JP2007182519A - Antiblocking photosetting resin composition, antiblocking structure obtained by applying and curing the composition to substrate and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technique for preventing the problems of e.g. the adhesion of laminar materials such as thermoplastic films, i.e. blocking phenomenon. <P>SOLUTION: The antiblocking curable resin composition contains a first component composed of at least one kind of resin and a second component selected from one or more kinds of monomers or oligomers. The resin of the first component is precipitated by phase separation after the application of the composition to form minute irregularity on the surface. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an anti-blocking photo-curable resin composition and a method for manufacturing an anti-blocking structure which is coated and cured on a base material.

  When a hard coating is applied to a thermoplastic film such as a PET film, the film may be wound into a roll and stored in the manufacturing process. When another layered body is layered on a resin base layer such as a PET film with a hard coat, the adhesive or chemical force is applied between the layers, resulting in an adhering state and using each layered body In addition, a force for peeling off each layered body may be necessary, it may become difficult to peel off due to strong adhesion, or the layered body may be destroyed when it is peeled off.

  In such a case, a back coat is formed by applying a paint kneaded with particulate matter such as silica of about 1 μm on the opposite surface of the substrate that is not hard-coated, and the surface is uneven. By reducing the contact area between the layers, adhesion between the 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 back coat containing 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 .mu.m), the mechanical strength is reduced, the surface 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 above method, when particles are mixed in the back coat on the opposite side of the hard coat layer, there is also a technique for forming unevenness on the surface by mixing resin particles in the hard coat layer itself (Japanese Patent Application Laid-Open No. 2004-2001). No. 042653 (Patent Document 3) In the case of mixing particles, it is necessary to reduce the film thickness for forming irregularities on the surface, the film strength is weakened, the film is easily scratched, and the coating film properties are deteriorated. The photochemical properties may be impaired.

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

  An object of the present invention is to provide a technique capable of preventing a defect such as adhesion between layered bodies such as a thermoplastic film, that is, a blocking phenomenon without using a particulate substance.

  The present invention is a curable resin composition comprising a first component comprising at least one resin and a second component selected from the group consisting of at least one monomer or oligomer, and after application of the composition The anti-blocking curable resin composition in which the resin of the first component is precipitated by phase separation and forms fine irregularities on the surface, thereby achieving the above object.

  Both the first component and the second component preferably contain a (meth) acryloyl group.

  The curable resin composition preferably further contains at least one kind of inorganic particles or organic particles.

  Further, the difference between the SP value of the first component and the SP value of the second component is preferably 1.0 or more.

  It is preferable that the resin of the first component has a glass transition point (Tg) of 2 ° C. or higher and a weight average molecular weight of 2000 or higher.

  The inorganic particles or organic particles preferably have an average particle size of 0.5 μm or less.

  Moreover, it is preferable that the said antiblocking resin composition is photocurable.

  The present invention is also an antiblocking hard coat film obtained by curing the above antiblocking curable resin composition into a film, wherein the film has a total light transmittance of 90% or more and a haze of 2. An antiblocking hard coat film having a clear performance having 0% or less is also provided.

Further, it is also preferable that the surface of the hard coat film is Ra (arithmetic average height) 0.1 μm or less and R _z JIS (ten-point average roughness) 0.3 μm or less.

  The present invention also provides an anti-blocking layered structure obtained by applying the above-described anti-blocking curable resin composition on a substrate and curing it.

  The present invention also provides an antiblocking layered structure winding roll obtained by applying the antiblocking curable resin composition on a substrate and winding the cured antiblocking layered structure on a roll.

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

  The phase separation and curing are preferably performed by irradiating light.

  The anti-blocking curable resin composition of the present invention is an anti-blocking resin layer having unevenness on the surface only after being applied on a substrate and dried as necessary, and then cured (particularly photocured). A layer 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 resin 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.

The present invention will be described in more detail with reference to the following drawings. The drawings show the following:
FIG. 1 is a schematic cross-sectional view of the anti-blocking layered structure of the present invention.
FIG. 2 is an explanatory diagram of the parameter R _z JIS.
FIG. 3 is a schematic explanatory diagram of the total light transmittance.

