JP2010163535A - Antiblocking curable resin composition, antiblocking hard coat film, antiblocking layered structure, display including the antiblocking layered structure, and production method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technique by which a blocking phenomenon is prevented and deterioration of weatherability with time in a film and the layered structure thereof can be further reduced as a further improvement. <P>SOLUTION: In the antiblocking curable resin composition including a first component made of at least one or more resins and a second component made of at least one or more monomers, the second component includes a multifunctional reactive unsaturated double bond-containing monomer including tri- or more functional reactive unsaturated double bond-containing monomer having 3 to 6 molar equivalent 2C-4C alkylene oxide unit in one molecule of the monomer and the resin of the first component is deposited by phase separation after application of the composition to form fine ruggedness on the surface and to provide weatherability. There are also provided an antiblocking hard coat film, an antiblocking layered structure, a display including the antiblocking layered structure and production methods thereof. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention provides a curable resin composition (hereinafter referred to as an anti-blocking curable resin composition) capable of providing both anti-blocking properties and weather resistance, a hard coat film having both anti-blocking properties and weather resistance ( Hereinafter, the present invention relates to an anti-blocking hard coat film), an anti-blocking layered structure, a display device including the anti-blocking layered structure, and a manufacturing method thereof.

  When a hard coating is applied to a thermoplastic film such as a PET film, it may be stored in a manufacturing process, such as being wound into a roll. When another layered body is layered on a base material layer such as a PET film on which a hard coat has been formed, the adhesive force or chemical force acts between the layers, and it becomes an attached state, and when using each layered body In addition, a force for peeling off each layered body may be required, it may be difficult to peel off due to the strong adhesive force, or the layered body may be destroyed if it is forced to peel off.

  In such a case, a back coat layer is formed by applying a paint kneaded with a particulate matter of about 1 μm on the opposite surface of the base material that is not hard-coated, and the surface is uneven. By providing and reducing the contact area between each layer, adhesion between layered bodies may be prevented. For example, Japanese Patent Application Laid-Open No. 2004-151937 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2005-132897 (Patent Document 2) disclose a technique in which a backcoat layer containing a particulate matter is formed.

  The technique for preventing adhesion between layered bodies by using the above-mentioned granular material is effective, but since the unevenness of the particles must appear on the surface, the thickness of the coating film is smaller than the particle size (for example, 0 .About.5 μm), the mechanical strength of the backcoat layer is lowered, the substrate layer such as a PET film is easily scratched, and glare occurs. In the case of a thermoplastic resin layer that requires transparency, such a defect is a fatal defect because optical characteristics and transparency are lowered.

  In the method of mixing transparent resin fine particles in the back coat layer on the opposite side of the hard coat layer, there is also a technique for forming irregularities on the surface by mixing resin particles not only in the back coat layer but also in the hard coat layer itself. (Japanese Patent Laid-Open No. 2004-042653 (Patent Document 3)) The blended particles have an average particle size of 0.5 to 20 μm. When the particles are mixed, it is necessary to reduce the film thickness in order to form unevenness on the surface, the film strength becomes weak, the film is easily damaged, and the coating film properties are deteriorated. In addition, since the particle size of the particles is relatively large, even if transparent particles are used as in Patent Document 3, the optical characteristics may be impaired.

  In addition, in this field, in addition to the above, the long-term use of the apparatus provided with the film layer may cause aging deterioration and weather resistance deterioration such as cracking of the film. An improved technique is desired.

JP 2004-151937 A JP 2005-132897 A JP 2004-042653 A

  The present invention prevents defects such as adhesion between layered bodies such as a thermoplastic film, that is, blocking phenomenon, and as a further improvement, can reduce the deterioration of weather resistance of the film and its layered structure over time. The issue is to provide

  As a result of diligent research, the inventors of the present invention have used a curable resin composition containing a first component made of at least one or more resins and a second component made of at least one or more monomers, after applying the composition, The component resin is precipitated by phase separation, and it is found that anti-blocking properties can be obtained by forming fine irregularities on the surface (Japanese Patent Application No. 2006-002480). It has been found that by using a reactive unsaturated double bond group-containing monomer as the second component monomer, it is possible to reduce deterioration in weather resistance due to aging of the film and its layered structure. Accordingly, the present invention provides the following.

A curable resin composition comprising a first component comprising at least one or more resins, and a second component comprising at least one or more monomers,
The second component contains a multifunctional reactive double bond group-containing monomer having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule. An unsaturated double bond group-containing monomer
An antiblocking curable resin composition in which the resin of the first component is precipitated by phase separation after application of the composition to form fine irregularities on the surface, and has weather resistance.

［式１中、
ｎ、ｍおよびｐは、それぞれ独立して、２〜４の整数であり、
ｘ、ｙおよびｚは、それぞれ独立して、０〜３の整数であり、但し、ｘ、ｙおよびｚの和が３〜６であることを条件とし、および
Ｒ^１は、水酸基を有していてもよい炭素数１〜３のアルキル基であり、
Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素またはメチル基である。］
で示されるモノマーであることが好ましい。 In the anti-blocking curable resin composition of the present invention, a trifunctional or higher functional unsaturated double bond group-containing monomer having 3 to 6 molar equivalents of the above-mentioned alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule Is the following formula 1

[In Formula 1,
n, m and p are each independently an integer of 2 to 4,
x, y and z are each independently an integer of 0 to 3, provided that the sum of x, y and z is 3 to 6, and R ¹ has a hydroxyl group. An alkyl group having 1 to 3 carbon atoms,
R ² , R ³ and R ⁴ are each independently hydrogen or a methyl group. ]
It is preferable that it is a monomer shown by these.

  In the antiblocking curable resin composition of the present invention, it is preferable that the curable resin composition further contains at least one kind of inorganic particles or organic particles.

  In the anti-blocking curable resin composition of the present invention, the difference between the SP value of the first component and the SP value of the second component is preferably 1.0 or more.

  In the antiblocking curable resin composition of the present invention, the SP value of the first component is preferably smaller than the SP value of the second component.

  The antiblocking curable resin composition of the present invention is preferably photocurable.

  Moreover, this invention relates to the antiblocking hard coat film obtained by hardening | curing said antiblocking curable resin composition in a film form.

  In the antiblocking hard coat film of the present invention, the haze is preferably 2.0% or less.

  The present invention further relates to an antiblocking layered structure obtained by applying the above-described antiblocking curable resin composition onto a substrate and curing the composition.

  The present invention further relates to an antiblocking layered structure winding roll obtained by applying the above-described antiblocking curable resin composition on a substrate and winding the cured antiblocking layered structure into a roll.

  The present invention also relates to a method for producing an antiblocking layered structure obtained by applying the antiblocking curable resin composition described above on a substrate, drying and phase-separating, and then curing. .

  In the method for producing an antiblocking layered structure of the present invention, the phase separation and curing are preferably performed by irradiating light.

  The present invention is also a display device comprising the above antiblocking layered structure and a light source, wherein the substrate contained in the antiblocking layered structure is a translucent substrate, The present invention also relates to a display device that emits light from the back surface of the substrate.

  The curable resin composition capable of providing the anti-blocking property and weather resistance of the present invention can be applied on a substrate, dried as necessary, and then cured (particularly, photocured). An anti-blocking layer which is a resin layer having unevenness can be provided. The obtained anti-blocking hard coat film is harder than the conventional one and hardly scratches. In addition, since no particulate matter having an average particle diameter of more than 0.5 μm is used, the optical properties are not impaired and the performance of the resin itself can be used. Even when a plurality of anti-blocking layered structures obtained by combining this anti-blocking hard coat film with a base material are stacked, the effect of preventing the blocking phenomenon (for example, interlayer adhesion) is exhibited. When the anti-blocking layered structure of the present invention is a wound roll, a blocking phenomenon (for example, difficulty in peeling from the wound roll) does not occur.

  In addition, when irregularities are formed on the surface according to the present invention, the irregular arrangement is naturally determined, so that irregular irregular shapes can be formed on the surface of the coating film having fine irregularities.

  In addition to the above-described effects, the present invention provides a hard coat film obtained as a further improvement by the fact that the second component of the curable resin composition contains the monomer of the above formula 1 (second component (a)). In addition, it is possible to reduce deterioration of weather resistance due to deterioration over time of the layered structure, and it can be applied to applications in which performance such as transparency and weather resistance is particularly required.

1 is a schematic cross-sectional view of an antiblocking layered structure of the present invention. It is a schematic explanatory drawing of a total light transmittance ( _Tt (%)). It is the schematic which shows one Embodiment of the display apparatus of this invention. It is the schematic which shows one Embodiment of the touchscreen using this invention. 3 is a three-dimensional image of a coating surface having fine irregularities in the anti-blocking layered structure of Example 1 by a color 3D laser microscope. It is a three-dimensional image by the color 3D laser microscope of the coating-film surface which has a fine unevenness | corrugation in the antiblocking layered structure of Example 4. FIG. 6 is a three-dimensional image of a coating surface having fine irregularities in the anti-blocking layered structure of Example 5 by a color 3D laser microscope.

