JP2009013384A - Easily slipable anti-blocking photocurable resin composition, anti-blocking structure with the same coated and cured on base material, and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technology that can improve slippability in a film and a layered structure thereof, capable of preventing a problem such as adhesion between layered bodies such as a thermoplastic film, that is, a blocking phenomenon. <P>SOLUTION: The anti-blocking curable resin composition contains first and second components and a silicone compound, wherein the first component includes at least one or more resins, the second component includes one or more selected from the group consisting of one or more monomers or oligomers, and the composition is applied, followed by precipitation of the resin of the first component by phase separation, to form minute irregularities on a surface. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a curable resin composition having anti-blocking properties, a hard coat film, a layered structure, and methods for producing them.

  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 a particulate matter of about 1 μm on the opposite surface of the substrate that is not hard-coated, and the surface is uneven. In some cases, adhesion between the layered bodies may be prevented by reducing the contact area between the layers. For example, Japanese Unexamined Patent Application Publication No. 2004-151937 (Patent Document 1) and Japanese Unexamined Patent Application Publication No. 2005-132897 (Patent Document 2) disclose a technique in which a back coat containing particulate matter is formed.

  The above-described technique for preventing adhesion between layered bodies due to the use of the 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.

  The present inventors have already provided a curable resin composition having an anti-blocking property that can be used for a hard coat film (Japanese Patent Application No. 2006-002480). In the technique of this patent application, fine unevenness is naturally generated on the surface by phase separation when the resin composition is cured, and blocking can be prevented. Although the technique of this patent application has solved the problem of manufacturing a hard coat film, when this hard coat film is used on the surface of a touch panel, especially in the case of a so-called pen touch panel that touches with a pen, surface slippage is caused. Sex is required. In particular, since the nib is often a polyacetal, a highly slippery polyacetal is required. Such performance cannot be achieved by the technology of the previous patent application. Therefore, it has been desired to study a curable resin composition having anti-blocking property with high slipperiness with respect to polyacetal obtained by improving the technique of the above application.

JP 2004-151937 A JP 2005-132897 A JP 2004-042653 A Japanese Patent Application No. 2006-002480

  An object of the present invention is to provide a film capable of preventing defects such as adhesion between layered bodies such as a thermoplastic film, that is, a blocking phenomenon, and a technique capable of improving slipperiness in the layered structure. .

  As a result of intensive studies, the present inventors have found that a curable resin composition comprising a first component comprising at least one or more resins and a second component selected from the group consisting of one or more monomers or oligomers (Japanese Patent Application No. 2006-2006). No. 002480), by adding (compounding) a silicone compound, after application of the composition, the first component resin is precipitated by phase separation, and anti-blocking is formed by forming fine irregularities on the surface of the resulting film. It was found that the slipperiness can be improved in the formed film and the layered structure. Accordingly, the present invention provides the following.

An antiblocking curable resin composition comprising a first component, a second component and a silicone compound,
The first component is made of at least one resin,
The second component comprises one or more selected from the group consisting of one or more monomers or oligomers;
An antiblocking curable resin composition in which the resin of the first component is precipitated by phase separation after application of the composition and forms fine irregularities on the surface.

  Said antiblocking curable resin composition whose said silicone type compound is a reactive silicone compound containing a (meth) acryloyl group.

  Said antiblocking curable resin composition whose content of the said silicone type compound is 0.01-10 weight part with respect to 100 weight part of total amounts of a said 1st component and a 2nd component.

  The anti-blocking curable resin composition as described above, wherein the curable resin composition further contains at least one kind of inorganic particles and / or organic particles.

  Said antiblocking curable resin composition 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 as described above, 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.

  Said antiblocking curable resin composition which is photocurable.

  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 2.0% or less. Anti-blocking hard coat film with clear performance.

  An anti-blocking layered structure obtained by applying the above-described anti-blocking curable resin composition onto a substrate and curing it.

  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 manufacturing method of the antiblocking layered structure obtained by apply | coating said antiblocking curable resin composition on a base material, making it dry and phase-separating, and hardening after that.

  Said manufacturing method with which said phase separation and hardening are 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 reduces the surface friction coefficient of the film to be formed and its layered structure by adding a silicone compound to the above curable resin composition with the above-described anti-blocking property as an essential performance. be able to. That is, slipperiness can be added.

The present invention will be described in more detail with reference to the accompanying 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.
FIGS. 4-6 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 this invention.

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. 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 one or more selected from the group consisting of one or more monomers or oligomers.