Anti-blocking curable resin composition The anti-blocking curable resin composition of the present invention is applied on a resin substrate layer to form a film having fine irregularities. 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. The two components are phase separated.

  The first component is composed of at least one resin, and the second component is selected from the group consisting of at least one monomer or oligomer.

  As the first component resin, for example, (meth) acrylic resin, olefin resin, polyether resin, polyester resin, polyurethane resin, polysiloxane resin, polysilane resin, polyimide resin, or resin containing a fluorinated resin in a skeleton structure is used. be able to. These resins may be so-called oligomers having a low molecular weight. 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 fluorinated resin 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.

  The second component is a monomer or oligomer, and the monomer is a polyfunctional monomer, for example, a dealcoholization reaction product of a polyhydric alcohol and (meth) acrylate, specifically, dipentaerythritol hexa (meth) acrylate, Trimethylolpropane tri (meth) acrylate and the like can be used. As the oligomer, a urethane (meth) acrylate oligomer, a polyester (meth) acrylate oligomer or a low molecular weight product of the resin mentioned in the first component, particularly the number of repeating units is 3 to 10, and the weight average molecular weight is less than 8,000. Is. The oligomer may be a copolymer composed of two or more of the aforementioned skeleton structures of the resin, or may be a copolymer composed of the skeleton structure and other monomers.

  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. Further, the term “functional group that reacts with each other” here means that the reaction does not proceed only by mixing only the first component and the second component, but the polymerization initiator, curing agent, catalyst, and 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-1phenyl-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 and peroxide thermal polymerization initiators such as benzoyl peroxide. Examples of the catalyst that can be used include an acid, a base catalyst, and a metal catalyst. Examples of the photosensitizer that can be used 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 affects the thermoplastic resin as a substrate, a curing reaction that does not use heat, particularly a photocuring reaction, is preferred.

  Moreover, it is preferable that resin of the 1st component is 2000-100000 by weight average molecular weight, More preferably, it is 5000-50000.

  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 added.

  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.

  The first component resin is more preferably an unsaturated double bond-containing acrylic copolymer. The monomer or oligomer of the second component is more preferably a polyfunctional unsaturated double bond-containing monomer or an oligomer thereof. The “oligomer” in the present specification refers to a polymer having a repeating unit and having 3 to 10 repeating units.

  The unsaturated double bond-containing acrylic copolymer is, for example, 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. , A resin obtained by reacting a (meth) acryl monomer with another monomer having an ethylenically unsaturated double bond and an epoxy group, a monomer having a (meth) acryl monomer and another ethylenically unsaturated double bond and an isocyanate group And the like, and the like. One of these unsaturated double bond-containing acrylic copolymers may be used alone, or two or more thereof may be mixed and used.

  As the multifunctional unsaturated double bond-containing monomer, the above multifunctional monomer, for example, a dealcoholization reaction product of polyhydric alcohol and (meth) acrylate, specifically, dipentaerythritol hexa (meth) acrylate, Dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like can be used. In addition, an acrylate monomer having a polyethylene glycol skeleton such as polyethylene glycol # 200 diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used. One of these polyfunctional unsaturated double bond-containing monomers may be used alone, or two or more thereof may be mixed and used.

  As another example of the first component and the second component useful in the present invention, it is preferable to use a resin in which both the first component and the second component contain a (meth) acrylic resin in a skeleton structure. The first component is more preferably an unsaturated double bond-containing acrylic copolymer, and the second component is more preferably a polyfunctional unsaturated double bond-containing monomer.

  Preferred organic solvents when the first component and the second component are the above combinations include, for example, ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol An ether solvent such as anisole, phenetol propylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; One of these solvents may be used alone, or two or more organic solvents may be mixed and used.