Antiblocking curable resin composition The antiblocking curable resin composition of this invention is apply | coated on a base material, and forms the film which has a fine unevenness | corrugation. This antiblocking curable resin composition contains at least two kinds of components, a first component and a second component. When the anti-blocking curable resin composition is applied onto the substrate, the first component and the second component are based on the difference in physical properties between the first component and the second component. It has the feature that the components are phase separated.

  The first component is composed of at least one or more resins, and the second component is composed of at least one or more monomers.

As the first component resin of the first component, for example, a resin containing (meth) acrylic resin, olefin resin, polyether resin, polyester resin, polyurethane resin, polysiloxane resin, polysilane resin, polyimide resin or fluorine resin in a skeleton structure Etc. can be used. These resins may be so-called oligomers having a low molecular weight. The “oligomer” in the present specification refers to a polymer having a repeating unit and having 3 to 10 repeating units. As a resin containing a (meth) acrylic resin in its skeleton structure, a resin obtained by polymerizing or copolymerizing a (meth) acrylic monomer, a resin obtained by copolymerizing a (meth) acrylic monomer and another monomer having an ethylenically unsaturated double bond Etc. Examples of the resin containing an olefin resin in the skeleton structure include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ionomer, ethylene / vinyl alcohol copolymer, and ethylene / vinyl chloride copolymer. . The resin containing a polyether resin in the skeleton structure is a resin containing an ether bond in the molecular chain, and examples thereof include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. The resin containing a polyester resin in the skeleton structure is a resin containing an ester bond in the molecular chain, and examples thereof include an unsaturated polyester resin, an alkyd resin, and polyethylene terephthalate. A resin including a polyurethane resin in a skeleton structure is a resin including a urethane bond in a molecular chain. The resin containing a polysiloxane resin in the skeleton structure is a resin containing a siloxane bond in the molecular chain. A resin containing a polysilane resin in a skeleton structure is a resin containing a silane bond in a molecular chain. A resin including a polyimide resin in a skeleton structure is a resin including an imide bond in a molecular chain. The resin containing a fluororesin in the skeleton structure is a resin containing a structure in which part or all of hydrogen of polyethylene is replaced with fluorine. The resin may be a copolymer composed of two or more of the above skeleton structures, or may be a copolymer composed of the above skeleton structures and other monomers.

  As the first component resin, a (meth) acrylic resin is preferable, and an unsaturated double bond-containing acrylic copolymer is particularly preferable. The unsaturated double bond-containing acrylic copolymer is not particularly limited. For example, a resin obtained by polymerizing or copolymerizing a (meth) acrylic monomer, or having a (meth) acrylic monomer and another ethylenically unsaturated double bond. Resin copolymerized with monomer, (meth) acrylic monomer and other ethylenically unsaturated double bond and epoxy group-containing resin, (meth) acrylic monomer and other ethylenically unsaturated double Examples thereof include a resin obtained by reacting a monomer having a bond and an isocyanate group. One of these unsaturated double bond-containing acrylic copolymers may be used alone, or two or more thereof may be mixed and used.

Second component In the antiblocking curable resin composition of the present invention, the second component is composed of at least one monomer, and includes a polyfunctional reactive unsaturated double bond group-containing monomer as the monomer. Features. In the present invention, the polyfunctional reactive unsaturated double bond group-containing monomer as the second component is a trifunctional or higher functional monomer having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule. It is particularly preferred that it contains a reactive unsaturated double bond group-containing monomer (hereinafter sometimes referred to as the second component (a)).

  A trifunctional or higher functional unsaturated double bond group-containing monomer (a) having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule is, for example, a trifunctional or higher polyhydric alcohol. Can be prepared by introducing an alkylene oxide skeleton having 2 to 4 carbon atoms and reacting this with (meth) acrylate.

  The trifunctional or higher functional unsaturated double bond group-containing monomer (a) having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule is represented by the following formula 1, for example. Monomer.

In the above formula 1,
n, m and p are each independently an integer of 2 to 4,
x, y and z are each independently an integer of 0 to 3, provided that the sum of x, y and z is 3 to 6, and R ¹ has a hydroxyl group. An alkyl group having 1 to 3 carbon atoms,
R ² , R ³ and R ⁴ are each independently hydrogen or a methyl group.

  Examples of the trifunctional or higher functional unsaturated double bond group-containing monomer having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule, that is, the second component (a) include, for example, tri Ethylene glycol-trimethylolpropane tri (meth) acrylate, tripropylene glycol-trimethylolpropane tri (meth) acrylate, hexaethylene glycol-trimethylolpropane tri (meth) acrylate, hexapropylene glycol-trimethylolpropane tri (meth) acrylate 2 or more types may be used in combination.

  In the present invention, a polyfunctional reactivity containing a trifunctional or more reactive unsaturated double bond group-containing monomer (a) having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule. The anti-blocking curable resin composition is prepared using the unsaturated double bond group-containing monomer as a second component, thereby reducing the weather resistance due to aging in the film layer formed by the composition. Can do.

By using the antiblocking curable resin composition of the present invention, the weather resistance of the resulting film layer can be improved without using a weather resistance stabilizer such as an ultraviolet absorber. As the ultraviolet absorber, for example, a benzotriazole ultraviolet absorber, a triazine ultraviolet absorber, a benzophenone ultraviolet absorber, a benzoate ultraviolet absorber, a hindered amine ultraviolet absorber and the like are generally used in the resin field and the like. Yes. However, many of these ultraviolet absorbers are colored by absorbing ultraviolet rays, such as hindered amine ultraviolet absorbers. Therefore, in the coating composition used for forming a film layer of a liquid crystal display device or the like that requires high visibility, the use of these ultraviolet absorbers is very limited.
However, according to the present invention, it is possible to improve the weather resistance of the formed film layer without using such a weather resistance stabilizer such as an ultraviolet absorber.

  In the present invention, as the second component, a trifunctional or higher functional unsaturated double bond group-containing monomer (a) having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule; It is preferable to use together with other polyfunctional reactive unsaturated double bond group-containing monomer (b). By using the other polyfunctional reactive unsaturated double bond group-containing monomer (b) in combination, the surface hardness of the resulting film layer can be ensured.

  Multifunctional reactive unsaturated double bond group-containing monomer (b) other than the above-mentioned trifunctional or more reactive unsaturated double bond group-containing monomer (a) (hereinafter, the second component ( b)), for example, a trifunctional or higher polyfunctional unsaturated double bond group-containing monomer which is a dealcoholization reaction product of a polyhydric alcohol and (meth) acrylate. Can be mentioned. Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, tripropylene Examples include glycol di (meth) acrylate, nanoethylene glycol di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and neopentyl glycol di (meth) acrylate. These polyfunctional reactive unsaturated double bond group-containing monomers (b) may be used alone or in combination of two or more.

  A trifunctional or higher functional unsaturated group having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in the monomer molecule in the second component polyfunctional reactive unsaturated double bond group-containing monomer. The ratio between the double bond group-containing monomer (a) and the other polyfunctional reactive unsaturated double bond group-containing monomer (b) is (a) :( b) = 3: 97 to 40:60. Is preferred. When the ratio of (a) is lower than 3, sufficient weather resistance improvement effects may not be obtained. Moreover, when the ratio of (a) exceeds 40, there exists a possibility that the surface hardness of the film layer obtained may become low.

  Moreover, it is preferable that the 1st component and 2nd component in this invention have a functional group which mutually reacts, respectively. By causing these functional groups to react with each other, the resistance of the coating film having fine unevenness obtained by the antiblocking curable resin composition can be increased. As a combination of such functional groups, for example, a functional group having active hydrogen (hydroxyl group, amino group, thiol group, carboxyl group, etc.) and an epoxy group, a functional group having active hydrogen and an isocyanate group, and an ethylenically unsaturated group Ethylenically unsaturated group (polymerization of ethylenically unsaturated group occurs), silanol group and silanol group (condensation polymerization of silanol group occurs), silanol group and epoxy group, functional group having active hydrogen and functional group having active hydrogen Groups, active methylene and acryloyl groups, oxazoline groups and carboxyl groups. As the “functional group that reacts with each other” here, the reaction does not proceed only by mixing only the first component and the second component, but a polymerization initiator, a curing agent, a catalyst, and a photosensitizer are combined. And those that react with each other by mixing. Examples of the polymerization initiator that can be used here include a photopolymerization initiator and a thermal polymerization initiator. Examples of the photopolymerization initiator include 2-hydroxy-2methyl-1-phenyl-propan-1-one, 1 -Hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like. Examples of the thermal polymerization initiator include azo thermal polymerization initiators such as azobisisobrityronitrile, peroxide thermal polymerization initiators such as benzoyl peroxide, and the like. Examples of usable catalysts include acids, base catalysts, metal catalysts, and examples of usable photosensitizers include benzophenone and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, and coumarin and derivatives thereof. . Examples of the curing agent that can be used include a melamine curing agent, a (block) isocyanate curing agent, and an epoxy curing agent.

  When each of the first component and the second component has functional groups that react with each other, the mixture of the first component and the second component is thermosetting, photocurable (UV curable, visible light curable, infrared It has curability such as curability. Since thermosetting can affect a thermoplastic resin that can serve as a substrate, it is preferable to perform a curing reaction that does not use heat, particularly a photocuring reaction.

  The first component resin has a weight average molecular weight (Mw) of 2000 or more, preferably 2000 to 100,000, more preferably 5000 to 50000. In this invention, the weight average molecular weight of resin can be determined as a conversion value by a polystyrene standard using GPC measurement.

  Examples of the difference in physical properties of the first component and the second component that cause phase separation between the first component and the second component include a case where the SP value and the weight average amount of each component have a certain difference. .

  The SP value is an abbreviation for solubility parameter (solubility parameter) and is a measure of solubility. The SP value indicates that the polarity is higher as the numerical value is larger, and the polarity is lower as the numerical value is smaller.

  For example, the SP value can be measured by the following method [references: SUH, CLARKE, J. et al. P. S. A-1, 5, 1671-1681 (1967)].

Measurement temperature: 20 ° C
Sample: Weigh 0.5 g of resin in a 100 ml beaker, add 10 ml of good solvent using a whole pipette, and dissolve with a magnetic stirrer.
solvent:
Good solvent: dioxane, acetone, etc. Poor solvent: n-hexane, ion-exchanged water, etc. Muddy point measurement: The poor solvent is added dropwise using a 50 ml burette, and the point at which turbidity occurs is defined as the amount of addition.

  The SP value δ of the resin is given by the following equation.

Vi: Molecular volume of the solvent (ml / mol)
φi: Volume fraction of each solvent at cloud point δi: SP value of solvent ml: Low SP poor solvent mixed system mh: High SP poor solvent mixed system

  When the difference between the physical properties of the first component and the second component that causes phase separation between the first component and the second component is the difference in SP value, the difference between the SP value of the first component and the SP value of the second component Is preferably 1.0 or more. The difference in SP value is more preferably 1.5 or more. The upper limit of the difference in SP value is not particularly limited, but is generally 8 or less. When the difference between the SP value of the first component and the SP value of the second component is 1.0 or more, the compatibility of the resins is low, thereby the first component after application of the antiblocking curable resin composition It is believed that a phase separation between the second component and the second component occurs. By phase separation, the resin of the first component can be precipitated.

  The SP value of the first component is preferably smaller than the SP value of the second component. As described above, it is preferable to use the monomer represented by the above formula 1 as the second component, and in accordance with the purpose, the numerical values of n and m and / or x, y and z can be changed as appropriate. That's fine.

  The resin of the first component preferably has a lower limit of the glass transition temperature (Tg) of 2 ° C. or higher, preferably 10 ° C. or higher, more preferably 50 ° C. or higher. On the other hand, the upper limit of the glass transition point is 200 ° C., preferably 150 ° C. The glass transition temperature can be obtained by a method similar to the method for measuring Tg by ordinary dynamic viscoelasticity. This Tg can be measured using, for example, RHEOVIBRON MODEL RHEO2000, 3000 (trade name, manufactured by Orientec). When the glass transition temperature is lower than 2 ° C, the antiblocking performance may be lowered.

  The anti-blocking curable resin composition of the present invention may contain a commonly used resin in addition to the first component and the second component. The anti-blocking curable resin composition of the present invention uses the first component and the second component as described above to form a resin layer having irregularities without including other resin particles. It is characterized by being able to. Therefore, it is preferable that the antiblocking curable resin composition of the present invention does not contain other resin particles. However, the antiblocking curable resin composition of the present invention may contain at least one or more inorganic particles, organic particles, or a composite thereof, as necessary. These particles are not particularly added for the purpose of forming irregularities on the surface, but are added to form more uniform and fine irregularities by controlling phase separation and precipitation. These particles have an average particle size of 0.5 μm or less, preferably 0.01 to 0.3 μm, when the coating needs transparency. When it exceeds 0.5 μm, the transparency slightly decreases.

  Examples of inorganic particles include silica (including organosilica sol), alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide) / Tin oxide), ATO (antimony oxide / tin oxide), at least one selected from the group consisting of tin oxide, indium oxide and antimony oxide.

  Examples of the organic particles include at least one selected from the group consisting of acrylic, olefin, polyether, polyester, urethane, polyester, silicone, polysilane, polyimide, and fluorine particles.

  The anti-blocking curable resin composition of the present invention is obtained by mixing the first component and the second component together with a solvent, a polymerization initiator, a catalyst, a photosensitizer, a curing agent, and the like as necessary. Can be prepared. The ratio of the first component and the second component in the anti-blocking curable resin composition is preferably 0.1: 99.9-50: 50, more preferably 0.3: 99.7-20: 80. 0.5: 99.5-10: 90 is more preferable. When using a polymerization initiator, a catalyst, a photosensitizer and the like, with respect to 100 parts by weight of the first component, the second component, and other resin as necessary (collectively referred to as “resin component”), 0.01 to 20 parts by weight, preferably 1 to 10 parts by weight can be added. When using a hardening | curing agent, 0.1-50 weight part with respect to 100 weight part of said resin components, Preferably 1-30 weight part can be added. When using a solvent, 1-9900 weight part with respect to 100 weight part of said resin components, Preferably it can add 10-900 weight part.

  The solvent in the anti-blocking curable resin composition used in the present invention is not particularly limited, and the first component and the second component, the material of the base material used as the base of the coating, the coating method of the composition, etc. Is selected in a timely manner. Specific examples of the solvent used include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, Ether solvents such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate; dimethylformamide, diethylformamide Amide solvents such as N-methylpyrrolidone; methyl cellosol , Ethyl cellosolve, cellosolve solvents such as butyl cellosolve; methanol, ethanol, propanol, isopropanol, alcohol solvents such as butanol; and the like; dichloromethane, halogenated solvents such as chloroform. These solvents may be used alone or in combination of two or more. Of these solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferably used.

  Various additives can be added to the antiblocking curable resin composition of the present invention as necessary. Examples of such additives include conventional additives such as antistatic agents, plasticizers, surfactants, antioxidants and ultraviolet absorbers.

Anti-blocking hard coat film When the anti-blocking curable resin composition of the present invention is cured into a film, an anti-blocking hard coat film is obtained. As the curing method and conditions, those described in the description of the anti-blocking layered structure below are used.

Anti-blocking layered structure The anti-blocking layered structure of the present invention has a substrate and a coating film (hard coat film of the present invention) having fine irregularities. The coating film having fine irregularities can be formed from the antiblocking curable resin composition.

  As the substrate, various plastic films and plastic plates can be used. Examples of plastic films include triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyethersulfone film, polyacrylic resin film, polyurethane resin film, polyester film Polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyether ketone film, (meth) acrylonitrile film, cycloolefin polymer (COP) film and the like can be used. Examples of plastic plates include acrylic plates, triacetyl cellulose plates, polyethylene terephthalate plates, diacetylene cellulose plates, acetate butyrate cellulose plates, polyethersulfone plates, polyurethane plates, polyester plates, polycarbonate plates, polysulfone plates, polyethers. Examples include a plate, a polymethylpentene plate, a polyetherketone plate, and a (meth) acrylonitrile plate. In addition, although the thickness of a base material layer can be selected timely according to a use, generally it is used at about 25-1000 micrometers.

  The film having fine irregularities is formed by applying the above-described antiblocking curable resin composition on a substrate. The application method of the anti-blocking curable resin composition can be selected as appropriate according to the anti-blocking curable resin composition and the state of the coating process. For example, the dip coating method, the air knife coating method, the curtain coating It can be applied by a method, a roller coating method, a bar coating method, a wire bar coating method, a gravure coating method, an extrusion coating method (US Pat. No. 2,681,294).

  The thickness of the film having fine irregularities is not particularly limited, and can be set as appropriate in consideration of various factors. For example, the antiblocking curable resin composition can be applied so that the dry film thickness is 0.01 to 20 μm.

  The coating film applied to the substrate layer may be phase-separated at room temperature, or the coating film may be dried before curing and phase-separated before curing. In the case of drying or heating before curing the coating film, it is dried at 30 to 200 ° C., more preferably 40 to 150 ° C. for 0.01 to 30 minutes, more preferably 0.1 to 10 minutes. Can be separated. When the mixture of the first component and the second component is photocurable, drying before curing and phase separation in advance can effectively remove the solvent in the film having fine irregularities, and There is an advantage that unevenness of a desired size can be provided.

As another method of phase separation before curing, a method of irradiating the coating film with light and causing phase separation can also be used. As light to irradiate, for example, light having an exposure amount of 0.1 to 3.5 J / cm ² , preferably 0.5 to 1.5 J / cm ² can be used. The wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 360 nm or less can be used. For example, when 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one or the like is used as a photoinitiator, the irradiation light is irradiated with light having a wavelength near 310 nm. Further, it is more preferable to irradiate light having a wavelength near 360 nm. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like. By irradiating light in this way, phase separation and curing will occur. There is an advantage that unevenness of the surface shape due to drying unevenness of the solvent contained in the antiblocking curable resin composition can be avoided by irradiating light to cause phase separation.