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. An unsaturated double bond-containing acrylic copolymer introduces a reactive group (for example, an epoxy group, a hydroxyl group, a carboxyl group, etc.) into the acrylic copolymer that serves as a basic skeleton, and the reactive group is converted into an unsaturated diazo group. A compound having a heavy bond and having a functional group corresponding to a reactive group (hydroxyl group or carboxyl group for epoxy group, epoxy group or isocyanate group for hydroxyl group, hydroxyl group or epoxy group for carboxyl group) Formed by reacting with. Introduction of an epoxy group into the acrylic copolymer is performed by reacting an acrylic monomer with glycidyl methacrylate. Introducing a hydroxyl group is performed by reacting an acrylic monomer with a hydroxyl group-containing monomer (for example, 2-hydroxylethyl methacrylate). The introduction of a carboxyl group is performed by reacting an acrylic monomer with acrylic acid or methacrylic acid. An acrylic copolymer having a reactive group is a monomer having a functional group corresponding to the reactive group (for example, 2-hydroxyethyl methacrylate for an epoxy group, glycidyl methacrylate or isocyanatoethyl (meth) acrylate for a hydroxyl group). The carboxyl group is reacted with glycidyl (meth) acrylate to introduce a double bond group, and these unsaturated double bond-containing acrylic copolymers may be used alone or in combination of two kinds. You may mix and use the above.

  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.

Second component The second component comprises one or more selected from the group consisting of one or more monomers or oligomers, and the monomer is a polyfunctional monomer such as a polyhydric alcohol and a (meth) acrylate. Alcohol reactants, specifically pentaerythritol triacrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Neopentyl glycol di (meth) acrylate or 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. These polyfunctional monomers may be used individually by 1 type, and 2 or more types may be mixed and used for them. As the oligomer, urethane (meth) acrylate oligomer, polyester (meth) acrylate oligomer and low molecular weight products of the resins 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.

Silicone compound The silicone compound used in the present invention can be used without particular limitation as long as it is a compound having a siloxane (Si-O) bond, and examples thereof include a non-reactive silicone compound and a reactive silicone compound.

Non-reactive silicone compounds generally have the formula:
_{R 1 - ((R 3)} (R 4) SiO) n -R 2
[Where:
R ₁ , R ₂ , R ₃ and R _{4 each} independently represent an alkyl group having 1 to 25 carbon atoms or an alkoxy group having 1 to 25 carbon atoms, and may be the same or different from each other. ,
n is an integer from 1 to 150]
It is a compound represented by these.

Reactive silicone compounds have at least one polymerizable group or functional group and generally have the formula:
R ₅ -((R ₇ ) (R ₈ ) SiO) _m -R ₆
[Where:
R ₅ , R ₆ , R ₇ and R ₈ independently represent a polymerizable group, a functional group, an alkyl group having 1 to 25 carbon atoms, or an alkoxy group having 1 to 25 carbon atoms, and are each the same _May be different, but at least one of R ₅ , R ₆ , R ₇ and R ₈ is a polymerizable group or functional group,
m is an integer from 1 to 150]
As the polymerizable group, the (meth) acryloyl group, the (meth) acryloyloxy group, the vinyl group, and the functional group include an amino group, a hydroxyl group, an epoxy group, a mercapto group, and the like. A polymerizable group is preferable, and a (meth) acryloyl group is particularly preferable.

  The number average molecular weight (Mn) of the silicone compound is 100 to 10000, preferably 1000 to 5000.

  As the silicone compound, a reactive silicone compound is preferable because it is incorporated into the matrix and stabilized, and a reactive silicone compound containing a (meth) acryloyl group is particularly preferable.

  Moreover, you may use a commercial item as a silicone type compound, for example, BYK (trademark) -306,307,310,330 (The Big Chemie Japan Co., Ltd. make, polyether modified polydimethylsiloxane), BYK (registration). Trademarks) -UV3500, UV3510 (manufactured by Big Chemie Japan Co., Ltd., polyether-modified acrylic group-containing polydimethylsiloxane), TEGO (registered trademark) RAD 2100, 2200N, 2250, 2600, 2700 (Tegochem Service Co., Ltd.) Silicone), Silaplane (registered trademark) (reactive silicone manufactured by Chisso Corporation), for example, FM-7711, FM-7721, FM-7725, FM-0711, FM-0721, FM-0725, TM-0701, TM-0701T etc. are mentioned, It is not limited to these.