  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 function is 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 antiblocking curable resin composition of the present invention can form a resin layer having irregularities without using resin particles or the like by using the first component and the second component as described above. There is a feature. Therefore, it is preferable that the antiblocking curable resin composition of this invention does not contain a resin particle. 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, alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide / tin oxide), ATO There may be mentioned at least one selected from the group consisting of (antimony oxide / tin oxide), 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 antiblocking curable resin composition of the present invention is prepared by mixing the first component and the second component together with a solvent, a polymerization initiator, a catalyst, a photosensitizer and a curing agent as necessary. The 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 a polymerization initiator, a catalyst, and a photosensitizer are used, the first component, the second component, and other resin as necessary (referred to collectively as “resin component”) are 100 parts by weight. 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 portion that is the base of the coating, the coating method of the composition, etc. Selected in a timely manner in consideration. Specific examples of the solvent used include, for example, 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, and phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; dimethylformamide, diethylformamide Amide solvents such as N-methylpyrrolidone; methyl cellosol , Ethyl cellosolve, cellosolve solvents such as butyl cellosolve; methanol, ethanol, alcohol solvents such as propanol; 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 resin substrate layer and a film having fine irregularities. The coating film having fine irregularities is formed from the antiblocking curable resin composition.

  As the resin base material layer, 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, A polycarbonate film, a polysulfone film, a polyether film, a polymethylpentene film, a polyether ketone film, a (meth) acrylonitrile film, and the like can be used. In addition, although the thickness of the resin base material layer can be appropriately selected according to the use, it is generally used at about 25 to 1000 μm.

  The film having fine irregularities is formed by applying the anti-blocking curable resin composition on the resin base material layer. 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, such as dip coating, air knife coating, curtain coating, The coating can be performed by a roller 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 resin base material 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 preferably irradiated with light having a wavelength near 310 nm. 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 unevenness in drying 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. Light irradiation can also be used for the purpose of phase separation as described above.

  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 3 having fine irregularities and a resin base layer 5. Since the unevenness on the surface of the anti-blocking layered structure of the present invention is determined spontaneously, an irregular uneven shape can be formed on the surface of the resin layer.

The uneven shape on the surface of the film having fine unevenness can be evaluated using parameters of R _z JIS (10-point average roughness). Here, R _z JIS is a parameter standardized in Annex 1 Table 1 of JIS B0601. This R _z JIS is an index representing the height roughness of the irregularities on the surface. FIG. 2 is an explanatory diagram of the parameter R _z JIS. In this figure, the solid curve indicates the cross section of the coating film having fine irregularities. The ten-point average roughness (R _z JIS) can be measured according to Appendix 1 of JIS B0601, using, for example, an ultra-deep shape measuring microscope manufactured by Keyence Corporation. Note that JIS B0601 is a Japanese industrial standard created by translating ISO 4287 without changing the technical contents and the format of the standard form.

The anti-blocking layered structure of the present invention preferably has an R _a (arithmetic average height) of 0.1 μm or less. If R _a is more than 0.1 [mu] m, the haze value of the film is increased, thereby impairing the transparency. R _a is more preferably 0.07 μm or less. The lower limit is preferably 0.01 μm.

The anti-blocking layered structure of the present invention preferably has R _z JIS of 0.5 μm or less. Here, R _z JIS is a 10-point average roughness of a roughness curve, and is a parameter defined in JIS B0601-2001. R _z JIS is more preferably 0.3 μm or less, and further preferably 0.2 μm or less. The lower limit is preferably 0.01 μm. The antiblocking layered structure of the present invention may contain particles having an average particle diameter of 0.5 μm or less in order to control the uneven shape as an aggregation prevention due to resin precipitation by phase separation. This particle is not for exhibiting anti-blocking properties, and no glare occurs. When the value of R _z JIS (ten-point average roughness) of the anti-blocking layered structure exceeds 0.5 μm, the anti-blocking layered structure is given a cloudiness, haze is increased, and transparency is impaired. This causes a problem such as

When the anti-blocking layered structure of the present invention is transparent, the total light transmittance is 85% or more, preferably 90% or more when expressed by the total light transmittance and haze in order to express the transparency. It 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 is shown in FIG.

  The total light transmittance can be measured using, for example, a haze meter (manufactured by Suga Test Instruments Co., Ltd.).

  ADVANTAGE OF THE INVENTION According to this invention, since the haze is low as above-mentioned, the antiblocking hard coat film which has the outstanding clear performance which does not impair the transparency of a base material can be adjusted.

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 K7105.

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

  The haze can be measured, for example, using a haze meter (manufactured by Suga Test Instruments 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.

Winding roll The antiblocking layered structure of the present invention exhibits an antiblocking function when a plurality of resin base material layers are used. Various forms of the anti-blocking layered structure are conceivable. For example, a roll of a resin base material is conceivable.

  In the case of such a wound roll, a method of winding in a roll shape after applying and curing the anti-blocking curable resin composition of the present invention on the resin substrate layer can be considered.

  The following examples further illustrate the present invention, but the present invention is not limited thereto. Unless otherwise specified, “parts” represents parts by weight.

Preparation Example 1
Preparation of Acrylic Copolymer A mixture consisting of 1263.6 g of isobornyl methacrylate, 18.9 g of methyl methacrylate and 67.5 g of methacrylic acid was mixed. This mixture was dropped at a constant rate over 3 hours in 2430 g of propylene glycol monomethyl ether heated to 110 ° C. in a nitrogen atmosphere in a 5000 ml reaction vessel equipped with a stirring blade, a nitrogen introduction tube, a cooling tube and a dropping funnel. Then, it was made to react at 110 degreeC for 30 minutes.

  A 540 g solution of propylene glycol monomethyl ether containing 67.5 g of tertiary butyl peroxy-2-ethyl hexaate was dropped for 30 minutes to obtain an acrylic copolymer having a number average molecular weight of 2700 and a weight average molecular weight of 5200. This resin had an SP value of 10.2, Tg of 113 ° C.

Preparation Example 2
Preparation of unsaturated double bond-containing acrylic copolymer A mixture of 441.6 g of isobornyl methacrylate, 8.4 g of methyl methacrylate, 120 g of ethylhexyl acrylate, and 30 g of methacrylic acid was mixed. This mixture was added to 1080 g of propylene glycol monomethyl ether heated to 110 ° C. under a nitrogen atmosphere in a 5000 ml reaction vessel equipped with a stirring blade, a nitrogen introduction tube, a cooling tube and a dropping funnel, and then tertiary butyl peroxy-2-ethylhexa. The solution was added dropwise at a constant rate over 3 hours simultaneously with a 240.0 g solution of propylene glycol monomethyl ether containing 6.0 g of ate, and then reacted at 110 ° C. for 1 hour.

  Thereafter, a 51 g solution of propylene glycol monomethyl ether containing 0.6 g of tertiary butyl peroxy-2-ethyl hexaate was added dropwise and reacted at 110 ° C. for 30 minutes.

  To the reaction solution, 6 g of propylene glycol monomethyl ether solution containing 4.5 g of tetrabutylammonium bromide and 0.17 g of hydroquinone was added, and a solution of 51.9 g of glycidyl methacrylate and 15.0 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 6700 and a weight average molecular weight of 15000 was obtained. The SP value of this resin was 9.8 and Tg was 55 ° C.

Preparation Example 3
Preparation of unsaturated double bond-containing acrylic copolymer 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 dropped 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 bond-containing acrylic copolymer having a number average molecular weight of 5,500 and a weight average molecular weight of 18,000 was obtained. This resin had SP value: 9.7 and Tg: 92 ° C.

Preparation Example 4
Preparation of unsaturated double bond-containing acrylic copolymer A mixture consisting of 97.2 g of isobornyl methacrylate, 2.8 g of methyl methacrylate, 90.0 g of ethylhexyl acrylate, 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 dropped 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 17.3 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 4,800 and a weight average molecular weight of 9,200 was obtained. The SP value of this resin was 9.9 and Tg was 2 ° C.

