CN111527154A - Active energy ray-curable hard coating agent and laminate - Google Patents
Active energy ray-curable hard coating agent and laminate Download PDFInfo
- Publication number
- CN111527154A CN111527154A CN201880083623.6A CN201880083623A CN111527154A CN 111527154 A CN111527154 A CN 111527154A CN 201880083623 A CN201880083623 A CN 201880083623A CN 111527154 A CN111527154 A CN 111527154A
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- CN
- China
- Prior art keywords
- acrylate
- hard coating
- coating agent
- meth
- active energy
- Prior art date
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- 239000011248 coating agent Substances 0.000 title claims abstract description 81
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 115
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000007787 solid Substances 0.000 claims abstract description 21
- 125000006551 perfluoro alkylene group Chemical group 0.000 claims abstract description 20
- 239000011164 primary particle Substances 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 12
- -1 ester acrylate Chemical class 0.000 claims description 46
- 125000000524 functional group Chemical group 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 125000004185 ester group Chemical group 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- 239000010410 layer Substances 0.000 description 22
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 19
- 239000003960 organic solvent Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- 101100366710 Arabidopsis thaliana SSL12 gene Proteins 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 9
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- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 8
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
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- 238000005259 measurement Methods 0.000 description 4
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- 238000010992 reflux Methods 0.000 description 4
- 231100000241 scar Toxicity 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
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- 150000001298 alcohols Chemical class 0.000 description 3
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- 229910052731 fluorine Inorganic materials 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
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- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 3
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- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Abstract
An active energy ray-curable hard coating agent which contains alumina particles (A), an acrylate (B) having a perfluoroalkylene group, and a multifunctional urethane acrylate (C), and satisfies the following (1) and (2). (1) The alumina particles (A) have a crystal structure of theta-type and/or alpha-type and a primary particle diameter of 5 to 50 nm. (2) The hard coating agent contains 5 to 50 mass% of alumina particles (A) and 0.05 to 5 mass% of acrylate (B) per 100 mass% of the solid content of the hard coating agent. (wherein the polyfunctional urethane acrylate (C) does not include the acrylate (B) having a perfluoroalkylene group.).
Description
Technical Field
The present invention relates to an active energy ray-curable hard coating agent and a laminate.
More specifically, the present invention relates to an active energy ray-resistant curable hard coating agent that can be applied to a display of a TV, a notebook computer, a mobile phone, a smartphone, or the like, or a back surface case thereof, and a laminate using the same.
Background
Hard coating is required to be applied to an image display surface of a display of a TV, a notebook computer, a mobile phone, a smart phone, or the like, or a back surface housing thereof so as not to be damaged during handling. Therefore, a hard coat laminate is disposed on the surface of the device. The laminate has a structure in which a hard coat layer is laminated on a light-transmitting substrate such as polyethylene terephthalate or triacetyl cellulose.
The hard coating stack has various desirable properties. For example, a laminate having a fine uneven structure formed on the surface thereof can be used as a hard coat layer, and can also be used as an antiglare film having an antiglare layer. Further, a light diffusion layer or a low refractive index layer may be used in a stacked manner. An optical laminate having a desired function has been developed by using functional layers such as these hard coat layers and antiglare layers as a single layer or by combining a plurality of layers.
On the other hand, it is predicted that the top surface of the display or the back surface case thereof will be subjected to severe operation due to a load such as a physical stimulus, a mechanical stimulus, or a chemical stimulus. For example, a cleaning cloth impregnated with a glass cleaning agent (various surfactant-based, organic solvent-based, etc.) is used to wipe off dirt such as dust and fingerprints adhering to the surface of the device. Further, the surface of the device has a problem that the displayed image is easily deformed or the appearance quality is deteriorated due to sweat, fingerprint, or the like, and when a conventional general surface treatment agent is used, the stain such as fingerprint is not easily removed but rather spreads, which is a problem of the device. Therefore, the surface of a hard coat film mounted on a device is required to have high scratch resistance and stain resistance. Further, when the above hard coat laminate is manufactured or used, a failure may occur due to cracking or the like during processing and use. Therefore, the hard coat laminate is required to have bending resistance as crack prevention in addition to antifouling property.
Conventionally, the hard coating agent constituting the hard coating layer is a coating agent cured by active energy rays, and various methods have been proposed as a method for realizing surface treatment for imparting scratch resistance and stain resistance. For example, in order to improve fingerprint resistance, a coating hard coating agent containing a fluorine-based compound having a UV-curable functional group has been proposed (patent document 1). In addition, in order to improve antistatic properties and antifouling properties, a hard coating agent containing an ionizing radiation-curable fluorinated acrylate and a conductive metal oxide has been proposed (patent document 2). Further, as a method for separately forming a coating layer for imparting stain resistance on the abrasion-resistant coating layer, a method has been proposed in which a copolymer of an acrylic ester having a perfluoro group and silica is separately coated on a low reflection layer mainly composed of silica (patent document 3).
However, there is still no active energy ray-curable hard coating agent for forming a hard coating layer having high scratch (rubbing) resistance and stain resistance and further having bending resistance.
Documents of the prior art
Patent document
Patent document 1: japanese patent application laid-open No. 2011-505452
Patent document 2: japanese patent laid-open publication No. 2011-84048
Patent document 3: japanese laid-open patent publication No. H07-16940
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing an active energy ray-curable hard coating agent for producing a hard coating layer that can achieve both high scratch resistance, stain resistance, and flex resistance.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the problems can be solved by using an active energy ray-curable hard coating agent described below, and have completed the present invention.
The present invention relates to an active energy ray-curable hard coating agent which contains alumina particles (A), an acrylate (B) having a perfluoroalkylene group, and a multifunctional urethane acrylate (C), and satisfies the following (1) and (2).
(1) The alumina particles (A) have a crystal structure of theta-type and/or alpha-type and a primary particle diameter of 5 to 50 nm.
(2) The hard coating agent contains 5 to 50 mass% of alumina particles (A) and 0.05 to 5 mass% of acrylate (B) per 100 mass% of the solid content of the hard coating agent.
(wherein the polyfunctional urethane acrylate (C) does not include the acrylate (B) having a perfluoroalkylene group.)
The present invention relates to the hard coating agent, wherein the multifunctional urethane acrylate (C) has a functional group number of 4 to 15 and a molecular weight of 500 to 15000.
The present invention relates to the hard coating agent, further comprising a polyfunctional ester acrylate (D).
The present invention relates to the hard coating agent, wherein the polyfunctional ester acrylate (D) has an ester structure derived from a carboxylic acid having a ring structure having 6 or more carbon atoms.
The present invention relates to a laminate having a substrate and a hard coat layer comprising the hard coating agent.
Effects of the invention
According to the present invention, an active energy ray-curable hard coating agent for producing a hard coating layer that can achieve both high scratch resistance and stain resistance and also high flex resistance can be provided.
Detailed Description
The embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is not limited to these contents as long as the gist thereof is not exceeded.
Hereinafter, each element constituting the present invention will be described in detail.
The present invention relates to an active energy ray-curable hard coating agent which contains alumina particles (A), an acrylate (B) having a perfluoroalkylene group, and a multifunctional urethane acrylate (C), and satisfies the following (1) and (2).
(1) The alumina particles (A) have a crystal structure of theta-type and/or alpha-type and a primary particle diameter of 5 to 50 nm.
(2) The hard coating agent contains 5 to 50 mass% of alumina particles (A) and 0.05 to 5 mass% of acrylate (B) per 100 mass% of the solid content of the hard coating agent.
(wherein the polyfunctional urethane acrylate (C) does not contain the acrylate (B) having a perfluoroalkylene group.)
In the hard coating agent of the present invention, high scratch resistance is achieved by making the crystal structure of the alumina particles (a) be of the θ type and/or the α type. In addition, by using the urethane acrylate (C) together, flexibility is imparted to the hard coat layer, and the bendability is improved. Further, the use of the acrylate (B) having a perfluoroalkylene group improves the stain resistance. Even if they are used simultaneously, the characteristics and features are not degraded.
< active energy ray-curable hard coating agent >
The active energy ray-curable hard coating agent is a composition containing a resin that is cured by a crosslinking reaction or the like by irradiation with an active energy ray such as an ultraviolet ray or an electron ray. After the active energy ray-curable hard coating agent is applied, it is cured by irradiation with an active energy ray such as an ultraviolet ray or an electron ray, thereby forming a hard coating layer. Examples of the resin include resins typified by ultraviolet-curable resins and electron beam-curable resins, and resins cured by ultraviolet irradiation are preferable in terms of excellent mechanical film strength (scratch resistance and pencil hardness). Examples of such a resin include a resin having a plurality of acrylate groups, and an acrylate monomer.
In the following description, (meth) acrylate refers to a combination of methacrylate and acrylate, and (meth) acrylic acid refers to a combination of methacrylic acid and acrylic acid.
< alumina particle (A) >)
In the present invention, alumina (Al)2O3) The crystal structure of the particles (a) is θ type and/or α type, and the primary particle diameter is 5 to 50nm, whereby the haze (haze) and coloring of the hard coat layer are reduced.
The alumina particles (A) preferably have a BET specific surface area of 10 to 100m2(ii) in terms of/g. In addition, Al2O3The purity is preferably 99.5% or more. By setting the range, the abrasion resistance of the hard coat layer is improved. The alumina particles (A) are contained in an amount of 5 to 50% by mass, preferably 10 to 40% by mass, based on the total mass of the solid content of the hard coating agent. The solid content means the total mass of nonvolatile components in the hard coating agent.
< acrylate having perfluoroalkylene (B) >)
The acrylate (B) having a perfluoroalkylene group can impart stain resistance to the hard coat layer through a fluorine atom, and the acrylate group contributes to the hard coat property by supporting curability. Therefore, the acrylate (B) having a perfluoroalkylene group is required to be contained in an amount of 0.05 to 5% by mass based on the total mass of the solid components of the hard coating agent. The acrylate (B) having a perfluoroalkylene group means an acrylate containing a perfluoroalkylene group and having a (meth) acrylate group. The perfluoroalkylene group means an alkylene group substituted with a fluorine atom.
The acrylic ester (B) is preferably contained in an amount of 0.3 to 3% by mass based on the total mass of the solid components of the hard coating agent. The number of (meth) acrylate groups contained in the acrylate (B) in its molecular structure (referred to as the number of functional groups) is preferably 1 to 6, and more preferably 2 to 6. The weight average molecular weight is preferably 400 to 5000, more preferably 500 to 2000. The acrylate (B) is preferably a urethane acrylate having a urethane bond. Thereby contributing to the bendability or scratch resistance of the hard coat layer. The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 10. Further, it preferably has a perfluoroalkyleneoxy structural unit represented by the following chemical formula (1).
Chemical formula (1)
-(CF2-CF2-O)n- (n is an integer of 1 to 10.)
Examples of the acrylate (B) include MEGAFAC RS-75, MEGAFAC RS-76-E and MEGAFAC RS-90 manufactured by DIC (Co., Ltd.), KY-1203 manufactured by shin-Etsu chemical Co., Ltd.