  The content of the silicone compound contained in the composition of the present invention is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of the first component and the second component. is there. When the content is less than 0.01 part by weight, the coefficient of friction of the formed film cannot be reduced, and there is a possibility that the film cannot be provided with slipperiness. Moreover, when content exceeds 10 weight part, although slip property can be provided to the film formed, there exists a possibility that physical properties, such as the hard-coat property of a film, may fall.

  In the present invention, by adding a silicone compound, the static friction coefficient of a film that can be formed from the antiblocking curable resin composition can be reduced, and slipperiness can be imparted to the film. In the present specification, the static friction coefficient and the slip property of the film will be described in detail in the description of the anti-blocking layered structure below.

  The first component resin has a weight average molecular weight of 2,000 or more, preferably 2,000 to 100,000, more preferably 5,000 to 50,000.

  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. By phase separation, the resin of the first component can be precipitated.

  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.

  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 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 and / or 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 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 resin substrate layer and a coating (hard coat 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 Polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyether ketone film, (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 appropriately selected according to the anti-blocking curable resin composition and the state of the coating process, for example, dip coating method, air knife coating method, curtain coating method. It can be applied 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. Further, 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. 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 not more than 0.07 .mu.m. 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, the haze value is increased, and the transparency is impaired. This causes problems 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.).

  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 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.

  Moreover, the anti-blocking hard coat film of the present invention and the layered structure thereof have improved surface slipperiness due to the polymerizable silicone contained in the second component.

  The sliding property of the film can be evaluated by, for example, the static friction coefficient (μ) of the film surface. The static friction coefficient is, for example, a portable friction meter (Haydon Tribogear) Type: 94i-2 (Shinto Kagaku Co., Ltd.). It is possible to measure with a tribometer.

  The static friction coefficient (μ) of the film surface is larger than 0 and not larger than 0.3, preferably not larger than 0.25, more preferably not larger than 0.2. When the coefficient of static friction is 0.3 or less, excellent slipperiness that cannot be obtained with a conventional film can be obtained.

  The hard coat film and the layered structure of the present invention having excellent sliding properties can be effectively applied to applications such as a touch panel. As the operation of the touch panel, in addition to the operation with the finger, the operation with the pen using polyacetal as the pen tip is generally used. However, the conventional technique has a problem that the pen tip is caught on the film. However, by using the present invention, slipperiness is greatly improved and the above-mentioned problems of the prior art can be solved.

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 is conceivable in which the anti-blocking curable resin composition of the present invention is applied and cured on a resin base layer and then wound into a roll.

  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 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 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 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 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
1 part by weight of the acrylic copolymer of Preparation Example 1 (SP value of this resin: 10.2, Tg: 113 ° C., weight average molecular weight Mw = 5200) as the first component, and Aronix M305 (Toagosei Co., Ltd.) as the second component 99 parts by weight of pentaerythritol triacrylate manufactured by Co., Ltd., SP value: 12.7) and 0.1% FM-7711 (reactive silicone manufactured by Chisso Co., Ltd., number average molecular weight Mn = 1000) as a silicone compound. Part by weight, 7 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photoinitiator is mixed with isopropyl alcohol as a solvent, and the non-volatile component ratio is determined. A solution was prepared so as to be 40% by weight.

This solution was applied to a PET film substrate (100 μm) at 23 ° C. with a bar coater (No. 10), dried at 80 ° C. for 1 minute so that the film thickness was 5 μm, and the solvent was removed and dried. Thereafter, the film was cured by exposing to ultraviolet rays (350 nm) with an ultrahigh pressure mercury lamp so as to have an energy of 300 mJ / cm ² . About the obtained anti-blocking layered structure (base material: PET film substrate and anti-blocking hard coat film), ΔSP value, total light transmittance (%), haze (%), static friction coefficient (μ), Ra , R _z JIS94, AB (anti-blocking) property, slip property, 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 type, number average molecular weight, and blending amount (blending amount with respect to the total amount of the first component and the second component) of the silicone compound are described as other components. The amounts are listed 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.

Total light transmittance (Tt)
Using a haze meter (manufactured by Suga Test Instruments Co., Ltd.), the incident light intensity (T ₀ ) with respect to the film and the total transmitted light intensity (T ₁ ) transmitted through the film were measured, and the total light transmittance (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., HGM-3DP), the diffuse light transmittance (T _d (%)) and the total light transmittance (T _t (%)) of the film are measured, and the haze is calculated. did.

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 applied), 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.
○: Anti-blocking property ×: No anti-blocking property

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.