Preparation Example 5
Preparation of unsaturated double bond-containing acrylic copolymer 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. The solution was added dropwise at a constant rate over 3 hours simultaneously with an 80.0 g solution of propylene glycol monomethyl ether containing 20.0 g of ate, 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 17.3 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 1650 and a weight average molecular weight of 2800 was obtained. The SP value of this resin was 10.5 and Tg was 113 ° C.

Example 1
99 parts by weight of pentaerythritol triacrylate (SP value of this monomer: 12.7) which is a polyfunctional unsaturated double bond-containing monomer and the acrylic copolymer of Preparation Example 1 (SP value of this resin: 9.9, Tg) : 113 ° C., Mw = 5200) and 1 part by weight of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photoinitiator and isopropyl alcohol as a solvent And a solution was prepared so that the nonvolatile component ratio was 40% by weight.

This solution was bar-coated on a PET film substrate with a bar coater (No. 8) at 23 ° C., dried at 80 ° C. for 1 minute so that the film thickness was 5 μm, and the solvent was removed and dried. Then, this film was exposed and cured with an ultrahigh pressure mercury lamp so as to have an energy of 400 mJ / cm ² with ultraviolet rays. About the obtained anti-blocking layered structure (base material: PET film substrate and anti-blocking hard coat film), ΔSP value, total light transmittance (%), haze (%), Ra, R _z JIS94, AB property , White unevenness (appearance), hardness and steel wool resistance were evaluated by the methods described below. The results are shown in Table 1. Table 1 also describes the blending amount, SP value, Tg (only the first component) and molecular weight (only the first component) for the first component and the second component. In addition, the types of particles, average particle diameters and blending amounts are also shown in Table 1.

  Moreover, the three-dimensional image by the ultra-deep shape measuring microscope on the film surface which has the fine unevenness | corrugation of the antiblocking layered structure of Example 1 is shown in FIG.

Light transmittance (Tt)
Using a haze meter (manufactured by Suga Test Instruments Co., Ltd.), the incident light intensity (T ₀ ) with respect to the anti-glare film and the total transmitted light intensity (T ₁ ) transmitted through the anti-glare film were measured. The rate (T _t (%)) was calculated.

Ｈ：ヘイズ（曇価）（％）
Ｔ_ｄ：拡散透光率（％）
Ｔ_ｔ：全光線透過率（％） Haze (cloudiness value)
Using a haze meter (manufactured by Suga Test Instruments Co., Ltd.), the diffuse transmittance (T _d (%)) of the antiglare film and the total light transmittance (T _t (%)) were measured, and the haze was calculated.

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

Arithmetic mean height (Ra)
The arithmetic average height (Ra) of the roughness curve of the unevenness on the surface was measured according to JIS-601 using an ultra-deep shape measuring microscope manufactured by Keyence, and an Ra value was obtained.

Ten-point average roughness (R _z JIS)
The ten-point average roughness (R _z JIS) of the unevenness on the surface was measured according to Appendix 1 of JIS-B0601 using a KEYENCE-made ultra-deep shape measuring microscope, and an R _z JIS value was obtained.

AB structure The structure obtained from the above composition was cut into a size of 2 × 5 cm, overlapped on the surface of the PET film (non-adhesive layer uncoated), sandwiched between glass plates at 200 g / cm ² at room temperature, After standing for 24 hours, the blocking phenomenon (AB property) was visually evaluated.

The structure obtained from the above composition was observed from an acute angle (substantially horizontal) direction in a white spot light room, and the cloudiness of the film was visually evaluated.

The hardness was evaluated based on JIS-K5400. (Pencil hardness test)

Steel wool resistance (# 0000) was evaluated 10 times by rubbing steel wool (# 0000) under a load of 500 gf / cm ² , to determine whether scratches would be caused.

Example 2
99.0 parts by weight of a polyfunctional unsaturated double bond-containing monomer pentaerythritol triacrylate (SP value of this monomer: 12.7) and an unsaturated double bond-containing acrylic copolymer of Preparation Example 2 (of this resin) 1 part by weight of SP value: 9.8, Tg: 55 ° C., Mw = 15000) and 2-methyl-1 (4- (methylthio) phenyl) -2-morpholinopropan-1-one as a photoinitiator 7 A solution was prepared by mixing parts by weight with isopropyl alcohol as a solvent so that the nonvolatile component ratio was 40% by weight.

This solution was bar-coated on a PET film substrate with a bar coater (No. 8) at 23 ° C., dried at 80 ° C. for 1 minute so that the film thickness was 5 μm, and the solvent was removed and dried. Then, this film was exposed and cured with an ultrahigh pressure mercury lamp so as to have an energy of 400 mJ / cm ² with ultraviolet rays.

  Evaluation similar to Example 1 was performed and the results are shown in Table 1.

Example 3
99 parts by weight of a polyfunctional unsaturated double bond-containing monomer pentaerythritol triacrylate (SP value of this monomer: 12.7) and an unsaturated double bond-containing acrylic copolymer of Preparation Example 3 (SP value of this resin) : 9.7, Tg: 92 ° C., Mw = 18000) and 7 parts by weight of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photoinitiator Was mixed with methyl isobutyl ketone as a solvent to prepare a solution such that the nonvolatile component ratio was 50% by weight.

This solution was bar-coated on a PET film substrate with a bar coater (No. 8) at 23 ° C., dried at 80 ° C. for 1 minute so that the film thickness was 5 μm, and the solvent was removed and dried. Then, this film was exposed and cured with an ultrahigh pressure mercury lamp so as to have an energy of 400 mJ / cm ² with ultraviolet rays.

  Evaluation similar to Example 1 was performed and the results are shown in Table 1.

Example 4
98.5 parts by weight of a polyfunctional unsaturated double bond-containing monomer pentaerythritol triacrylate (SP value of this monomer: 12.7) and an unsaturated double bond-containing acrylic copolymer of Preparation Example 3 (of this resin) SP value: 9.7, Tg: 92 ° C., Mw = 18000) and 1.5 parts by weight of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1- photoinitiator 7 parts by weight of ON was mixed with methyl isobutyl ketone as a solvent to prepare a solution so that the nonvolatile component ratio was 50% by weight.

This solution was bar-coated on a PET film substrate with a bar coater (No. 8) at 23 ° C., dried at 80 ° C. for 1 minute so that the film thickness was 5 μm, and the solvent was removed and dried. Then, this film was exposed and cured with an ultrahigh pressure mercury lamp so as to have an energy of 400 mJ / cm ² with ultraviolet rays.

  Evaluation similar to Example 1 was performed and the results are shown in Table 1. Moreover, the three-dimensional image by the ultra-deep shape measuring microscope on the coating surface which has the fine unevenness | corrugation of the antiblocking layered structure of Example 4 is shown in FIG.

Example 5
98.5 parts by weight of a polyfunctional unsaturated double bond-containing monomer pentaerythritol triacrylate (SP value of this monomer: 12.7) and an unsaturated double bond-containing acrylic copolymer of Preparation Example 3 (of this resin) SP value: 9.7, Tg: 92 ° C., Mw = 18000) and 1.5 parts by weight of organosilica sol (MIBK-ST: particle diameter 20 nm, manufactured by Nissan Chemical Industries, Ltd.) and a photoinitiator. A solution in which 7 parts by weight of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one is mixed with methyl isobutyl ketone as a solvent so that the nonvolatile component ratio is 50% by weight. Was made.

This solution was bar-coated on a PET film substrate with a bar coater (No. 8) at 23 ° C., dried at 80 ° C. for 1 minute so that the film thickness was 5 μm, and the solvent was removed and dried. Then, this film was exposed and cured with an ultrahigh pressure mercury lamp so as to have an energy of 400 mJ / cm ² with ultraviolet rays.

  Evaluation similar to Example 1 was performed and the results are shown in Table 1. Moreover, the three-dimensional image by the ultra-deep shape measuring microscope on the coating surface which has the fine unevenness | corrugation of the antiblocking layered structure of Example 5 is shown in FIG.

Example 6
98.5 parts by weight of a polyfunctional unsaturated double bond-containing monomer pentaerythritol triacrylate (SP value of this monomer: 12.7) and an unsaturated double bond-containing acrylic copolymer of Preparation Example 3 (of this resin) 1.5 parts by weight of SP value: 9.7, Tg: 92 ° C., Mw = 18000) and 10 parts by weight of silica particles (nip seal E-220A: particle diameter 1.5 μm, manufactured by Nippon Silica Industry Co., Ltd.) 7 parts by weight of 2-methyl-1 (4- (methylthio) phenyl) -2-morpholinopropan-1-one as an agent is mixed with methyl isobutyl ketone as a solvent, and the non-volatile component ratio becomes 50% by weight. A solution was prepared as follows.

This solution was bar-coated on a PET film substrate with a bar coater (No. 8) at 23 ° C., dried at 80 ° C. for 1 minute so that the film thickness was 5 μm, and the solvent was removed and dried. Then, this film was exposed and cured with an ultrahigh pressure mercury lamp so as to have an energy of 400 mJ / cm ² with ultraviolet rays.

  The same evaluation as in Example 1 was performed, and the results are shown in Table 2.

Example 7
98.5 parts by weight of a polyfunctional unsaturated double bond-containing monomer pentaerythritol triacrylate (SP value of this monomer: 12.7) and an unsaturated double bond-containing acrylic copolymer of Preparation Example 4 (of this resin) SP value: 9.9, Tg: 2 ° C., Mw = 9200) and 1.5 parts by weight of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1- photoinitiator 7 parts by weight of ON was mixed with methyl isobutyl ketone as a solvent to prepare a solution so that the nonvolatile component ratio was 50% by weight.

This solution was bar-coated on a PET film substrate with a bar coater (No. 8) at 23 ° C., dried at 80 ° C. for 1 minute so that the film thickness was 5 μm, and the solvent was removed and dried. Then, this film was exposed and cured with an ultrahigh pressure mercury lamp so as to have an energy of 400 mJ / cm ² with ultraviolet rays.

  The same evaluation as in Example 1 was performed, and the results are shown in Table 2.

Example 8
98.5 parts by weight of a polyfunctional unsaturated double bond-containing monomer pentaerythritol triacrylate (SP value of this monomer: 12.7) and the unsaturated double bond-containing acrylic copolymer of Preparation Example 5 (of this resin) SP value: 10.5, Tg: 113 ° C., Mw = 2800) and 1.5 parts by weight of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1- photoinitiator 7 parts by weight of ON was mixed with methyl isobutyl ketone as a solvent to prepare a solution so that the nonvolatile component ratio was 50% by weight.

This solution was bar-coated on a PET film substrate with a bar coater (No. 8) at 23 ° C., dried at 80 ° C. for 1 minute so that the film thickness was 5 μm, and the solvent was removed and dried. Then, this film was exposed and cured with an ultrahigh pressure mercury lamp so as to have an energy of 400 mJ / cm ² with ultraviolet rays.

  The same evaluation as in Example 1 was performed, and the results are shown in Table 2.

Comparative Example 1
100 parts by weight of pentaerythritol triacrylate (SP value: 12.7 of this monomer) which is a polyfunctional unsaturated double bond-containing monomer and 2-methyl-1 [4- (methylthio) phenyl] -2 which is a photoinitiator -7 parts by weight of morpholinopropan-1-one was mixed with methyl isobutyl ketone as a solvent to prepare a solution having a nonvolatile component ratio of 50% by weight.

This solution was bar-coated on a PET film substrate with a bar coater (No. 8) at 23 ° C., dried at 80 ° C. for 1 minute so that the film thickness was 5 μm, and the solvent was removed and dried. Then, this film was exposed and cured with an ultrahigh pressure mercury lamp so as to have an energy of 400 mJ / cm ² with ultraviolet rays.

  The same evaluation as in Example 1 was performed, and the results are shown in Table 2.

Comparative Example 2
100 parts by weight of pentaerythritol triacrylate (SP value of this monomer: 12.7), which is a polyfunctional unsaturated double bond-containing monomer, and 10 weights of organosilica sol (MIBK-ST: particle size 20 nm, manufactured by Nissan Chemical Industries, Ltd.) And 7 parts by weight of 2-methyl-1 (4- (methylthio) phenyl) -2-morpholinopropan-1-one as a photoinitiator are mixed with methyl isobutyl ketone as a solvent, and the non-volatile component ratio is 50 A solution was prepared so as to have a weight%.

This solution was bar-coated on a PET film substrate with a bar coater (No. 8) at 23 ° C., dried at 80 ° C. for 1 minute so that the film thickness was 5 μm, and the solvent was removed and dried. Then, this film was exposed and cured with an ultrahigh pressure mercury lamp so as to have an energy of 400 mJ / cm ² with ultraviolet rays.

  The same evaluation as in Example 1 was performed, and the results are shown in Table 2.

  As is clear from the above Examples and Comparative Examples, layered structures having high antiblocking properties are obtained in Examples 1-8. In the method for forming irregularities by phase separation using the resin (first component) described in the present invention, when Examples 4 and 5 are compared, the irregularities formed in the presence of particles (Example 5) are more irregular. By controlling the structure, it is possible to obtain a clear anti-blocking structure with no cloudiness.

1 is a schematic cross-sectional view of an antiblocking layered structure of the present invention. It is explanatory drawing of parameter _RzJIS . It is a schematic explanatory drawing of a total light transmittance. It is a three-dimensional image by the ultra-deep shape measuring microscope on the coating surface which has the fine unevenness | corrugation of the antiblocking layered structure of Example 1. FIG. It is a three-dimensional image by the ultra-deep shape measuring microscope on the coating surface which has the fine unevenness | corrugation of the antiblocking layered structure of Example 4. FIG. It is a three-dimensional image by the ultra-deep shape measuring microscope on the coating surface which has the fine unevenness | corrugation of the antiblocking layered structure of Example 5. FIG.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Anti blocking layered structure, 3 ... Film which has fine unevenness, 5 ... Resin base material layer.

Claims (13)

  A curable resin composition comprising a first component comprising at least one resin and a second component selected from the group consisting of at least one monomer or oligomer, wherein the first component after application of the composition Anti-blocking curable resin composition in which the resin is precipitated by phase separation and forms fine irregularities on the surface.   The antiblocking curable resin composition according to claim 1, wherein the first component and the second component both contain a (meth) acryloyl group.   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 according to any one of claims 1 to 3, wherein a difference between the SP value of the first component and the SP value of the second component is 1.0 or more.   The antiblocking curable resin composition according to claim 1, wherein the resin of the first component has a glass transition temperature (Tg) of 2 ° C or higher and a weight average molecular weight of 2000 or higher.   The antiblocking curable resin composition according to claim 3, wherein the inorganic particles or the organic particles have an average particle diameter of 0.5 μm or less.   The antiblocking curable resin composition according to claim 1, wherein the antiblocking resin composition is photocurable.   An anti-blocking hard coat film obtained by curing the anti-blocking curable resin composition according to any one of claims 1 to 7, wherein the film has a total light transmittance of 90% or more, An anti-blocking hard coat film having a clear performance having a haze of 2.0% or less. The antiblocking hard coat film according to claim 8, wherein the surface of the hard coat film is R _a (arithmetic average height) of 0.1 µm or less and R _z JIS (ten-point average roughness) of 0.3 µm or less.   The antiblocking layered structure which apply | coated and hardened | cured the antiblocking curable resin composition in any one of Claims 1-7 on a base material.   The antiblocking layered structure winding roll which apply | coated the antiblocking curable resin composition in any one of Claims 1-7 on a base material, and wound the cured antiblocking layered structure on a roll .   The manufacturing method of the antiblocking layered structure obtained by apply | coating the antiblocking curable resin composition in any one of Claims 1-7 on a base material, making it dry and phase-separating, and hardening after that. The manufacturing method according to claim 12, wherein the phase separation and curing are performed by irradiating light.

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