< multifunctional urethane acrylate (C) >
The polyfunctional urethane acrylate (C) is an oligomer having a urethane bond and a (meth) acrylate group. Wherein a polyfunctional urethane acrylate having a perfluoroalkylene group is excluded. The content of the urethane acrylate resin is preferably 5 to 95% by mass, more preferably 50 to 95% by mass, based on 100% by mass of the solid content of the hard coating agent. In addition, from the viewpoint of coating properties, the weight average molecular weight is preferably 500 to 15000. The number of functional groups of the multifunctional urethane acrylate (C) is preferably 4 to 15. The number of functional groups is synonymous with the above. In addition, the weight average molecular weight is preferably 600 to 15000, more preferably 1000 to 5000. The weight average molecular weight refers to a measurement value obtained by Gel Permeation Chromatography (GPC). The mass ratio ((A)/(C)) of the alumina particles (A) to the polyfunctional urethane acrylate (C) is preferably 10/90 to 90/10, and more preferably 10/90 to 50/50.
Examples of the polyfunctional urethane acrylate (C) include: urethane acrylate obtained by reacting diisocyanate with (meth) acrylate having a hydroxyl group; urethane acrylate obtained by reacting an isocyanate group-containing urethane prepolymer obtained by reacting a polyol with a polyisocyanate under the condition that the isocyanate group is excessive, with a (meth) acrylate having a hydroxyl group, and the like. Alternatively, the hydroxyl group-containing urethane prepolymer may be obtained by reacting a polyol with a polyisocyanate under such a condition that the hydroxyl group is excessive, with a (meth) acrylate having an isocyanate group.
The following description will describe a method for producing a urethane acrylate, but the method is not limited to these examples. For example, the urethane acrylate can be obtained by stirring a diisocyanate and a hydroxyl group-containing (meth) acrylate in the presence of a suitable urethane catalyst under an oxygen atmosphere at 60 to 100 ℃ for 4 to 8 hours.
Specific examples of the urethanization catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1, 4-diazabicyclo [ 2.2.2 ] octane, and 2,6, 7-trimethyl-1, 4-diazabicyclo [ 2.2.2 ] octane. Among these, dibutyltin dilaurate and the like are particularly preferable.
Examples of the diisocyanate include aliphatic diisocyanates and aromatic diisocyanates, examples of the aliphatic diisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate, examples of the aromatic diisocyanates include toluene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate, and the bonding position of the isocyanate group to the aromatic ring may be any of the ortho-position, meta-position, and para-position. In addition, the diisocyanates can also form isocyanurate rings as trimers.
Among them, preferred are tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and isocyanurate bodies of hexamethylene diisocyanate.
Examples of the hydroxyl group-containing (meth) acrylate include trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and the like, Hydroxyl group-containing (meth) acrylates such as 12-hydroxylauryl (meth) acrylate, ethyl- α - (hydroxymethyl) acrylate, monofunctional glyceryl (meth) acrylate, a (meth) acrylate having a hydroxyl group at the terminal thereof by ring-opening addition of these (meth) acrylates to caprolactone, and an alkylene oxide addition (meth) acrylate obtained by repeatedly adding an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide to the above hydroxyl group-containing (meth) acrylate.
Among them, at least one selected from trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate is preferably contained.
As a commercially available product of the above multifunctional urethane acrylate having 4 to 15 functional groups and a molecular weight of 500 to 15000, the following can be exemplified.
Manufactured by Xinzhongcun chemical industry (ltd): NK Oligo U6LPA, NK Oligo U10PA, NK Oligo U10HA, NKoligo UA-33H, NK Oligo UA-53H; manufactured by Industrial Co Ltd: art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-9000H, Art Resin UN-901T, Art Resin UN-904, Art Resin UN-905, Art Resin UN-952, Art Resin HDP, ArtResin HDP-3, Art Resin H61; manufactured by Nippon synthetic chemical industry Co., Ltd.: violet UV-7600B, violet UV-7610B, violet UV-7620EA, violet UV-7630B, violet UV-1700B, violet UV-6300B, violet UV-7640B, violet UT-5670, violet UV-5671; manufactured by Kyoeisha chemical Co., Ltd.: UA-306H, UA-306T, UA-306I; manufactured by MIWON corporation: PU610, PU620, MU 9800.
< polyfunctional ester acrylate (D) >
The active energy ray-curable hard coating agent preferably further contains a polyfunctional ester acrylate (D). The polyfunctional ester acrylate (D) means an oligomer having a (meth) acrylate group and containing a (poly) ester structure. Among them, those having a perfluoroalkylene group and a urethane bond are excluded. Among them, preferred are those having a functional group number of 4 to 15 and a molecular weight of 600 to 15000.
Examples of the polyfunctional ester acrylate (D) include condensates of a polybasic acid, a polyhydric alcohol, and a hydroxyl group-containing (meth) acrylate, and condensates of a polybasic acid and a hydroxyl group-containing (meth) acrylate.
The polybasic acid includes aliphatic, alicyclic and aromatic acids, and each of them can be used without particular limitation. Examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic anhydride, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, and maleic anhydride.
The polyhydric alcohol includes dihydric alcohols and trihydric or higher alcohols, and as the dihydric alcohol, alcohols obtained by introducing two or more hydroxyl groups into branched alkanes, such as neopentyl glycol, 3-methyl-1, 5-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 2-methyl-1, 8-octanediol, 3' -dimethylolheptane, 2-butyl-2-ethyl-1, 3-propanediol, butylethylpentanediol, 2-ethyl-1, 3-hexanediol, and trimethylolpropane, are preferable in terms of adhesion to a substrate, heat resistance, and the like.
The trihydric or higher alcohol is preferably glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, or the like, and may be used in combination with a dihydric alcohol.
The polyfunctional ester acrylate (D) can be produced by a known method in which a polyester is obtained by polycondensing a polybasic acid and a polyhydric alcohol, and the intended polyfunctional ester acrylate (D) is obtained by condensation reaction of a carboxyl residue with a hydroxyl group of the above-mentioned hydroxyl group-containing (meth) acrylate. Alternatively, the target polyfunctional ester acrylate (D) can be obtained by condensation reaction of a polybasic acid with the hydroxyl group of the hydroxyl group-containing (meth) acrylate. However, the manner of the manufacturing method is not limited to these.
The hydroxyl group-containing (meth) acrylate may be the same as described above, and preferably includes at least one selected from trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.
The polyfunctional ester acrylate (D) preferably contains an ester structure derived from a carboxylic acid having a ring structure of 6 or more carbon atoms. Examples of the ring structure having 6 or more carbon atoms include a cyclohexane structure, a cyclohexene structure, and a benzene structure, but are not limited thereto. Examples of the carboxylic acid having a ring structure having 6 or more carbon atoms include cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, phthalic acid, pyromellitic acid, and biphenyltetracarboxylic acid.
The number of functional groups of the multifunctional ester acrylate is preferably 5 to 10, and the weight average molecular weight is preferably 500 to 15000. The polyfunctional ester acrylate (D) is preferably contained in the polyfunctional urethane acrylate (C) and the polyfunctional ester acrylate (D) in a mass ratio (C)/(D) of 10/90 to 99/1, more preferably 70/30 to 98/2, based on the total amount of the solid content of the active energy ray-curable hard coating agent.
< other monomers >
The active energy ray-curable hard coating agent of the present invention may contain, as another monomer, a 6-functional or lower (meth) acrylate monomer having a molecular weight of less than 600. Examples of the 5 to 6-functional (meth) acrylate monomer include dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, and examples of the 3 to 4-functional (meth) acrylate monomer include ditrimethylolpropane tetraacrylate, trimethylolpropane tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate.
Examples of the 2-functional (meth) acrylate monomer include trimethylolpropane di (meth) acrylate, dicyclopentyldimethylene di (meth) acrylate, 5-ethyl-2- (2-hydroxy-1, 1-dimethylethyl) -5- (hydroxymethyl) -1, 3-dioxa di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) methacrylate, ethylene glycol di (meth) acrylate, and mixtures, Polyethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerol dimethacrylate, hexanediol di (meth) acrylate, and dimethylol tricyclodecane di (meth) acrylate, and the like. Preferable specific examples include trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane triacrylate, and PO-modified trimethylolpropane tri (meth) acrylate. These (meth) acrylates may be used alone or in combination of two or more.
Examples of the monofunctional (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-stearyl (meth) acrylate, n-butoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.
< organic solvent >
The active energy ray-curable hard coating agent of the present invention may contain an organic solvent as a liquid medium. The organic solvent to be used is preferably used as a mixed solvent, and known organic solvents such as aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester organic solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate and isobutyl acetate, alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol and n-butanol, and glycol ether organic solvents such as propylene glycol monomethyl ether can be used. Particularly preferably, the organic solvent contains a glycol ether organic solvent.
Examples of the glycol ether organic solvents include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol dipropyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol dibutyl ether, ethylene glycol isoamyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, methoxyethoxyethanol, and ethylene glycol monoallyl ether; propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and butoxypropanol; among them, methylpropanediol and 3-methoxy-1-butanol are preferable.
< photopolymerization initiator >
The active energy ray-curable hard coating agent preferably further contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has a function of initiating vinyl polymerization of a (meth) acryloyl group for forming an active energy ray-curable film by photoexcitation, and preferably contains at least one selected from a monocarbonyl compound-based initiator, a dicarbonyl compound-based initiator, an acetophenone compound-based initiator, a benzoin ether compound-based initiator, an acylphosphine oxide compound-based initiator, and an aminocarbonyl compound-based initiator, for example.
Commercially available photopolymerization initiators include Omnirad73, 481, 659, 248, 264, 4817, BDK, TPO-L, 380, Omnipol910, BP, 2702, Escapure ONE, 1001M, A198, and KIP150 manufactured by IGM Resins.
The photopolymerization initiator is not limited to the above-mentioned compounds, and may be any photopolymerization initiator as long as it has an ability to initiate polymerization by ultraviolet rays. One kind of these photopolymerization initiators may be used, or two or more kinds may be mixed and used. The amount of the photopolymerization initiator used is not particularly limited, but is preferably in the range of 1 to 20 mass% based on the total mass of solid components other than the metal oxide in the active energy ray-curable hard coating agent for forming a hard coating layer of the present invention. A known organic amine or the like may be added as a sensitizer. Further, in addition to the above radical polymerization initiator, a cationic polymerization initiator may be used in combination.
< other resins used in combination >
The active energy ray-curable hard coating agent of the present invention may contain other resins, and examples thereof include, but are not limited to, photocurable resins other than the above-mentioned epoxy acrylate resins, chlorinated polypropylene resins, polyolefin resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, rosin-based resins, rosin-modified maleic acid resins, terpene resins, phenol-modified terpene resins, ketone resins, cyclized rubbers, chlorinated rubbers, butyrals, petroleum resins, and modified resins thereof. These resins may be used alone or in combination of two or more, and the content thereof is not particularly limited as long as the effect of the present invention is not impaired, and is preferably 1 to 20% by weight based on the total mass of the resin solid content of the active energy ray-curable hard coating agent.
< additive >
The active energy ray-curable hard coating agent of the present invention may further contain various additives within a range not impairing the object and effect of the present invention. Specifically, there may be mentioned a polymerization inhibitor, a photosensitizing agent, a leveling agent, a surfactant, an antibacterial agent, an anti-blocking agent, a plasticizer, an ultraviolet absorber, an infrared absorber, an antioxidant, a silane coupling agent, a conductive polymer, a conductive surfactant, an inorganic filler, a pigment, a dye, or the like.
Production of active energy ray-curable hard coating agent
The active energy ray-curable hard coating agent of the present invention has no problem as long as it can be uniformly stirred and mixed or dispersed, and can be produced, for example, by uniformly stirring the alumina particles (a), the acrylate (B) having a perfluoroalkylene group, and the polyfunctional urethane acrylate (C) constituting the active energy ray-curable hard coating agent, and further, in some cases, the polyfunctional ester acrylate (D) and other monomers using a predetermined stirrer disperser, homogenizer, three-roll mill, sand mill, gamma mill, or the like.
The alumina particles (a) may be used by mixing a pentaerythritol acrylate compound, an acrylate resin such as urethane acrylate and polyester acrylate, and an organic solvent, and dispersing them in advance, or may be used by mixing a commercially available organic solvent dispersion.
< production of hard coating >
Next, a method for producing a hard coat layer by curing an active energy ray-curable hard coating agent will be described. The method for producing the hard coat layer includes, for example, the following steps: a step of coating the active energy ray-curable hard coating agent on a base material; and a step of curing the active energy ray-curable hard coating agent on the substrate by irradiating the active energy ray with the active energy ray. More specifically, the active energy ray-curable hard coating agent can be formed by applying the active energy ray-curable hard coating agent to a substrate so that the film thickness after drying is preferably 0.1 to 30 μm, more preferably 1 to 10 μm, and then performing a curing treatment.
As the coating method, a known method can be used, and for example, a batch method, a method using a wire bar or the like, or various coating methods such as micro gravure coating, die coating, curtain coating, lip coating, slit coating, spin coating, or spray coating can be used.
The curing method may be carried out by a known technique, for example, by irradiating with an active energy ray such as an ultraviolet ray, an electron ray, or a visible ray having a wavelength of 400 to 500 nm. As a source (light source) of ultraviolet rays and visible rays having a wavelength of 400 to 500nm, for example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used. As the electron source, a thermionic emission gun, an electrolytic emission gun, or the like can be used. The cumulative quantity of the irradiated active energy rays is preferably 50 to 1000mJ/cm in terms of easy process control2Within the range of (1). These active energy rays may be irradiated with infrared rays, far infrared rays, hot air, or heat treatment by high-frequency heating or the like.
The hard coat layer may be formed by applying an active energy ray-curable hard coating agent to a substrate, naturally or forcibly drying the same, and then performing a curing treatment, or may be naturally or forcibly dried after applying the same, but it is more preferable to perform a curing treatment after naturally or forcibly drying the same. In particular, when curing is performed using an electron beam, it is more preferable to perform the curing treatment after natural or forced drying in order to prevent the inhibition of curing by water or the decrease in strength of the coating film due to the residual organic solvent. The curing treatment may be performed simultaneously with or after the coating.
< substrate >
Examples of the substrate of the present invention include a polyester film, a triacetyl cellulose film, a polyolefin film, a cycloolefin film, an acrylic film, and a polycarbonate film, but are not limited to the above substrates. In particular, polyester films, especially polyethylene terephthalate (PET) films, can be preferably used on the surface of the display. The thickness of the above-mentioned base material may be appropriately selected depending on the intended use, and a range of 20 μm to 300 μm is suitable, and a range of 50 μm to 250 μm is preferable, and a range of 50 μm to 200 μm is more preferable. In addition, an acrylic/polycarbonate sheet, in particular, can be preferably used in the back cover. The thickness of the substrate may be appropriately selected depending on the intended use, and a range of 200 μm to 800 μm is suitable, and a range of 200 μm to 500 μm is preferable.
The substrate may further have a layer made of an organic substance and/or an inorganic substance on the surface thereof, and specific examples thereof include an easy-adhesion layer for improving adhesion with other layers. The easy-adhesion layer may be treated by corona discharge treatment, UV-ozone treatment, plasma treatment, primer treatment, or the like, or may be treated in combination.
Examples
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the present invention, parts and% are parts by weight and% by weight unless otherwise noted.
(average particle diameter)
The measurement was performed by transmission electron microscopy, and the average value of the primary particle diameters of 10 randomly selected particles was used. In addition, H-9500, a product of Hitachi high-tech technology, Inc., was used as the transmission electron microscope.
(specific surface area)
According to JIS Z8830: 2001 was determined by the method described in 2001.
(acid value)
The acid value (mgKOH/g) in the solid content was determined by potentiometric titration according to JIS K0070.
(weight average molecular weight)
The weight average molecular weight was determined by measuring the molecular weight distribution using a GPC (gel permeation chromatography) apparatus (HLC-8220, Tosoh corporation), and using polystyrene as a standard substance in terms of the molecular weight. The measurement conditions are shown below.
A chromatographic column: the following columns were connected in series for use.
TSKgel SuperAW2500 manufactured by Tosoh corporation
TSKgel SuperAW3000 manufactured by Tosoh corporation
TSKgel SuperAW4000 manufactured by Tosoh corporation
TSKgel guardcolum SuperAWH manufactured by Tosoh corporation
A detector: RI (differential refractometer)
The measurement conditions were as follows: the temperature of the chromatographic column is 40 DEG C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
(Synthesis example 1) < polyfunctional urethane acrylate PU3 >
In a flask equipped with a stirring blade, a thermometer, a reflux condenser, and an air introduction tube, 120 parts of a polyester polyol having a molecular weight of 3000 as a condensate of adipic acid and neopentyl glycol and 18 parts of isophorone diisocyanate were mixed. Further, n-propyl acetate was added as a solvent so that the solid content became 80%, and the reaction was carried out at 80 ℃ for 5 hours under a nitrogen atmosphere to synthesize a urethane prepolymer. Then, the flask was purged with air, 34 parts by weight of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name: Aronix M306, manufactured by Toyo Seisaku-sho) in a weight ratio of 70:30 was added to the flask so as to reach 200ppm, and the mixture was heated and stirred at 80 ℃ under an air atmosphere for 4 hours to obtain urethane acrylate PU 3. The PU3 had a number of functional groups of 6 and a weight average molecular weight of 6000.
(Synthesis example 2) < polyfunctional urethane acrylate PU4 >
In a flask equipped with a stirring blade, a thermometer, a reflux condenser, and an air inlet tube, 100 parts of isocyanurate body of hexamethylene diisocyanate (NCO groups: 3) and 69 parts of hydroxyethyl acrylate were mixed. N-propyl acetate was further mixed as a solvent so that the solid content became 60%. Then, methoxyhydroquinone was added so as to be 200ppm, and the mixture was heated and stirred at 90 ℃ for 6 hours while blowing air, to obtain urethane acrylate PU 4. The PU4 had a number of functional groups of 3 and a weight-average molecular weight of 1000.
(Synthesis example 3) < polyfunctional polyester acrylate PE1 >
Into a four-necked flask equipped with a stirrer, a reflux condenser, a dry air inlet tube and a thermometer were charged 80.0 parts of 3,3', 4, 4' -biphenyltetracarboxylic dianhydride, 250.0 parts of pentaerythritol triacrylate (product name: KAYARAD PET-30 of pentaerythritol triacrylate manufactured by Nippon chemical Co., Ltd., containing pentaerythritol tetraacrylate as a by-product) having a hydroxyl value of 122mgKOH/g, 0.24 parts of methylhydroquinone and 217.8 parts of cyclohexanone, and the temperature was raised to 60 ℃. Then, 1.65 parts of 1, 8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ℃ for 8 hours. Then, 78.3 parts of glycidyl methacrylate and 54.0 parts of cyclohexanone were added. Subsequently, 2.65 parts of dimethylbenzylamine as a catalyst was added thereto, the mixture was stirred at 100 ℃ for 6 hours, and the acid value of the reaction product was periodically measured while continuing the reaction, and when the acid value was 5.0mgKOH/g or less, the reaction was cooled to room temperature to stop the reaction. The obtained resin varnish was light yellow and transparent, and polyester acrylate PE1 (polyester acrylate: pentaerythritol tetraacrylate: 76:24 in mass ratio of solid content) having a solid content of 60% was obtained. PE1 had a number of functional groups of 8 and a weight average molecular weight of 3500.
(Synthesis example 4) < polyfunctional polyester acrylate PE2 >
In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air inlet tube and a thermometer, 100 parts of a polyester diol having a number average molecular weight of 1000 as a condensate of adipic acid and neopentyl glycol, 92 parts of pentaerythritol triacrylate having a hydroxyl value of 122mgKOH/g (product name of pentaerythritol triacrylate: KAYARAD PET-30, manufactured by Nippon chemical Co., Ltd., containing pentaerythritol tetraacrylate as a by-product), and 0.01 part of tetrabutyltitanate were mixed. Further, methyl hydroquinone was added so that the solid content became 250ppm, and toluene was added so that the solid content became 70%, and the mixture was stirred. The temperature was raised to 105 ℃ and dehydration reaction was carried out by using a drain pipe while carrying out oxygen bubbling. When the acid value was 5.0mgKOH/g or less, toluene was removed under reduced pressure from the solvent, and the mixture was cooled to 40 ℃ to obtain polyester acrylate PE2 (solid content mass ratio: polyester acrylate: pentaerythritol tetraacrylate: 83: 17). PE2 had a number of functional groups of 6 and a weight average molecular weight of 2300.
Example 1 preparation of active energy ray-curable hard coating agent S1
20 parts of alumina particles (4) (Theta type crystals of alumina particles made by Sumitomo chemical Co., Ltd., primary particle diameter of 10nm, BET specific surface area of 73m2(g), 70 parts of PU1 (product name UA-510H manufactured by Kyoeisha chemical Co., Ltd.) as a polyfunctional urethane acrylate, 4 parts of PE1 shown in Synthesis example 3 as a polyfunctional polyester acrylate, and 200 parts of propylene glycol monomethyl ether as an organic solvent were mixed, and after dispersion stirring, dispersion treatment was carried out using a sand mill to obtain a uniform slurry. Further, 5 parts of Esacure ONE (oligo [ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] made by IGM Resins) was used as a photopolymerization initiator]Acetone (II)])1 part of an acrylic ester having a perfluoroalkylene group (RS-90 manufactured by DIC having a- (CF) name2-CF2-O)n"urethane acrylate having 2 functional groups (n is 4 to 6) and propylene glycol monomethyl ether as an organic solvent were adjusted so that the solid content became 40%, to obtain an active energy ray-curable hard coating agent S1.
(examples 2 to 13) < production of active energy ray-curable hard coating agent S2 to 13 >
An active energy ray-curable hard coating agent was produced by the same procedure as in example 1 except that the raw materials and the composition ratio described in table 1 were used. Note that the abbreviations in the tables are as follows.
(alumina particle (A))
Alumina particles (1): sumitomo chemical company alumina particle alpha type crystal primary particle diameter 30nm
Alumina particles (2): sumitomo chemical company alumina particle alpha type crystal primary particle diameter 50nm
(acrylate (B) having a perfluoroalkylene group)
FA 1: 3-perfluorohexyl-2-hydroxypropyl methacrylate (weight average molecular weight 500) manufactured by Dajin
(polyfunctional urethane acrylate (C))
PU 1: the product name UA-510H manufactured by Kyoeisha chemical company is 10, the number of urethane acrylate functional groups consisting of hexamethylene diisocyanate and dipentaerythritol pentaacrylate is 10, and the weight average molecular weight is 1800
PU 2: the product name UA-306I manufactured by Kyoeisha chemical company is that the number of urethane acrylate functional groups consisting of isophorone diisocyanate and pentaerythritol triacrylate is 6, and the weight average molecular weight is 900
PU 5: corongro chemical company product name UF8001-G urethane acrylate functional number 2 weight average molecular weight 4500
Comparative examples 1 to 9 preparation of active energy ray-curable hard coating agents R1 to R9
An active energy ray-curable hard coating agent was produced by the same procedure as in example 1 except that the raw materials and the composition ratio described in table 1 were used. Note that the abbreviations in the tables are as follows.
(alumina particles)
Alumina particles (3): sumitomo chemical company alumina particle alpha type crystal primary particle size 70nm
Alumina particles (5): sumitomo chemical company alumina particle gamma type crystal primary particle diameter 20nm
Alumina particles (6): primary particle diameter of amorphous crystal of alumina particle 20nm, produced by Douglas chemical Co
(inorganic particles such as other metal oxide particles)
Zirconium oxide: the primary particle size of zirconia particles prepared by AITEC corporation is 20nm
Silica particles: silica particles having a primary particle diameter of 10nm manufactured by CIK Nano Tek Co
(polyfunctional urethane acrylate)
PU 5: functional urethane acrylate having a weight average molecular weight of 4500, UF-8001-G2, a product name of Kyoeisha chemical Co., Ltd
Example 14 production of laminate SS1
The active energy ray-curable hard coating agent S1 was applied to a Polyester (PET) film (Lumiror U483, manufactured by Toray corporation) having a thickness of 125 μm so that the dried film thickness became 4.5 μm using a bar coater #4, and then irradiated with 500mJ/cm using a high pressure mercury lamp2Laminate SS1 was produced by the ultraviolet ray of (4).
Examples 15 to 26 < production of laminates SS2 to SS13 >
Laminates SS2 to SS13 were produced in the same manner as in example 1, except that the active energy ray-curable hard coating agents S2 to S13 shown in table 1 were used.
Comparative examples 10 to 18 production of laminates RR1 to RR9
Laminates RR1 to RR9 were produced by the same procedure as in example 1, except that the active energy ray-curable hard coating agents R1 to R9 described in table 1 were used.
[ evaluation ]
The laminates SS1 to SS13 (examples) and RR1 to RR9 (comparative examples) obtained as described above were used for the following evaluations. The evaluation results are shown in tables 2 and 3.
< scratch resistance >
Using laminates SS1 to SS13 (examples) and RR1 to RR9 (comparative examples), the laminates were placed in a vibration tester, and steel wool No.0000 was used to apply a load of 1kg/cm2Scraping was performed 5000 times. The taken-out laminate is treated in accordance withThe occurrence of the flaw was judged by visual evaluation in the next five stages.
[ evaluation standards ]
5: no scar was observed at all. (very good)
4: 1-2 scars were generated. (good)
3: 3-10 scars were generated. (slight bad)
2: more than 11 scars were produced. (failure)
1: the coating film was peeled off and the substrate film was exposed. (extremely poor)
It should be noted that 4 and 5 are levels that have no practical problem.
< Water contact Angle (initial) >)
The contact angle values obtained by measuring the water contact angles of laminates SS1 to SS13 (examples) and RR1 to RR9 (comparative examples) with a full-automatic contact angle meter DM-701 manufactured by synechia chemical company were evaluated by visual observation in the following five stages. The evaluation was performed as an alternative evaluation of the antifouling property. Therefore, the following steps are carried out: the larger the contact angle, the more easily water is repelled and the more difficult it is to soil.
[ evaluation standards ]
5: contact angle of 105 degrees or more (very good)
4: contact angle of 100 DEG or more and less than 105 DEG (good)
3: the contact angle is 90 DEG or more and less than 100 DEG (slightly poor)
2: contact angle of 80 DEG or more and less than 90 DEG (bad)
1: contact angle of less than 80 ° (extremely poor)
It should be noted that 4 and 5 are levels that have no practical problem.
< Water contact Angle (after scratch resistance test) >
The water contact angles of the samples after the scratch resistance test were measured using laminates SS1 to SS13 (examples) and RR1 to RR9 (comparative examples), and the obtained contact angle values were judged by the following five-stage visual evaluation. The evaluation was performed as an alternative evaluation of the antifouling property. Therefore, the following steps are carried out: the larger the contact angle, the more easily water is repelled and the more difficult it is to soil.
[ evaluation standards ]
5: contact angle of more than 100 degrees (very good)
4: contact angle of 90 DEG or more and less than 100 DEG (good)
3: the contact angle is 80 DEG or more and less than 90 DEG (slightly poor)
2: contact angle of 70 DEG or more and less than 80 DEG (bad)
1: contact angle of less than 70 ° (extremely poor)
It should be noted that 4 and 5 are levels that have no practical problem.
< flexibility resistance >
The bending resistance test when the laminated surface of the active energy ray-curable hard coating agent in the laminate was bent outward was evaluated using laminates SS1 to SS13 (examples) and RR1 to RR9 (comparative examples) and using a coating film bending Tester (PI-801 manufactured by Tester industries, inc.). The mandrel diameter without cracks was judged by the following five-stage visual evaluation.
[ evaluation standards ]
5: the diameter of the mandrel is less than
(very good)
4: the diameter of the mandrel is
Above and less than 15mm (good)
3: the diameter of the mandrel is
Above and less than 20mm (slightly poor)
2: the diameter of the mandrel is
Above and less than 25mm (bad)
1: the diameter of the mandrel is
Above (extremely bad)
It should be noted that 4 and 5 are levels that have no practical problem.
< transparency >
The transparency of each of laminates SS1 to SS13 (examples) and RR1 to RR9 (comparative examples) was evaluated by the haze (haze) of the coating film. The haze value was measured using a haze meter SH7000 manufactured by Nippon Denshoku industries Ltd. Based on the obtained haze value, the transparency was judged by the following five-stage visual evaluation.
[ evaluation standards ]
5: haze value less than 0.5 (very good)
4: haze value of 0.5 or more and less than 1.0 (good)
3: haze value of 1.0 or more and less than 2.0 (slightly poor)
2: haze value of 2.0 or more and less than 3.0 (bad)
1: haze value of 3.0 or more (extremely poor)
It should be noted that 4 and 5 are levels that have no practical problem.
From the results of table 2, in the examples, all of the scratch resistance, stain resistance, bending property, and transparency were excellent. Particularly, when the scraping conditions were the basic conditions of generally 100 scrapes, even 5000 scrapes were good, and a remarkable effect was exhibited. Further, the flexibility was also considered, and the expected performance was exhibited.
On the other hand, the results in table 3 show that in the comparative examples, any of scratch resistance, stain resistance, bendability, and transparency is in a trade-off relationship, and the performance is insufficient in at least one or more items.
[ Table 1]
[ Table 2]
[ Table 3]
Claims (5)
1. An active energy ray-curable hard coating agent which contains alumina particles (A), an acrylate (B) having a perfluoroalkylene group, and a polyfunctional urethane acrylate (C) and satisfies the following (1) and (2),
(1) the alumina particles (A) have a crystal structure of theta-type and/or alpha-type and a primary particle diameter of 5 to 50nm,
(2) the hard coating agent contains 5-50 mass% of alumina particles (A) and 0.05-5 mass% of acrylate (B) in 100 mass% of solid content,
wherein the polyfunctional urethane acrylate (C) does not include the acrylate (B) having a perfluoroalkylene group.
2. The hard coating agent according to claim 1, wherein the multifunctional urethane acrylate (C) has a functional group number of 4 to 15 and a molecular weight of 500 to 15000.
3. The hard coating agent according to claim 1 or 2, further comprising a polyfunctional ester acrylate (D).
4. The hard coating agent according to claim 3, wherein the polyfunctional ester acrylate (D) has an ester structure derived from a carboxylic acid having a ring structure having 6 or more carbon atoms.
5. A laminate comprising a substrate and a hard coat layer comprising the hard coating agent according to any one of claims 1 to 4.
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| JP2017249500A JP6512281B1 (en) | 2017-12-26 | 2017-12-26 | Active energy ray-curable hard coat agent and laminate |
| PCT/JP2018/047712 WO2019131701A1 (en) | 2017-12-26 | 2018-12-26 | Active-energy-ray-curable hard coating agent, and layered body |
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| JP6773202B1 (en) * | 2019-12-12 | 2020-10-21 | 東洋インキＳｃホールディングス株式会社 | Transparent conductive films, optics, and electronics |
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| CN102844346A (en) * | 2010-03-31 | 2012-12-26 | Dic株式会社 | Active energy ray curable resin composition, cured article and film thereof |
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| JP2008068627A (en) * | 2007-09-18 | 2008-03-27 | Dainippon Printing Co Ltd | Flexible hard coat film |
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| KR101093721B1 (en) * | 2009-06-01 | 2011-12-19 | 도레이첨단소재 주식회사 | Double side hard coating film for protecting display |
| JP5490487B2 (en) | 2009-10-19 | 2014-05-14 | 株式会社巴川製紙所 | Optical laminate |
| JP2011194756A (en) * | 2010-03-22 | 2011-10-06 | Tomoegawa Paper Co Ltd | Hard coat film for decoration, decorative film, and decorative molded product |
| JP2014085638A (en) * | 2012-10-26 | 2014-05-12 | Fujicopian Co Ltd | Hard coat film |
| JP2014151588A (en) * | 2013-02-12 | 2014-08-25 | Nippon Synthetic Chem Ind Co Ltd:The | Laminate and use thereof |
| KR101537901B1 (en) * | 2014-04-30 | 2015-07-23 | 한국교통대학교산학협력단 | High heat ddssipative transparent sheet and method of producing the same |
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| JP6841102B2 (en) * | 2016-03-31 | 2021-03-10 | 東レ株式会社 | Method of manufacturing a laminate |
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| CN101074339A (en) * | 2006-05-18 | 2007-11-21 | 中国石油天然气集团公司 | Seawate-corrosive-resisting modified epoxy ceramic coating and its production |
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