  A coating film having fine irregularities is formed by curing a coating film obtained by applying the antiblocking curable resin composition or a dried coating film. When the mixture of the first component and the second component is thermosetting, heating at 40 to 280 ° C, more preferably 80 to 250 ° C, for 0.1 to 180 minutes, more preferably 1 to 60 minutes. Can be cured. When the mixture of a 1st component and a 2nd component is photocurable, it can be hardened by irradiating light using the light source which emits the light of the wavelength as needed. In addition, light irradiation may be as above-mentioned and can also be used in order to carry out phase separation.

  A schematic cross-sectional view of the antiblocking layered structure thus formed is shown in FIG. The anti-blocking layered structure (1) has a coating (that is, a hard coat film) (2) having a fine unevenness and a substrate (3). Since the fine unevenness on the surface of the anti-blocking layered structure of the present invention is naturally determined, the irregular uneven shape can be formed on the surface of the resin layer.

When the anti-blocking layered structure of the present invention is transparent, the total light transmittance is 85% or more, preferably 90% or more, and the haze is 2.0%. % Or less, preferably 1.8% or less, more preferably 1.5% or less. The total light transmittance (T _t (%)) is measured by measuring the incident light intensity (T ₀ ) with respect to the anti-blocking layered structure and the total transmitted light intensity (T ₁ ) transmitted through the anti-blocking layered structure, Calculated by the following formula. A schematic illustration of the total light transmittance (Tt (%)) is shown in FIG.

  The total light transmittance can be measured using, for example, a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.).

  According to the present invention, since the haze is low as described above, an antiblocking hard coat film having excellent clear performance without impairing the transparency of the substrate can be prepared.

Ｈ：ヘイズ（曇価）（％）
Ｔ_ｄ：拡散透光率（％）
Ｔ_ｔ：全光線透過率（％） The haze can be calculated from the following formula in accordance with JIS K7136.

H: Haze (cloudiness value) (%)
T _d : Diffuse transmittance (%)
T _t : Total light transmittance (%)

  The haze can be measured using, for example, a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.).

  In the anti-blocking layered structure of the present invention, the arrangement of irregular irregularities on the surface of the coating film having fine irregularities is determined spontaneously.

  The anti-blocking layered structure of the present invention comprises a hard coat film layer containing the first component and the second component described above and a base material, and includes the second component, particularly the second component (b). The deterioration of weather resistance due to aging of the film can be reduced.

Winding roll The anti-blocking layered structure of the present invention exhibits anti-blocking performance when used in a plurality. Various forms of the anti-blocking layered structure are conceivable. For example, the anti-blocking layered structure may be wound and rolled.

  In the case of such a wound roll, a method is conceivable in which the antiblocking curable resin composition of the present invention is coated and cured on a base material layer and then wound into a roll.

Display Device The present invention further relates to a display device including the above-described anti-blocking layered structure and a light source. In this case, the substrate included in the anti-blocking layered structure is desirably a light-transmitting substrate. Moreover, it is preferable that a light source is arrange | positioned on the back surface of a base material, ie, the surface on the opposite side to the fine uneven | corrugated layer of a base material, and irradiates light toward a base material there.

  As the translucent substrate, a translucent plastic film and a plastic plate are preferable among the above-described substrates, and glass or the like may be used as necessary. As translucent plastic films, triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyethersulfone film, polyacrylic resin film, polyurethane resin Film, polyester film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyetherketone film, (meth) acrylonitrile film, and cycloolefin polymer (COP) film are preferred. In particular, acrylic plates, triacetyl cellulose plates, polyethylene terephthalate plates, diacetylene cellulose plates, acetate plates Rate cellulose plates, polyether sulfone plate, polyurethane plate, polyester plate, polycarbonate plate, polysulfone plates, polyether board, polymethyl pentene plate, polyetherketone plate, (meth) acrylonitrile plate preferable. It is preferable to use a PET film as the translucent substrate from the viewpoint of strength. In addition, although the thickness of a translucent base material can be selected timely according to a use, generally it is used at about 25-1000 micrometers.

  The light source that can be combined with the anti-blocking layered structure is not particularly limited as long as it can emit light. Examples of the light source include a light emitting diode, a cold cathode tube, a hot cathode tube, and an EL. Etc. The display device of the present invention may further include a retardation plate, a brightness enhancement film, a light guide plate, a light diffusing plate, a light diffusing sheet, a light collecting sheet, a reflecting plate, and the like. Further, a liquid crystal module, a backlight unit, or the like may be used as the light source.

  An example of an embodiment of the display device of the present invention is shown in FIG. As shown in FIG. 3, the display device of the present invention includes the anti-blocking layered structure (10) of the present invention. The anti-blocking layered structure (10) includes a coating film (20) having fine irregularities formed by the anti-blocking curable resin composition of the present invention, and a substrate (30). The display device of the present invention preferably includes a liquid crystal module and a backlight unit as the light source (50). As shown in FIG. 3, the display device of the present invention may further include a light transmissive member (40) such as a cover panel. In the present invention, the same member as the substrate (30) may be used as the light transmissive member (40). Moreover, in this invention, you may provide a fine uneven | corrugated film on both sides of a base material (30). In the present invention, the direction of the unevenness of the fine uneven film (20) is not particularly limited.

  As the light transmissive member, various light transmissive plates, light transmissive films, and the like can be used. For example, tempered glass, acrylic plate, triacetyl cellulose plate, polyethylene terephthalate plate, diacetylene cellulose plate, acetate butyrate cellulose plate, polyethersulfone plate, polyurethane plate, polyester plate, polycarbonate plate, polysulfone plate , Polyether plate, polymethylpentene plate, polyether ketone plate, (meth) acrylonitrile plate and the like. Examples of light transmissive films include triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyether sulfone film, polyacrylic resin film, polyurethane resin film, Examples include a polyester film, a polycarbonate film, a polysulfone film, a polyether film, a polymethylpentene film, a polyether ketone film, a (meth) acrylonitrile film, and a cycloolefin polymer (COP) film. As the light transmissive member, an acrylic plate, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a cycloolefin polymer (COP) film, and tempered glass are more preferably used. In addition, although the thickness of a light transmissive member can be selected timely according to a use, it is generally used at about 25-1000 micrometers.

  The liquid crystal module includes the light source, and further has a configuration in which polarizing plates / liquid crystal cells / polarizing plates are arranged in this order. The liquid crystal cell is not particularly limited as long as it is generally used in a liquid crystal display device. For example, a TN (Twisted Nematic) type liquid crystal cell, an STN (Super Twisted Nematic) type liquid crystal cell, a HAN (Hybrid Alignment Nematic) type liquid crystal cell, an IPS (In Plane Switching) type liquid crystal cell, and a VA (vertical type liquid crystal cell). Examples thereof include a MVA (Multiple Vertical Alignment type liquid crystal cell) and an OCB (Optical Compensated Bend) type liquid crystal cell.

  The coating film (20) having fine irregularities formed by the antiblocking curable resin composition of the present invention has an arithmetic average roughness (Ra) of the surface roughness curve of the coating film having fine irregularities of less than 0.01 μm. It is preferable that it is 0.001-0.009 micrometer, and it is especially preferable that it is 0.002-0.008 micrometer. Here, the arithmetic mean roughness (Ra) of the roughness curve is a parameter defined in JIS B 0601-2001. When the arithmetic mean roughness (Ra) of the surface roughness curve of the coating having fine irregularities is 0.01 μm or more, there is a possibility that problems such as generation of glare and whitening of the coating may occur. If the value of Ra is less than the particularly preferable range, a blocking phenomenon occurs, which is not preferable.

  Arithmetic average roughness (Ra) of the roughness curve is a sample of only the reference length in the direction of the average line from the roughness curve, the X axis in the direction of the average line of this extracted portion, and Y in the direction of the vertical magnification. When the axis is taken and the roughness curve is expressed by y = f (x), the value obtained by the following formula is expressed in micrometers (μm).

  The arithmetic mean roughness (Ra) of the roughness curve of the surface of the coating film having fine irregularities formed by the antiblocking curable resin composition of the present invention is, for example, a high-precision fine shape measuring instrument manufactured by Kosaka Laboratory, Or it can measure based on JISB0601-2001 using the color 3D laser microscope made from Keyence Corporation.

  In addition, the coating film having fine irregularities formed by the antiblocking curable resin composition preferably has an Sm of 0.01 to 100 μm, more preferably 0.1 to 10 μm, and 0.3 to 1 μm is particularly preferable. Here, Sm is the average length of the roughness curve elements on the surface, and is generally referred to as the average interval between the peaks and valleys of the roughness curve or the average interval between the irregularities. When Sm falls below or exceeds the above desired range, there is a possibility that the light source such as the liquid crystal module and the light transmissive member cannot be sufficiently prevented from sticking.

