JP3998697B2 - Antiglare coating composition, antiglare film and method for producing the same - Google Patents

Antiglare coating composition, antiglare film and method for producing the same Download PDF

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JP3998697B2
JP3998697B2 JP2005517515A JP2005517515A JP3998697B2 JP 3998697 B2 JP3998697 B2 JP 3998697B2 JP 2005517515 A JP2005517515 A JP 2005517515A JP 2005517515 A JP2005517515 A JP 2005517515A JP 3998697 B2 JP3998697 B2 JP 3998697B2
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antiglare
film
coating composition
sp
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JPWO2005073763A1 (en
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浩正 南野
雅史 大畑
靖二 山道
圭一 岡島
晃 松村
寛之 橋口
和幸 菅
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日本ペイント株式会社
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/0427Coating with only one layer of a composition containing a polymer binder
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0205Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0221Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having an irregular structure
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0268Diffusing elements; Afocal elements characterized by the fabrication or manufacturing method
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0273Diffusing elements; Afocal elements characterized by the use
    • G02B5/0278Diffusing elements; Afocal elements characterized by the use used in transmission
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0273Diffusing elements; Afocal elements characterized by the use
    • G02B5/0294Diffusing elements; Afocal elements characterized by the use adapted to provide an additional optical effect, e.g. anti-reflection or filter
    • GPHYSICS
    • G02OPTICS
    • G02FDEVICES OR ARRANGEMENTS, THE OPTICAL OPERATION OF WHICH IS MODIFIED BY CHANGING THE OPTICAL PROPERTIES OF THE MEDIUM OF THE DEVICES OR ARRANGEMENTS FOR THE CONTROL OF THE INTENSITY, COLOUR, PHASE, POLARISATION OR DIRECTION OF LIGHT, e.g. SWITCHING, GATING, MODULATING OR DEMODULATING; TECHNIQUES OR PROCEDURES FOR THE OPERATION THEREOF; FREQUENCY-CHANGING; NON-LINEAR OPTICS; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating, or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating, or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating, or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133504Diffusing, scattering, diffracting elements

Description

  The present invention is formed from an antiglare coating composition capable of imparting antiglare properties to transparent substrates such as various transparent plastic films, transparent plastic plates and glass, and the antiglare coating composition. The present invention relates to an antiglare film having an antiglare layer.

  Liquid crystal display devices (liquid crystal displays) have advantages such as thinness, light weight, and low power consumption, and are used in various fields such as computers, word processors, televisions, mobile phones, and portable information terminal devices. In these liquid crystal display devices, an anti-glare (AG) film that roughens the surface, a low reflection (LR) film that adjusts the refractive index, and a non-reflective film (AR). Anti Reflection) and the like are provided. As a result, problems such as a decrease in contrast due to reflection of external light and reflection of the background reflected on the display surface are solved.

  As a method for producing an antiglare film for improving the display performance of a liquid crystal display device, in general, a method of roughening the surface by processing such as cutting, embossing molding, bonding or the like at the time of film production, or including resin particles And a method of roughening the surface of the film by providing a layer on the film. Currently, the latter method of providing a layer containing resin particles on a film is widely used.

  Japanese Patent Application Laid-Open No. 2002-221610 (Patent Document 1) discloses an antiglare film in which an antiglare layer including a translucent resin and a translucent fine particle is laminated, the translucent resin and the translucent fine particle. The difference between the refractive index and the antiglare film is 0.3 or less and the translucent resin protrudes from the surface of the antiglare layer by 0.1 to 0.3 μm. In the production of such an antiglare film, for example, there is a problem that the fine particles used are not uniformly dispersed. In order to uniformly disperse the resin in the solution, it is necessary to take care such as controlling and adjusting the solution viscosity. If the fine particles are aggregated without being uniformly dispersed, the uneven shape on the surface may be out of the desired range, resulting in problems such as reduced transmitted image clarity and so-called white blurring.