Slip (measurement of coefficient of static friction)
Using a portable friction meter (Haydon Tribogear) Type: 94i-2 (manufactured by Shinto Kagaku Co., Ltd.) as a slipperiness, the coefficient of static friction (μ) between the contact of the friction meter and the film coating surface Was measured.
○: Slip property (Static friction coefficient: 0.3 or less)
×: No slipperiness (Coefficient of static friction: 0.4 or more)

Examples 2-9
Similarly to Example 1, anti-blocking layered structures of Examples 2 to 9 were prepared, and the same evaluation as in Example 1 was performed. The results are shown in Tables 1 and 2. In Examples 2 to 9, the acrylic copolymer used in Example 1 was changed to the one shown in the table, and the monomers and silicone compounds used were the same as those in Example 1, and Example 5 and In Example 9, the following silica particles were used, and in Example 6, the following acrylic particles were used.

Comparative Example Similarly to Example 1, anti-blocking layered structures of Comparative Examples 1 to 3 were prepared, evaluated in the same manner as Example 1, and the results are shown in Table 3. In Comparative Example 1, the unsaturated double bond-containing acrylic copolymer of Preparation Example 3 was used as the first component, the same component as in Example 1 was used as the second component, and the silicone compound was used. In Comparative Example 2 and Comparative Example 3, the first component is not used.

＊１：ＦＭ−７７１１（チッソ（株）製反応性シリコーン）
＊２：アクリル系マイクロゲル（日本ペイント社製メチルメタクリレートとエチレングリコールジメタクリレートとから合成したもの）
＊３：オルガノシリカゾル（ＭＩＢＫ−ＳＴ：粒子径２０ｎｍ、日産化学工業株式会社製）

* 1: FM-7711 (reactive silicone manufactured by Chisso Corporation)
* 2: Acrylic microgel (synthesized from Nippon Paint's methyl methacrylate and ethylene glycol dimethacrylate)
* 3: Organosilica sol (MIBK-ST: particle size 20 nm, manufactured by Nissan Chemical Industries, Ltd.)

  The anti-blocking layered structure of the present invention containing the first component, the second component, and the silicone compound (Examples 1 to 9) is excellent in anti-blocking property and has excellent sliding properties, whereas it is silicone-based. In Comparative Example 1 containing no compound, anti-blocking properties can be obtained, but slip properties cannot be obtained. In Comparative Examples 2 and 3, which contain a silicone compound but do not contain the first component, the antiblocking property cannot be obtained although the slip property is obtained. Therefore, in the present invention, by adding a silicone compound to the first component and the second component, it was possible to further impart slip properties while maintaining high antiblocking properties.

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 (12)

An antiblocking curable resin composition comprising a first component, a second component and a silicone compound,
The first component is made of at least one resin,
The second component comprises one or more selected from the group consisting of one or more monomers or oligomers;
An antiblocking curable resin composition in which the resin of the first component is precipitated by phase separation after application of the composition and forms fine irregularities on the surface.   The antiblocking curable resin composition of Claim 1 whose said silicone type compound is a reactive silicone compound containing a (meth) acryloyl group.   The antiblocking curable resin composition of Claim 1 whose content of the said silicone type compound is 0.01-10 weight part with respect to 100 weight part of total amounts of a said 1st component and a 2nd component.   The anti-blocking curable resin composition according to any one of claims 1 to 3, wherein the curable resin composition further contains at least one kind of inorganic particles and / or organic particles.   The antiblocking curable resin composition according to any one of claims 1 to 4, 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 any one of claims 1 to 5, 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 any one of claims 1 to 6, which is photocurable.   It is an antiblocking hard coat film obtained by hardening | curing the antiblocking curable resin composition of any one of Claims 1-7 in a film form, Comprising: This film has a total light transmittance of 90. % Anti-blocking hard coat film having a clear performance with a haze of 2.0% or less.   An antiblocking layered structure obtained by applying the antiblocking curable resin composition according to any one of claims 1 to 7 on a substrate and curing the composition.   An antiblocking layered structure obtained by applying the antiblocking curable resin composition according to any one of claims 1 to 7 on a substrate and winding the cured antiblocking layered structure on a roll. Winding roll.   An antiblocking layered structure obtained by applying the antiblocking curable resin composition according to any one of claims 1 to 7 on a substrate, drying and phase-separating, and then curing. Production method.   The manufacturing method of Claim 11 with which the said phase separation and hardening are performed by irradiating light.

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