  Sm can be measured in accordance with JIS B0633 using, for example, a high-precision fine shape measuring instrument manufactured by Kosaka Laboratories or a color 3D laser microscope manufactured by Keyence Corporation. Note that JIS B0633 is a Japanese industrial standard created by translating ISO 4288 without changing the technical contents and the format of the standard form.

  In a preferred embodiment of the display device of the present invention shown in FIG. 3, the coating (20) having fine irregularities formed by the anti-blocking curable resin composition comprises a light transmissive member (40) and a substrate (30). Since it has an irregular, fine and dense uneven shape, it provides excellent anti-blocking properties. When pressed from the upper side of the light-transmitting member (40), light is emitted by the excellent anti-blocking properties. Sticking (blocking) of the permeable member (40) can be prevented. In the display device of the present invention, the sharpness of an image displayed by a light source such as a liquid crystal module is not deteriorated. In particular, in recent high-definition liquid crystal display devices, the pitch of light rays emitted from the liquid crystal has become finer. Therefore, in order to maintain image clarity, a finer and denser uneven shape is required. The film (20) having fine unevenness formed in the present invention has a fine and dense uneven shape, and therefore has an advantage that it is not accompanied by a decrease in image sharpness such as a decrease in contrast and a decrease in luminance.

  The display device of the present invention is applied to a flat panel display such as a liquid crystal display device (liquid crystal display), LED (light emitting diode display), ELD (electroluminescence display), VFD (fluorescent display), PDP (plasma display panel), etc. can do. Moreover, since the anti-blocking curable resin composition of the present invention that can be used for producing the display device of the present invention has weather resistance in addition to the anti-blocking property, these display devices are used outdoors. Can be used. For example, it can be installed outdoors or semi-outdoors as a panel display for the purpose of posting information such as advertisements.

  In addition, the outdoor or semi-outdoor use of the display device of the present invention includes a touch panel, which has a mechanism for operating equipment by holding down the display on the screen, for example, bank ATM, vending Machines, personal digital assistants (PDAs), copiers, facsimiles, game machines, information displays installed in facilities such as museums and department stores, car navigation systems, multimedia stations (multifunctional terminals installed in convenience stores), This is useful in mobile phones, railway vehicle monitoring devices, and the like.

  When the anti-blocking layered structure of the present invention is used for a touch panel, it is very useful. The touch panel generally provides information on a display (500) such as a liquid crystal display (LCD) (which may be a liquid crystal module) or a cathode ray tube display (CRT), as shown in the specific embodiment of the present invention of FIG. Based on the above, operation is performed by pressing the screen with a finger or the like from above. In general, the touch panel is required to have excellent performance such as visibility, anti-sticking property, that is, anti-blocking property.

  In addition, as shown in the specific embodiment of the present invention shown in FIG. 4, the touch panel includes an upper electrode including the anti-blocking layered structure (101) and the transparent conductive layer (401) of the present invention, and anti-blocking properties. The lower electrode including the layered structure (102) and the transparent conductive layer (402) is arranged with a certain distance between the transparent conductive layer (401) and the transparent conductive layer (402) via an air layer. It is what.

  As shown in FIG. 4, the upper electrode of the touch panel includes the anti-blocking layered structure (101) of the present invention and the transparent conductive layer (401), and the anti-blocking layered structure (101) is as described above. The anti-blocking curable resin composition of the present invention is applied on a substrate (301) to form coatings (201) and (202) having fine irregularities. As shown in FIG. 4, it is preferable that the coatings (201) and (202) form fine irregularities toward both sides (that is, opposite sides) of the substrate. Moreover, only one of the coating films (201) and (202) may be present on the substrate. The anti-blocking layered structure (101) of the upper electrode may further have a light transmissive member (600) on the opposite side of the transparent conductive layer (401). There is no limitation in particular as a light transmissive member (600), What was demonstrated above, for example, the above-mentioned light transmissive member useful as a cover panel etc., can be used. Moreover, you may further provide the coating layer formed from the arbitrary translucent coating composition well-known in the said field | area on the light transmissive member (600). Alternatively, the light transmissive member (600) may be a coat layer formed from any light transmissive coating composition known in the art. The translucent coating composition that can be used in the present invention and the coating layer formed from the translucent coating composition are not particularly limited as long as they have optical transparency, and examples of the coating layer include an anti-blocking coating. Examples include a layer, an antiglare coat layer, a hard coat layer, an antireflection layer (AR, LR layer), an antifouling layer, a near-infrared absorbing layer, an electromagnetic wave blocking layer, and an antistatic layer.

  As shown in FIG. 4, the lower electrode of the touch panel includes the anti-blocking layered structure (102) and the transparent conductive layer (402) of the present invention, and the anti-blocking layered structure (102) is as described above. The anti-blocking curable resin composition of the present invention is applied on a substrate (302) to form films (203) and (204) having fine irregularities. As shown in FIG. 4, it is preferable that the coating films (203) and (204) form fine irregularities toward both sides (that is, opposite sides) of the substrate. Further, only one of the films (203) and (204) may be present on the substrate. The anti-blocking layered structure (102) of the lower electrode further includes a display (500) on the opposite side of the transparent conductive layer (402). The display (500) is not particularly limited as long as it includes the above-described light source. For example, a liquid crystal display (LCD) (may be a liquid crystal module), a cathode ray tube display (CRT), an LED (light emitting diode) EL (Electro Luminescence), VFD (fluorescent display tube), PDP (plasma display) and the like.

  Each of the transparent conductive layers (401) and (402) is a metal doped with ITO (indium tin oxide), ZnO (zinc oxide) and SnO (tin oxide), antimony oxide, fluorine, aluminum oxide, gallium oxide or the like. A conductive transparent layer containing an oxide or the like is preferable.

  As the base materials (301) and (302), any of the above-mentioned base materials that can be used in the present invention can be used, but those having higher transparency are desirable.

  In general, the touch panel has a complex multilayer structure, and in the present invention, the anti-blocking layered structure of the present invention has excellent light transmittance and weather resistance, so that excellent light transmission required for the touch panel is achieved. And weather resistance can be achieved.

  Also, in general, the touch panel is operated by using the upper electrode and the lower electrode in contact with each other by pressing with a finger or the like from the upper side, and when sticking occurs at that time However, in the present invention, the problem is solved by the anti-blocking layered structure of the present invention.

  Therefore, since the touch panel of the present invention includes the above-described anti-blocking layered structures (101) and (102), it can provide excellent anti-blocking properties and can significantly prevent sticking, that is, blocking. be able to. Moreover, since the touchscreen of this invention contains the anti-blocking layered structure (101) and (102) and the light transmissive member (600) as needed, it can also provide the outstanding translucency. In the touch panel of the present invention, the direction of the unevenness of the fine uneven coating films (201) to (204) may be reversed (that is, even if the unevenness is formed toward the substrate (301) or (302)). Good). Moreover, you may use the same thing as a base material (301) or (302) as a light transmissive member (600).

  As described above, the anti-blocking layer formed from the anti-blocking curable resin composition of the present invention has excellent anti-blocking properties, and also has excellent translucency and weather resistance. It is very useful in the electrode and the bottom electrode. Further, as shown in FIG. 4, even when the transparent conductive layer is formed on the anti-blocking layer, the winding is very simple and very useful.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” represents parts by weight.

Preparation Example 1
Preparation of unsaturated double bond-containing acrylic copolymer (I) A mixture consisting of 187.2 g of isobornyl methacrylate, 2.8 g of methyl methacrylate and 10.0 g of methacrylic acid was mixed. This mixture was added to 360 g of propylene glycol monomethyl ether heated to 110 ° C. under a nitrogen atmosphere in a 1000 ml reaction vessel equipped with a stirring blade, a nitrogen introducing tube, a cooling tube and a dropping funnel. At the same time as an 80.0 g solution of propylene glycol monomethyl ether containing 2.0 g of ate, the solution was added dropwise at a constant rate over 3 hours, and then reacted at 110 ° C. for 1 hour.

  Thereafter, a 17 g solution of propylene glycol monomethyl ether containing 0.2 g of tertiary butyl peroxy-2-ethyl hexaate was added dropwise and reacted at 110 ° C. for 30 minutes.

  6 g of propylene glycol monomethyl ether solution containing 1.5 g of tetrabutylammonium bromide and 0.1 g of hydroquinone was added to the reaction solution, and further, 24.4 g of 4-hydroxybutyl acrylate glycidyl ether and propylene glycol monomethyl ether 5 were added while air bubbling. 0.0 g of the solution was added dropwise over 1 hour, followed by further reaction over 5 hours.

  An unsaturated double bond-containing acrylic copolymer having a number average molecular weight of 5500 and a weight average molecular weight (Mw) of 18000 was obtained. This resin had SP value: 9.7 and Tg: 92 ° C.