  On the other hand, when the surface is roughened by processing such as cutting, embossing, and bonding at the time of film production, it is difficult to provide irregularities on the rough surface at random, and the irregularities may be followed. is there. When the irregularity is followed, the light reflected by the irregular surface may interfere with each other, causing a problem in display display such as an increase in reflected light or a moire pattern. That is, the occurrence of the moire pattern is caused by the arrangement direction of the fine concavo-convex structure of the antiglare layer overlapping the arrangement direction of the pixels of the display device. This tends to occur when the fine concavo-convex structure is positioned so as to overlap the rule, while the pixels are regularly arranged. Further, when the antiglare layer is formed by stamping, a step of pressing the antiglare layer and a step of cleaning the mold used for the stamping are necessary, which is complicated. Furthermore, it is necessary to pay attention so that foreign matter does not adhere to the molding surface of the mold used for embossing.

  Japanese Patent Laid-Open No. 2003-004917 (Patent Document 2) discloses a polarizing plate with an antiglare layer comprising an antiglare film and a polarizer, wherein the arrangement direction of the fine uneven structure of the antiglare layer is that of the polarizer. A polarizing plate with an antiglare layer, which is 22.5 ° ± 12.5 ° with respect to the absorption axis direction or the transmission axis direction, is described. As described herein, in the case of providing a fine concavo-convex structure by processing, it is necessary to finely adjust the angle in the arrangement direction and the manufacturing process becomes complicated. In addition, it is considered that the probability of the occurrence of a moire pattern increases as the pixels of the display element become smaller due to the higher definition and colorization of the display screen. Therefore, a technology for solving this problem is required.

  Japanese Patent Laid-Open No. 2000-267086 (Patent Document 3) discloses a method of manufacturing an electrode substrate for a reflective liquid crystal display device, which includes a step of applying a mixed resin liquid in which a plurality of types of resins that are easily phase separated from each other are applied. Are listed. Japanese Patent Laid-Open No. 2001-305316 (Patent Document 4) describes a reflector having a resin layer in which irregularities are formed by a configuration in which at least two types of resin portions are dispersedly held. However, since these substrates or reflectors reflect reflections of the background on the display surface, and do not need to consider performance such as transmitted image clarity and blurring at all, these performances are regarded as important. The problem to be solved is different from the antiglare film.

JP 2002-221610 A JP 2003-004917 A JP 2000-267086 A JP 2001-305316 A

  An object of the present invention is to solve the above-described problems of the prior art. More specifically, an object of the present invention is to provide an antiglare coating composition that can easily form an antiglare film with improved reflection, white blurring, and the like.

The present invention is an antiglare coating composition that is applied on a transparent substrate to form an antiglare layer,
The antiglare coating composition includes a first component and a second component,
After applying the antiglare coating composition on the substrate, the first component and the second component are phase-separated based on the difference in physical properties of the first component and the second component, and random irregularities are formed on the surface. A resin layer is formed,
An antiglare coating composition is provided, whereby the above object is achieved.

  Preferably, the first component and the second component are each independently one or a combination of two or more selected from the group consisting of monomers, oligomers and resins.

  Moreover, it is preferable that the difference between the SP value of the first component and the SP value of the second component is 0.5 or more.

The antiglare coating composition of the present invention may further contain an organic solvent. The SP value (SP 1 ) of the first component, the SP value (SP 2 ) of the second component, and the SP value (SP sol ) of the organic solvent are as follows :
SP 1 <SP 2 and the difference between SP 1 and SP sol is 2 or less;
It is preferable that the relationship is satisfied.

  Preferably, the first component is an oligomer or a resin, and the second component is a monomer.

  The first component is preferably an unsaturated double bond-containing acrylic copolymer, and the second component is preferably a polyfunctional unsaturated double bond-containing monomer.

  It is also preferred that the first component is a silicone acrylic block copolymer and the second component is an acrylic copolymer.

  In the antiglare coating composition of the present invention, the first component and the second component are resins, and any one of the first component and the second component has a Tg lower than the environmental temperature at the time of coating the composition. It is also preferable that the other has a Tg higher than the environmental temperature at the time of coating the composition.

In the antiglare coating composition of the present invention, either the first component or the second component is a monomer,
It is also preferable that the difference in Tg between the first component and the second component is 20 ° C. or higher, and that the Tg of the component having a higher Tg in the first component and the second component is 20 ° C. or higher.

  The antiglare coating composition of the present invention may further contain a curing agent.

  Further, the antiglare coating composition of the present invention is preferably characterized by not containing resin particles.

  The present invention also provides an antiglare film. This antiglare film has a transparent substrate and an antiglare layer, and this antiglare layer is formed from the above antiglare coating composition.

  The haze of the antiglare film is preferably less than 20%.

Moreover, it is preferable that RzJIS94 (10-point average roughness) of an anti-glare film is 1.0 micrometer or less.

  Furthermore, the average length (Sm) of the roughness curve element on the surface of the antiglare film is preferably 100 μm or less.

  Furthermore, it is preferable that the scattered light intensity with respect to the scattering angle of the antiglare film does not have a maximum value.

The present invention also provides a method for producing an antiglare film. As an example of the manufacturing method, the following steps:
An application step of applying the antiglare coating composition to the transparent substrate, and a curing step of curing the obtained coating film;
The method of including is mentioned.

As another example of the manufacturing method,
Application step of applying the above antiglare coating composition to a transparent substrate,
A drying step for drying and phase-separating the obtained coating film, and a curing step for curing the dried coating film,
The method of including is also mentioned.

Furthermore, as another example of the manufacturing method,
An application step of applying the above antiglare coating composition to a transparent substrate, and a light irradiation step of irradiating the obtained coating film with light to cause phase separation and curing,
The method of including is also mentioned.

  This invention also provides the anti-glare film obtained by the manufacturing method of said anti-glare film.

  The present invention is also a polarizing plate having the above antiglare film and a polarizing element, wherein the surface of the antiglare film opposite to the antiglare layer provided on the transparent substrate is opposite to the surface of the polarizing element. A polarizing plate is also provided.

  The present invention also provides a planar translucent display, a light source device that irradiates the translucent display from the back, and the antiglare film laminated on the surface of the translucent display. A transmissive display device is also provided.

  The present invention also provides a liquid crystal display device in which the above antiglare film is used as the outermost layer of the display.

  The antiglare coating composition of the present invention can be provided with an antiglare layer, which is a resin layer having irregularities on the surface, by simply applying it on a substrate and drying it as necessary, followed by curing. Therefore, an antiglare layer having irregularities on the surface can be formed in a simpler process as compared with a method that undergoes two steps, such as forming a projection that becomes the foundation of irregularities after forming a resin layer. .

  Further, when irregularities are formed on the surface of the antiglare layer according to the present invention, the irregular arrangement is spontaneously determined, so that irregular irregular shapes can be formed on the surface of the antiglare layer. For this reason, it has the feature that the moire resulting from the regularity of uneven | corrugated arrangement | positioning does not generate | occur | produce. By using the antiglare coating composition of the present invention, an antiglare layer having irregularities on the surface can be easily formed, and an antiglare film can be easily produced using this. The resulting antiglare film has excellent performance such as no reflection, low haze (cloudiness), and high total light transmittance. Here, the haze refers to the ratio of the scattered light transmission amount to the total light transmission amount.

1 is a cross-sectional schematic view of an antiglare film of the present invention. It is explanatory drawing of parameter Rz JIS94 . It is a schematic explanatory drawing of a total light transmittance. It is a cross-sectional schematic diagram of the polarizing plate using the anti-glare film of this invention. 1 is a schematic cross-sectional view of a transmissive display device using the antiglare film of the present invention. It is a three-dimensional image by the ultra-deep shape measurement microscope on the anti-glare layer surface of the anti-glare film of Example 1. It is a three-dimensional image by the ultra-deep shape measurement microscope on the anti-glare layer surface of the anti-glare film of Example 2. It is a three-dimensional image by the ultra-deep shape measuring microscope on the anti-glare layer surface of the anti-glare film of Example 3.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Anti-glare film, 3 ... Anti-glare layer, 5 ... Transparent base material, 10 ... Polarizing plate, 12 ... Polarizing layer, 14 ... Transparent base material, 20 ... Liquid crystal display device, 22 ... Polarizing plate, 24 ... Liquid crystal panel, 26: Polarizing plate, 28: Backlight.

Antiglare coating composition The antiglare coating composition of the present invention is applied on a transparent substrate to form an antiglare layer. The antiglare coating composition contains at least two components, a first component and a second component. The first component and the second component are based on the difference in physical properties between the first component and the second component when the antiglare coating composition is applied on the substrate. And are phase-separated.

  Examples of the first component and the second component include a case where each is independently one or a combination of two or more selected from the group consisting of monomers, oligomers and resins.

  As the first component and the second component, for example, a monomer such as a polyfunctional monomer, (meth) acrylic resin, olefin resin, polyether resin, polyester resin, polyurethane resin, polysiloxane resin, polysilane resin, polyimide resin or fluorine resin Can be used. These resins may be so-called oligomers having a low molecular weight. As the polyfunctional monomer, for example, a dealcoholization reaction product of polyhydric alcohol and (meth) acrylate, specifically, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate or the like may be used. it can. 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 oligomer and 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 and the second component in the present invention, oligomers or resins containing the same kind of skeleton structure may be used, or oligomers or resins containing skeleton structures different from each other may be used. Further, either one of the first component and the second component may be a monomer, and the other one may be an oligomer or a resin.

  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 antiglare layer obtained by the coating 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. In addition, 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 those that react with each other by mixing a catalyst or a curing agent together. included. Examples of the catalyst that can be used here include a photoinitiator, a radical initiator, an acid / base catalyst, and a metal catalyst. 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.

  In the present invention, a resin containing a (meth) acrylic resin in the skeleton structure can be preferably used as the first component and the second component.

  Moreover, it is preferable that the molecular weight of a 1st component and a 2nd component is 100-100000 by molecular weight (When a 1st component and a 2nd component are resin, a weight average molecular weight).

  Differences in physical properties of the first component and the second component that cause phase separation between the first component and the second component, such as SP value, glass transition temperature (Tg), surface tension, number average molecular weight, etc. of each resin May 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: poor solvent such as dioxane, acetone, etc. n-hexane, ion-exchanged water, etc. Muddy point measurement: The poor solvent is added dropwise using a 50 ml burette, and the point at which turbidity occurs is defined as the amount of addition.

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

Vi: Molecular volume of 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 0.5 or more. The difference in SP value is more preferably 0.8 or more. The upper limit of the SP value difference is not particularly limited, but is generally 15 or less. When the difference between the SP value of the first component and the SP value of the second component is 0.5 or more, the compatibility of the resins with each other is low, whereby the first component and the second component are applied after the coating composition is applied. It is thought that this results in phase separation.

The antiglare coating composition of the present invention may further contain an organic solvent. Then, it included in the antiglare coating composition, the first component, the second component and an organic solvent, SP value of the first component (SP 1), SP value of the second component (SP 2) and SP organic solvent The value (SP sol ) is as follows :
SP 1 <SP 2 and the difference between SP 1 and SP sol is 2 or less;
It is more preferable that the relationship is satisfied. When the difference between SP 1 and SP sol is 2 or less, an antiglare film having low haze and excellent antiglare performance can be prepared. The difference between SP 1 and SP sol is more preferably 1 or less, that is, in the range of 0 to 1.

Note that SP 1 and SP sol need only have a difference of 2 or less. It may be SP 1 <SP sol , or SP 1 > SP sol .

  As an example of the first component and the second component satisfying the relationship of the above formula, there may be mentioned a case where the first component is an oligomer or a resin and the second component is a monomer. The first component oligomer or resin is more preferably an unsaturated double bond-containing acrylic copolymer. The monomer of the second component is more preferably a polyfunctional unsaturated double bond-containing monomer. 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 satisfying the relationship of the above formula, there is a case where both the first component and the second component are oligomers or resins. As the first component and the second component, it is preferable to use a resin containing 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. In the case of using two or more organic solvents, at least one kind of organic solvent used is may satisfy the condition that "the difference between the SP 1 and SP sol is 2 or less" above, using Not all organic solvents need meet the above conditions.

  When the first component and the second component are resins, the glass transition temperature (Tg) can be obtained by the same method as 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).

  In the case where the first component and the second component are resins, when the difference in physical properties between the first component and the second component that causes phase separation between the first component and the second component is a difference in Tg, the first component It is preferable that either one of the second component and the second component has a Tg lower than the environmental temperature at the time of applying the composition, and the other one has a Tg higher than the environmental temperature at the time of applying the composition. In this case, since the resin having a Tg higher than the environmental temperature is in a glass state in which molecular motion is controlled at the environmental temperature, the resin agglomerates in the coating composition after application, whereby the first component and the second component It is thought that this results in phase separation.

  As an example, in the case where the first component and the second component are resins, the Tg of a resin having an environmental temperature of 20 to 150 ° C. when the composition is applied and lower than the environmental temperature of the composition is − A case where the Tg of the resin having a Tg higher than the environmental temperature at the time of coating the composition is 70 to 120 ° C is 90 to 200 ° C. The ambient temperature is preferably 40 to 120 ° C, the Tg of a resin having a Tg lower than the ambient temperature is preferably -60 to 80 ° C, and the Tg of a resin having a Tg higher than the ambient temperature is 100 It is preferably ~ 150 ° C. In this case, a resin having a Tg lower than the environmental temperature at the time of applying the composition may be the first component, and a resin having a Tg higher than the environmental temperature at the time of applying the composition may be the second component, or vice versa. It may be.

  Further, when any one of the first component and the second component is a monomer, the difference in Tg between the first component and the second component is 20 ° C. or more, and in the first component and the second component, The Tg of the component having a higher Tg is preferably 20 ° C. or higher. The difference in Tg between the first component and the second component is more preferably 30 ° C. or more, and further preferably 50 ° C. or more. The upper limit of the difference in Tg between the first component and the second component is not particularly limited, and examples thereof include a case of 100 ° C. or lower. In this case, the component with the higher Tg is more controlled in molecular motion and thus agglomerates in the coating composition after application, thereby resulting in phase separation of the first and second components. It is done.

  As an example, in the case where either the first component or the second component is a monomer, the component having a lower Tg, that is, the Tg of the monomer is −70 to 0 ° C. and the resin having a higher Tg is used. The case where Tg is 20-200 degreeC is mentioned. In this case, as an environmental temperature at the time of application | coating of a composition, the case where it is 20-120 degreeC, for example is mentioned. More preferred examples include cases where the monomer component having a lower Tg has a Tg of -60 to 0 ° C and the resin having a higher Tg has a Tg of 30 to 150 ° C. In this case, as an environmental temperature at the time of application | coating of a composition, the case where it is 20-120 degreeC, for example is mentioned. In these cases, the monomer may be the first component or the second component.

  When the first component or the second component is a monomer, it is difficult to measure the glass transition temperature using the above method. In general, the glass transition temperature of a monomer is considered to be approximately equal to the melting point of the monomer. In the present specification, when the first component or the second component is a monomer, the Tg of the monomer is equal to the melting point of the monomer.

  When the difference in physical properties between the first component and the second component that causes phase separation between the first component and the second component is a difference in surface tension, the difference between the surface tension of the first component and the surface tension of the second component Is preferably 1 to 70 dyn / cm. More preferably, the difference is 5 to 30 dyn / cm. When the difference between the surface tension of the first component and the surface tension of the second component is 1 to 70 dyn / cm, the resin having a higher surface tension tends to agglomerate, whereby the first after application of the composition. It is believed that phase separation between the component and the second component results.

  The surface tension can be measured by obtaining a static surface tension measured by a ring method using a dynamometer manufactured by Big Chemie.

  The coating composition of the present invention may contain a commonly used resin in addition to the first component and the second component. The coating composition of the present invention is characterized by using the first component and the second component as described above to form a resin layer having irregularities without including resin particles. Therefore, it is preferable that the coating composition of the present invention does not contain resin particles.

  The coating composition of the present invention is prepared by mixing the first component and the second component together with a solvent, a catalyst, and a curing agent as necessary. The ratio of the first component to the second component in the coating composition is preferably 1:99 to 99: 1, more preferably 1:99 to 50:50, and still more preferably 1:99 to 20:80. When using a catalyst, 0.01 to 20 parts by weight, preferably 100 parts by weight of the first component, the second component and other resins as necessary (collectively referred to as “resin component”), preferably 1-10 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, it is 1-9900 weight part with respect to 100 weight part of said resin components, Preferably 100-900 weight part can be added.

  The solvent in the coating composition used in the present invention is not particularly limited, and is appropriately selected in consideration of 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, and the like. Is done. 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 antiglare coating composition of the present invention as necessary. Examples of such additives include conventional additives such as antistatic agents, plasticizers, surfactants, antioxidants, and ultraviolet absorbers.

Antiglare Film The antiglare film of the present invention has a transparent substrate and an antiglare layer. This antiglare layer is formed from the above antiglare coating composition.

  Various transparent plastic films, transparent plastic plates, glass and the like can be used as the transparent substrate. Examples of transparent 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 A film, a polycarbonate film, a polysulfone film, a polyether film, a polymethylpentene film, a polyether ketone film, a (meth) acrylonitrile film, or the like can be used. It is preferable to use triacetyl cellulose as the transparent substrate. The refractive index of triacetyl cellulose is about 1.48. Since triacetyl cellulose is widely used as a protective film for protecting the polarizing layer of the polarizing plate, an antiglare film obtained by using it as a transparent substrate can be used as it is as a protective film. In addition, although the thickness of a transparent base material can be selected timely according to a use, generally it is used at about 25-1000 micrometers.

  The antiglare layer is formed by applying the above antiglare coating composition on a transparent substrate. The application method of the coating composition can be selected as appropriate according to the coating composition and the state of the painting process. For example, the dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure method It can be applied by a coating method or an extrusion coating method (US Pat. No. 2,681,294).

  The thickness of the antiglare layer is not particularly limited, and can be set as appropriate in consideration of various factors. For example, the coating composition can be applied so that the dry film thickness is 0.01 to 20 μm.

  The coating film applied to the transparent substrate may be cured as it is, or the coating film may be dried before curing and phase-separated in advance before curing. When drying before hardening a coating film, it is 30-200 degreeC, More preferably, it is dried at 40-150 degreeC for 0.1-60 minutes, More preferably, it is 1-30 minutes, A solvent is removed, Phase separation can be achieved. When the mixture of the first component and the second component is photo-curable, drying before curing and phase separation in advance can effectively remove the solvent in the antiglare layer and There is an advantage that unevenness of a 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 1.5 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. By irradiating light to cause phase separation, there is an advantage that unevenness of the surface shape due to drying unevenness of the solvent contained in the coating composition can be avoided.

  The antiglare layer is formed by curing the coating film obtained by applying the coating composition or the 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 antiglare film thus formed is shown in FIG. The antiglare film 1 has an antiglare layer 3 and a transparent substrate 5. Since the unevenness on the surface of the antiglare film 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 antiglare layer can be evaluated using a parameter of R z JIS94 (10-point average roughness). Here, R z JIS94 is a parameter standardized in Annex 1 Table 1 of JIS B0601. This R z JIS94 is an index representing the height roughness of the irregularities on the surface. FIG. 2 is an explanatory diagram of the parameter R z JIS94 . In this figure, the solid curve shows the cross section of the antiglare layer. The ten-point average roughness (R z JIS94 ) can be measured in accordance with 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 antiglare film of the present invention preferably has R z JIS94 of 1.0 μm or less. When R z JIS94 exceeds 1.0 μm, the haze becomes high and white blurring may occur. R z JIS94 is more preferably 0.8 μm or less, and further preferably 0.5 μm or less. The lower limit is preferably 0.1 μm.

The antiglare film of the present invention preferably has a total light transmittance of 90% or more, and more preferably 95% or more. In particular, since the present invention does not contain resin particles, it is possible to achieve a high total light transmittance as described above. The total light transmittance (T t (%)) is calculated by the following equation by measuring the incident light intensity (T 0 ) with respect to the antiglare film and the total transmitted light intensity (T 1 ) transmitted through the antiglare film. . 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.).

  The antiglare film of the present invention preferably has a haze of less than 20%, more preferably 18% or less, still more preferably 15% or less, and particularly preferably 10% or less. According to the present invention, it is possible to prepare an antiglare film having excellent performance such as low haze and excellent antiglare property as described above. Advantages of low haze include that when an antiglare film is provided in a liquid crystal display device, the sharpness of the displayed image is not impaired and white blurring is less likely to occur. Such an antiglare film having a low haze has an advantage that the sharpness of an image displayed on a high-detail liquid crystal display device is not particularly impaired.

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 using, for example, a haze meter (manufactured by Suga Test Instruments Co., Ltd.).

The antiglare film of the present invention preferably has R Z JIS of 1.5 μm or less. Here, R Z JIS is the maximum height roughness of the roughness curve, and is a parameter defined in JIS B0601-2001. R Z JIS is more preferably 1.0 μm or less, and even more preferably 0.7 μm or less. The lower limit is preferably 0.1 μm. The antiglare film of the present invention is characterized in that it can be prepared without including particles such as resin particles. When forming unevenness on an antiglare film using resin particles or the like, the resin particles often aggregate during the preparation of the antiglare film. And the value of RZJIS (maximum height roughness) will become high by this aggregation. When the value of R Z JIS (maximum height roughness) of the antiglare film exceeds 1.5 μm, there is a possibility that the sharpness of an image transmitted through the antiglare film is deteriorated or a problem such as white blurring occurs. is there.

  In the antiglare film of the present invention, Sm is preferably 100 μm or less, and more preferably 50 μm or less. The lower limit is preferably 5 μm. Here, Sm is the average length of the roughness curve elements on the surface, and is generally referred to as the average interval between the peaks and valleys of the roughness curve or the average interval between the irregularities. Sm can be measured according to JIS B0633 using, for example, an ultra-deep shape measuring microscope manufactured by Keyence Corporation. Note that JIS B0633 is a Japanese industrial standard created by translating ISO 4288 without changing the technical contents and the format of the standard form.

  In the antiglare film of the present invention, the arrangement of irregular irregularities on the surface of the antiglare layer is determined spontaneously. And it is preferable that the anti-glare film of this invention does not have the maximum value of the scattered light intensity with respect to a scattering angle. When light is irradiated from the normal direction to the surface of the antiglare film, that is, from the direction perpendicular to the film surface, the transmitted light has a direction in which the irradiated light travels as it is, that is, a direction where the scattering angle is 0 °. