] The present invention will be described in detail below through examples and comparative examples. However, the above-mentioned description of the preferred embodiments and the following examples are provided for illustrative purposes only and are not intended to limit the present invention. Therefore, the scope of the present invention is not limited to the embodiments or examples specifically described herein, but is limited only by the claims. Furthermore, in each example and comparative example, numerical values ​​such as parts and % are based on mass unless otherwise specified.

[0199] (Example 1-1: Production of low-reflection coating agent) The mixture contained 40 parts by mass of a carboxyl group-containing poly(meth)acrylate (product name "Aronix M-510", manufactured by Toagosei Co., Ltd.) as an acidic group-containing poly(meth)acrylate, 42 parts by mass of hollow silica particles (product name "Sururia 4320", 20% by mass methyl isobutyl ketone sol, manufactured by JGC Catalysts and Chemicals Co., Ltd.) as hollow inorganic particles, 10 parts by mass of solid alumina particles (product name "NANOBYK-3610", 30% by mass methoxypropyl acetate, manufactured by BYK Chemie), 4 parts by mass of a (meth)acryloyl group-containing perfluoropolyether (product name "KY-1203", manufactured by Shin-Etsu Chemical Co., Ltd., 20% by mass), and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (product name "Omnirad 127D" manufactured by IGM Resins) was mixed with 4 parts by mass and diluted with methyl isobutyl ketone to produce a low-reflection coating agent with a solid content of 2% by mass.

[0200] Unless otherwise specified, Example 1 and Comparative Example 1 other than Example 1-1 were carried out in the same manner as Example 1-1, except for the changes shown in the table below.

[0201] (Stability test of low-reflection coating agent) The low-reflection coating agent was placed in a 20 mL screw tube and stored at room temperature of 50°C in a light-shielded environment for one month, after which the condition of the contents of the screw tube was evaluated. The evaluation criteria were as follows: 〇: All liquid, no gel-like areas ×: Part or all of the product has turned into a gel. As mentioned above, when hollow particles and solid alumina particles are present in one system, stability becomes an issue, which can be understood from the fact that the stability of the comparative example in which hollow particles and solid alumina particles are not present in one system is not poor.

[0202] [Table 1]

[0203] <Explanation of abbreviations> Aronix M-306: Pentaerythritol triacrylate, manufactured by Toagosei Co., Ltd. NK Ester A-TMMT: Pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. NK Ester A-DPH: Dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. ELCOM V8802: Solid silica particles, 40% by mass methyl isobutyl ketone sol, manufactured by JGC Catalysts and Chemicals Co., Ltd.

[0204] (Production Example 1: Production of anchoring agent) An anchoring agent with a solids content of 40% by mass was prepared by mixing 66 parts by mass of aliphatic urethane acrylate (product name "BEAMSET 577" manufactured by Arakawa Chemical Industries, Ltd.), 22 parts by mass of dipentaerythritol polyacrylate (product name "NK Ester A-9550W" manufactured by Shin-Nakamura Chemical Co., Ltd.), 9 parts by mass of (product name "NANOBYK-3610" 30% by mass methoxypropyl acetate manufactured by BYK Chemie), and 3 parts by mass of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxymethylpropanone (product name "Omnirad 2959" manufactured by IGM Resins) and diluting with methyl isobutyl ketone.

[0205] Unless otherwise specified, the Production Examples other than Production Example 1 and the Comparative Production Examples were carried out in the same manner as Production Example 1, except for the changes shown in the table below.

[0206] [Table 2]

[0207] (Example 2-1: Production of laminate) The anchoring agent prepared above was applied to a polyester (PET) film (product name "Lumirror 50U483", manufactured by Toray Industries, Inc.) using a bar coater so that the film thickness after drying would be 4 μm. After drying at 80°C for 1 minute, the coating was applied under a high-pressure mercury lamp (200 mJ / cm 2The low-reflection coating agent prepared above was applied to the anchor agent-coated surface of this anchor film using a bar coater so that the film thickness after drying would be 100 nm, and after drying at 80°C for 1 minute, the coating was cured using a high-pressure mercury lamp (600 mJ / cm) under a nitrogen flow. 2 ) to obtain a laminate.

[0208] Unless otherwise specified, Example 2 and Comparative Example 2 other than Example 2-1 were carried out in the same manner as Example 2-1, except that the composition of the coating agent kit was changed as shown in the table below.

[0209] The properties of the resulting laminate were evaluated for the following items, and the results are shown in the table below.

[0210] (Total light transmittance and haze) The total light transmittance and haze of the laminate were measured using a haze meter (product name "HZ-V3", manufactured by Suga Test Instruments Co., Ltd.) in accordance with the standard of JIS K 7361-1 (1997).

[0211] (Initial water contact angle) The laminate was fixed to a glass plate with the low-reflection coating surface facing upwards, and after neutralization, a 2 μL droplet of deionized water was gently attached using a contact angle meter "DropMaster DM500" manufactured by Kyowa Interface Science Co., Ltd., and the contact angle was measured after 1 second (analysis method: θ / 2 method).

[0212] (Water contact angle after steel wool test) The laminate was placed in the steel wool tester with the low-reflection coating surface facing upwards, and 1 kg / 4 cm was applied using #0000 steel wool. 2 The steel wool test was carried out by rubbing the test piece back and forth 500 times at a load of 1000 and a sliding distance of 4 cm. After the steel wool test, the water contact angle of the test piece was measured by the same method as for the initial water contact angle.

[0213] (Steel wool resistant) The laminate was placed in the steel wool tester with the low-reflection coating surface facing upwards, and 1 kg / 4 cm was applied using #0000 steel wool. 2 The steel wool test was carried out by rubbing the laminate back and forth over a sliding distance of 4 cm at a load of 1000 kJ / cm for the following number of times. After the test, the number of scratches on the laminate was visually confirmed and evaluated according to the following criteria. Good: 5 or fewer scratches after 1000 strokes ×: 6 or more scratches after 1000 strokes

[0214] [Table 3]

Claims

1. Solid alumina particles are contained in an amount of 5% by mass or more and 15% by mass or less of the solid content. The composition contains 20 to 70% by mass of one or more selected from the group consisting of hydroxyl group-containing poly(meth)acrylates and carboxyl group-containing poly(meth)acrylates, based on the solid content; a low-reflection coating agent in which the hydroxyl group-containing poly(meth)acrylate has a hydroxyl group value of 100 to 280 mgKOH / g; A coating agent kit comprising an anchor agent containing 2 to 18 mass % of solid alumina particles in the solid content.

2. A cured product of the low-reflection coating agent kit according to claim 1.

3. A laminate comprising the cured product according to claim 2.

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