Preparation Example 2
Preparation of unsaturated double bond-containing acrylic copolymer (II) A mixture consisting of 97.2 g of isobornyl methacrylate, 2.8 g of methyl methacrylate and 100 g of methacrylic acid was mixed. This mixture was added to 360 g of propylene glycol monomethyl ether heated to 110 ° C. under a nitrogen atmosphere in a 1000 ml reaction vessel equipped with a stirring blade, a nitrogen introducing tube, a cooling tube and a dropping funnel. At the same time as 80.0 g solution of propylene glycol monomethyl ether containing 2.5 g of ate was added dropwise at a constant rate over 3 hours, and then reacted at 110 ° C. for 1 hour.

  Thereafter, a 17 g solution of propylene glycol monomethyl ether containing 0.2 g of tertiary butyl peroxy-2-ethyl hexaate was added dropwise and reacted at 110 ° C. for 30 minutes.

  6 g of propylene glycol monomethyl ether solution containing 1.5 g of tetrabutylammonium bromide and 0.1 g of hydroquinone was added to the reaction solution, and a solution of 82.6 g of glycidyl methacrylate and 5.0 g of propylene glycol monomethyl ether was further added while air bubbling. The solution was added dropwise over 1 hour, and then further reacted over 5 hours.

  An unsaturated double bond-containing acrylic copolymer having a number average molecular weight of 8000 and a weight average molecular weight (Mw) of 18,000 was obtained. This resin had an SP value of 12.0 and Tg of 90 ° C.

Preparation Example 3
Preparation of acrylic resin particles A A reaction vessel equipped with a stirrer, a cooler, and a temperature controller was charged with 350 parts of deionized water and 1.5 parts of a nonionic surfactant MON2 (manufactured by Sanyo Chemical Co., Ltd.), and the stirring temperature Is dissolved while maintaining at 80 ° C., and an initiator: a solution prepared by dissolving 0.3 part of ammonium persulfate in 10 parts of deionized water is added. Next, a mixed solution composed of 80 parts of methyl methacrylate, 10 parts of ethylene glycol dimethacrylate, and 10 parts of n-butyl acrylate is dropped over 120 minutes. After dropping, stirring is continued at 80 ° C. for 120 minutes. An emulsion having a nonvolatile content of 22% and a particle size of 0.05 to 0.1 μm is thus obtained. The emulsion was dried to obtain acrylic resin particles A (average particle size: 80 nm).

Example 1
Unsaturated double bond-containing acrylic copolymer (I) of Preparation Example 1 (SP value: 9.7, Tg: 92 ° C., Mw = 18000) 1.5 parts, triethylene glycol-trimethylolpropane triacrylate (SP Value: 11.6) 20 parts, dipentaerythritol hexaacrylate (SP value: 12.1) 39.25 parts and pentaerythritol triacrylate (SP value: 12.7) 39.25 parts, 1 as photopolymerization initiator 5 parts of hydroxy-cyclohexyl-phenyl-ketone was mixed with methyl isobutyl ketone to prepare a solution having a non-volatile component ratio of 50% by weight.

This solution was applied to a PET film substrate (100 μm) at 23 ° C. with a bar coater (No. 8) and dried at 80 ° C. for 60 seconds so that the film thickness was 6 μm. Then, this film was exposed to ultraviolet light (350 nm) with a high-pressure mercury lamp so as to have an energy of 300 mJ / cm ² and cured to obtain an anti-blocking layered structure (base material: PET film substrate and anti-blocking hard Coated film) was obtained.

Example 2
Unsaturated double bond-containing acrylic copolymer (I) of Preparation Example 1 (SP value: 9.7, Tg: 92 ° C., Mw = 18000) 1.5 parts, triethylene glycol-trimethylolpropane triacrylate (SP Value: 11.6) 35 parts, dipentaerythritol hexaacrylate (SP value: 12.1) 31.75 parts and pentaerythritol triacrylate (SP value: 12.7) 31.75 parts, organosilica sol as inorganic particles ( MIBK-ST: Average particle size 20 nm, manufactured by Nissan Chemical Industries, Ltd.) 10 parts, 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator were mixed with methyl isobutyl ketone, and the nonvolatile component ratio was 50 weight. % Solution was prepared.

This solution was applied to a PET film substrate (100 μm) at 23 ° C. with a bar coater (No. 8) and dried at 80 ° C. for 60 seconds so that the film thickness was 6 μm. Then, this film was exposed to ultraviolet light (350 nm) with a high-pressure mercury lamp so as to have an energy of 300 mJ / cm ² and cured to obtain an anti-blocking layered structure (base material: PET film substrate and anti-blocking hard Coated film) was obtained.

Example 3
Unsaturated double bond-containing acrylic copolymer (I) of Preparation Example 1 (SP value: 9.7, Tg: 92 ° C., Mw = 18000) 1.5 parts, triethylene glycol-trimethylolpropane triacrylate (SP Value: 11.6) 5 parts, dipentaerythritol hexaacrylate (SP value: 12.1) 46.75 parts and pentaerythritol triacrylate (SP value: 12.7) 46.75 parts, Preparation Example 3 as organic particles 10 parts of acrylic resin particles A (average particle size 80 nm), manufactured by Nippon Paint Co., Ltd., and 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator are mixed with methyl isobutyl ketone to obtain a nonvolatile component ratio. A 50% by weight solution was prepared.

This solution was applied to a PET film substrate (100 μm) at 23 ° C. with a bar coater (No. 8) and dried at 80 ° C. for 60 seconds so that the film thickness was 6 μm. Then, this film was exposed to ultraviolet light (350 nm) with a high-pressure mercury lamp so as to have an energy of 300 mJ / cm ² and cured to obtain an anti-blocking layered structure (base material: PET film substrate and anti-blocking hard Coated film) was obtained.

Example 4
Unsaturated double bond-containing acrylic copolymer (I) of Preparation Example 1 (SP value: 9.7, Tg: 92 ° C., Mw = 18000) 1.5 parts, tripropylene glycol-trimethylolpropane triacrylate (SP Value: 11.2) 20 parts, dipentaerythritol hexaacrylate (SP value: 12.1) 39.25 parts and pentaerythritol triacrylate (SP value: 12.7) 39.25 parts, 1 as photopolymerization initiator 5 parts of hydroxy-cyclohexyl-phenyl-ketone was mixed with methyl isobutyl ketone to prepare a solution having a non-volatile component ratio of 50% by weight.

This solution was applied to a PET film substrate (100 μm) at 23 ° C. with a bar coater (No. 8) and dried at 80 ° C. for 60 seconds so that the film thickness was 6 μm. Then, this film was exposed to ultraviolet light (350 nm) with a high-pressure mercury lamp so as to have an energy of 300 mJ / cm ² and cured to obtain an anti-blocking layered structure (base material: PET film substrate and anti-blocking hard Coated film) was obtained.

Example 5
Unsaturated double bond-containing acrylic copolymer (I) of Preparation Example 1 (SP value: 9.7, Tg: 92 ° C., Mw = 18000) 1.5 parts, hexaethylene glycol-trimethylolpropane triacrylate (SP Value: 12.3) 20 parts, dipentaerythritol hexaacrylate (SP value: 12.1) 39.25 parts and pentaerythritol triacrylate (SP value: 12.7) 39.25 parts, 1 as photopolymerization initiator 5 parts of hydroxy-cyclohexyl-phenyl-ketone was mixed with methyl isobutyl ketone to prepare a solution having a non-volatile component ratio of 50% by weight.

This solution was applied to a PET film substrate (100 μm) at 23 ° C. with a bar coater (No. 8) and dried at 80 ° C. for 60 seconds so that the film thickness was 6 μm. Then, this film was exposed to ultraviolet light (350 nm) with a high-pressure mercury lamp so as to have an energy of 300 mJ / cm ² and cured to obtain an anti-blocking layered structure (base material: PET film substrate and anti-blocking hard Coated film) was obtained.

Example 6
Unsaturated double bond-containing acrylic copolymer (I) of Preparation Example 1 (SP value: 9.7, Tg: 92 ° C., Mw = 18000) 1.5 parts, hexapropylene glycol trimethylolpropane triacrylate (SP value) : 11.6) 20 parts, dipentaerythritol hexaacrylate (SP value: 12.1) 39.25 parts and pentaerythritol triacrylate (SP value: 12.7) 39.25 parts, 1- 5 parts of hydroxy-cyclohexyl-phenyl-ketone was mixed with methyl isobutyl ketone to prepare a solution having a nonvolatile component ratio of 50% by weight.

This solution was applied to a PET film substrate (100 μm) at 23 ° C. with a bar coater (No. 8) and dried at 80 ° C. for 60 seconds so that the film thickness was 6 μm. Then, this film was exposed to ultraviolet light (350 nm) with a high-pressure mercury lamp so as to have an energy of 300 mJ / cm ² and cured to obtain an anti-blocking layered structure (base material: PET film substrate and anti-blocking hard Coated film) was obtained.

Comparative Example 1
Unsaturated double bond-containing acrylic copolymer (I) of Preparation Example 1 (SP value: 9.7, Tg: 92 ° C., Mw = 18000) 1.5 parts, dipentaerythritol hexaacrylate (SP value: 12. 1) 49.25 parts and 49.25 parts of pentaerythritol triacrylate (SP value: 12.7) and 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator were mixed with methyl isobutyl ketone to make a nonvolatile A solution having a component ratio of 50% by weight was prepared.

This solution was applied to a PET film substrate (100 μm) at 23 ° C. with a bar coater (No. 8) and dried at 80 ° C. for 60 seconds so that the film thickness was 6 μm. Then, this film was exposed to ultraviolet light (350 nm) with a high-pressure mercury lamp so as to have an energy of 300 mJ / cm ² and cured to obtain an anti-blocking layered structure (base material: PET film substrate and anti-blocking hard Coated film) was obtained.
Comparative Example 2
Unsaturated double bond-containing acrylic copolymer (I) of Preparation Example 1 (SP value: 9.7, Tg: 92 ° C., Mw = 18000) 1.5 parts, trimethylolpropane triacrylate (SP value: 9. 8) 20 parts, 39.25 parts of dipentaerythritol hexaacrylate (SP value: 12.1) and 39.25 parts of pentaerythritol triacrylate (SP value: 12.7), 1-hydroxy-cyclohexyl as a photopolymerization initiator -5 parts of phenyl-ketone was mixed with methyl isobutyl ketone to prepare a solution having a non-volatile component ratio of 50% by weight.

This solution was applied to a PET film substrate (100 μm) at 23 ° C. with a bar coater (No. 8) and dried at 80 ° C. for 60 seconds so that the film thickness was 6 μm. Then, this film was exposed to ultraviolet light (350 nm) with a high-pressure mercury lamp so as to have an energy of 300 mJ / cm ² and cured to obtain an anti-blocking layered structure (base material: PET film substrate and anti-blocking hard Coated film) was obtained.
Comparative Example 3
Unsaturated double bond-containing acrylic copolymer (I) of Preparation Example 1 (SP value: 9.7, Tg: 92 ° C., Mw = 18000) 1.5 parts, tripropylene glycol diacrylate (SP value: 14. 1) 20 parts, 39.25 parts of dipentaerythritol hexaacrylate (SP value: 12.1) and 39.25 parts of pentaerythritol triacrylate (SP value: 12.7), 1-hydroxy-cyclohexyl as a photopolymerization initiator -5 parts of phenyl-ketone was mixed with methyl isobutyl ketone to prepare a solution having a non-volatile component ratio of 50% by weight.

This solution was applied to a PET film substrate (100 μm) at 23 ° C. with a bar coater (No. 8) and dried at 80 ° C. for 60 seconds so that the film thickness was 6 μm. Then, this film was exposed to ultraviolet light (350 nm) with a high-pressure mercury lamp so as to have an energy of 300 mJ / cm ² and cured to obtain an anti-blocking layered structure (base material: PET film substrate and anti-blocking hard Coated film) was obtained.
Comparative Example 4
Unsaturated double bond-containing acrylic copolymer (I) of Preparation Example 1 (SP value: 9.7, Tg: 92 ° C., Mw = 18000) 1.5 parts, nanoethylene glycol diacrylate (SP value: 14. 8) 20 parts, 39.25 parts of dipentaerythritol hexaacrylate (SP value: 12.1) and 39.25 parts of pentaerythritol triacrylate (SP value: 12.7), 1-hydroxy-cyclohexyl as a photopolymerization initiator -5 parts of phenyl-ketone was mixed with methyl isobutyl ketone to prepare a solution having a non-volatile component ratio of 50% by weight.

This solution was applied to a PET film substrate (100 μm) at 23 ° C. with a bar coater (No. 8) and dried at 80 ° C. for 60 seconds so that the film thickness was 6 μm. Then, this film was exposed to ultraviolet light (350 nm) with a high-pressure mercury lamp so as to have an energy of 300 mJ / cm ² and cured to obtain an anti-blocking layered structure (base material: PET film substrate and anti-blocking hard Coated film) was obtained.
Comparative Example 5
Unsaturated double bond-containing acrylic copolymer (I) of Preparation Example 1 (SP value: 9.7, Tg: 92 ° C., Mw = 18000) 1.5 parts, dipentaerythritol hexaacrylate (SP value: 12. 1) 49.25 parts and 49,25 parts of pentaerythritol triacrylate (SP value: 12.7), 5 parts of tinuvin (TINUVIN # 400, manufactured by Ciba) as an ultraviolet absorber, 1-hydroxy-cyclohexyl as a photopolymerization initiator -5 parts of phenyl-ketone was mixed with methyl isobutyl ketone to prepare a solution having a non-volatile component ratio of 50% by weight.

This solution was applied to a PET film substrate (100 μm) at 23 ° C. with a bar coater (No. 8) and dried at 80 ° C. for 60 seconds so that the film thickness was 6 μm. Then, this film was exposed to ultraviolet light (350 nm) with a high-pressure mercury lamp so as to have an energy of 300 mJ / cm ² and cured to obtain an anti-blocking layered structure (base material: PET film substrate and anti-blocking hard Coated film) was obtained.
Comparative Example 6
50 parts of dipentaerythritol hexaacrylate (SP value: 12.1) and 50 parts of pentaerythritol triacrylate (SP value: 12.7), and 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator A solution having a non-volatile component ratio of 50% by weight was prepared by mixing with ketone.

This solution was applied to a PET film substrate (100 μm) at 23 ° C. with a bar coater (No. 8) and dried at 80 ° C. for 60 seconds so that the film thickness was 6 μm. Thereafter, the film was exposed to ultraviolet light (350 nm) with a high-pressure mercury lamp so as to have an energy of 300 mJ / cm ² and cured to obtain a layered structure (base material: PET film substrate and hard coat film). .

Comparative Example 7
Unsaturated double bond-containing acrylic copolymer (II) of Preparation Example 2 (SP value: 12.0, Tg: 90 ° C., Mw = 18000), 1.5 parts, triethylene glycol-trimethylolpropane triacrylate (SP Value: 11.6) 20 parts, dipentaerythritol hexaacrylate (SP value: 12.1) 39.25 parts and pentaerythritol triacrylate (SP value: 12.7) 39.25 parts, 1 as photopolymerization initiator 5 parts of hydroxy-cyclohexyl-phenyl-ketone was mixed with methyl isobutyl ketone to prepare a solution having a non-volatile component ratio of 50% by weight.

This solution was applied to a PET film substrate (100 μm) at 23 ° C. with a bar coater (No. 8) and dried at 80 ° C. for 60 seconds so that the film thickness was 6 μm. Then, this film is exposed and cured with ultraviolet light (350 nm) with a high-pressure mercury lamp so as to have an energy of 300 mJ / cm ² , and a layered structure having no anti-blocking property (base material: PET film substrate and hard coat) Film).

  The layered structures obtained in Examples and Comparative Examples were evaluated for initial appearance, haze (%), appearance after weathering test (25 cycles), steel wool resistance, and anti-blocking (AB) properties. Each evaluation method and evaluation criteria are as follows, and the results are shown in the following table.

  In the table, ΔSP indicates the difference between the SP value of the first component (SP1) and the SP value of the second component (SP2 (average value)) [ΔSP = (SP2) − (SP1)].

Initial appearance About the antiblocking hard coat film obtained by the said Example and comparative example, the coating-film external appearance before performing the following ASTM G154 conformity weather test was evaluated visually based on the following reference | standard.
○: Defects such as peeling or cracking of the coating film are not observed ×: Defects such as peeling or cracking of the coating film are observed

Ｈ：ヘイズ（曇価）（％）
Ｔ_ｄ：拡散透光率（％）
Ｔ_ｔ：全光線透過率（％） Haze (cloudiness) (%)
Using a turbidimeter (Nippon Denshoku Industries Co., Ltd. Model NDH-2000), the film's diffuse transmittance (T _d (%)) and the total light transmittance (T _t (%)) were measured, and haze Was calculated.

H: Haze (cloudiness value) (%)
T _d : Diffuse transmittance (%)
T _t : Total light transmittance (%)

なお、全光線透過率（％）は、日本電色工業株式会社製、型式ＮＤＨ−２０００「ホウホウ３」に基づいて測定した。 The total light transmittance (Tt) (%), using a turbidimeter (Nippon Denshoku Industries Co., Ltd. Model NDH-2000), the incident light intensity _(T 0) as, for films shown in the schematic diagram of FIG. 2 And the total transmitted light intensity (T ₁ ) transmitted through the film can be calculated by the following formula.

The total light transmittance (%) was measured based on Nippon Denshoku Industries Co., Ltd. model NDH-2000 “Houhou 3”.

Appearance after weathering test Weathering test according to ASTM (American Standards Testing Material) G154 (1 cycle: irradiating light at a wavelength of 313 nm for 4 hours at 60 ° C and then maintaining for 4 hours in a dark room at 50 ° C for 25 cycles) The appearance of the coating film after the evaluation was visually evaluated based on the following criteria.
○: There is no significant change in the appearance of the coating film before and after the weather resistance test. Δ: Part of the coating film is peeled or cracked. ×: Many coating films are peeled or cracked.

Steel Wool Resistance In the obtained anti-blocking hard coat film, the degree of scars on the surface generated after steel wool # 0000 was reciprocated 10 times with a load of 500 gf / cm ² was visually evaluated.
○: No scars are confirmed △: Some scars are confirmed ×: Many scars are confirmed

Anti-blocking (AB) structure A structure obtained from the above composition was cut into a size of 2 × 5 cm, and the coated surface was superposed on the surface of the PET film (non-adhesive layer uncoated) and sandwiched between glass plates at 200 gf / cm. ^{It was} allowed to stand at room temperature for 24 hours under ^two conditions, and the blocking phenomenon (AB property) was visually evaluated.
○: Anti-blocking property ×: No anti-blocking property

FIG. 5 shows a three-dimensional image of the coating surface having fine irregularities in the anti-blocking layered structure of Example 1 by a color 3D laser microscope (manufactured by Keyence Corporation, VK-9700).
FIG. 6 shows a three-dimensional image of the coating surface having fine irregularities in the anti-blocking layered structure of Example 4 by a color 3D laser microscope (manufactured by Keyence Corporation, VK-9700).
FIG. 7: shows the three-dimensional image by the color 3D laser microscope (the Keyence Corporation make, VK-9700) of the coating-film surface which has a fine unevenness | corrugation in the antiblocking layered structure of Example 5. FIG.
5-7 all show that the anti-blocking layered structure of the present invention has irregular and fine dense irregularities.

  As shown in the above table, each of the compositions of Examples 1 to 6 of the present invention includes an unsaturated double bond-containing acrylic copolymer (I) (SP value: 9.7) as the first component. As a second component, a trifunctional or higher functional unsaturated double bond group-containing monomer having 2 to 6 mole equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule (second component (a)) Is provided as an essential component, and in addition to excellent anti-blocking (AB) properties, a film having excellent weather resistance is provided. Moreover, since the film obtained from the composition of Examples 1-6 of this invention is excellent in initial stage appearance, and has a haze (cloudiness value) of 2.0% or less, it has the outstanding transparency (clear) property. Therefore, it is very beneficial when a film obtained from the composition of the present invention is applied to a display device. Moreover, since the film obtained from the composition of Examples 1-6 of this invention has the outstanding steel wool resistance, it is excellent also in abrasion resistance.

  On the other hand, in the compositions of Comparative Examples 1 to 5, the unsaturated double bond-containing acrylic copolymer (I) (SP value: 9.7) was blended as the first component. Two components (a) were not blended. Moreover, the composition of Comparative Example 6 was not blended with both the first component and the second component (a). As a result, as shown in the above table, the weather resistance decreased in Comparative Examples 1 to 4, and the steel wool resistance also decreased in Comparative Examples 3 and 4.

  In the composition of Comparative Example 5, the second component (a) was not blended, but instead, tinuvin (TINUVIN), which is a commonly used ultraviolet absorber, was blended. Although it could be suppressed, the steel wool resistance was significantly reduced.

  Thus, from the results of Comparative Examples 1 to 5 and Examples 1 to 6, it was found that weather resistance and steel wool resistance were dramatically improved by blending the second component (a) into the composition. It was.

  Moreover, in these Comparative Examples 1-5, compared with Examples 1-6, there exists a tendency for a haze (%) to rise and it exists in the tendency for the transparency of a film to fall.

  Since Comparative Example 6 did not contain both the first component and the second component (a), the film formed from this composition naturally showed no anti-blocking property.

  In Comparative (Reference) Example 7, unsaturated double bond-containing acrylic copolymer (II) (SP value: 12.0) was used as the first component, and triethylene glycol-trimethylol was used as the second component. Propane triacrylate (SP value: 11.6), dipentaerythritol hexaacrylate (SP value: 12.1), and pentaerythritol triacrylate (SP value: 12.7) (second component SP value (average value): 12.2), and the SP value (12.0) of the first component is smaller than the SP value (12.2) of the second component, but the value of the difference ΔSP is 0.2, It is less than 1.0 which is a preferable value of ΔSP of the present invention, and indicates that an excellent antiblocking property cannot be obtained.

  These results remarkably show that both excellent antiblocking properties and weather resistance can be obtained by blending both the first component and the second component (a) as essential components in the composition. Such an effect obtained by the present invention was a very surprising and remarkable effect that cannot be obtained by the prior art.

A backlight unit (manufactured by USHIO INC., Model number: FP-401) is used as a light source for producing a display device, and a photomask (black matrix with a resolution of 106 ppi) is mounted on the backlight unit. The anti-blocking layered structure produced in -6 or Comparative Examples 1 to 7 is placed with the substrate facing down and the anti-blocking layer having fine irregularities facing up, but water is placed between the substrate and the photomask. And laminated with air removed. Furthermore, on the antiblocking layer which has fine unevenness | corrugation, PET film (easy-adhesion layer non-application | coating) was further laminated | stacked as a light transmissive member, and the display apparatus was produced. It was confirmed from the upper side of the display device, that is, the upper side of the PET film, whether or not it was stuck with a finger (that is, whether there was blocking). As a result, in the case of using the anti-blocking layered structure produced in Examples 1 to 6, no sticking (blocking) was observed, and Comparative Examples 1 to 7, particularly Comparative Examples 6 and 7 When the produced layered structure was used, remarkable sticking (blocking) was observed. From the above results, it was found that the anti-blocking layered structure of the present invention is very useful for a display device and is also very useful when used for a touch panel.

  The anti-blocking curable resin composition of the present invention and the anti-blocking layered structure formed therefrom have excellent translucency and anti-blocking properties as well as excellent weather resistance, a hard coat film, a winding roll, It is useful as a display device, particularly as a touch panel.

DESCRIPTION OF SYMBOLS 1 Antiblocking layered structure 2 Film which has fine unevenness 3 Base material 10 Antiblocking layered structure 20 Film which has fine unevenness 30 Base material 40 Light-transmissive member (optional)
DESCRIPTION OF SYMBOLS 50 Light source 101 Antiblocking layered structure 102 Antiblocking layered structure 201 Film with fine unevenness 202 Film with fine unevenness 203 Film with fine unevenness 204 Film with fine unevenness 301 Base material 302 Base material 401 Transparent conductive layer 402 Transparent conductive layer 500 Display 600 Light transmissive member

Claims (13)

A curable resin composition comprising a first component comprising at least one or more resins, and a second component comprising at least one or more monomers,
The second component contains a multifunctional reactive double bond group-containing monomer having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule. An unsaturated double bond group-containing monomer
An antiblocking curable resin composition in which the resin of the first component is precipitated by phase separation after application of the composition to form fine irregularities on the surface, and has weather resistance. A trifunctional or more reactive unsaturated double bond group-containing monomer having 3 to 6 mole equivalents of the alkylene oxide unit having 2 to 4 carbon atoms in a monomer molecule is represented by the following formula 1

[In Formula 1,
n, m and p are each independently an integer of 2 to 4,
x, y and z are each independently an integer of 0 to 3, provided that the sum of x, y and z is 3 to 6, and R ¹ has a hydroxyl group. An alkyl group having 1 to 3 carbon atoms,
R ² , R ³ and R ⁴ are each independently hydrogen or a methyl group. ]
The antiblocking curable resin composition of Claim 1 which is a monomer shown by these.   The anti-blocking curable resin composition according to claim 1 or 2, wherein the curable resin composition further contains at least one kind of inorganic particles or organic particles.   The antiblocking curable resin composition of any one of Claims 1-3 whose difference of SP value of a 1st component and SP value of a 2nd component is 1.0 or more.   The antiblocking curable resin composition according to any one of claims 1 to 4, wherein the SP value of the first component is smaller than the SP value of the second component. The antiblocking curable resin composition according to any one of claims 1 to 5, which is photocurable.   The antiblocking hard coat film obtained by hardening | curing the antiblocking curable resin composition of any one of Claims 1-6 in a film form.   The antiblocking hard coat film according to claim 7, wherein the haze is 2.0% or less.   An antiblocking layered structure obtained by applying the antiblocking curable resin composition according to any one of claims 1 to 6 on a substrate and curing the composition.   The antiblocking layered structure which apply | coated the antiblocking curable resin composition of any one of Claims 1-6 on a base material, and wound the hardened | cured antiblocking layered structure in roll shape Winding roll.   An antiblocking layered structure obtained by applying the antiblocking curable resin composition according to any one of claims 1 to 6 on a substrate, drying and phase-separating, and then curing. Production method.   The method for producing an antiblocking layered structure according to claim 11, wherein the phase separation and curing are performed by irradiating light.   A display device comprising the anti-blocking layered structure according to claim 9 and a light source, wherein the substrate included in the anti-blocking layered structure is a light-transmitting substrate, and the light source is the substrate. A display device that emits light from the back of a material.

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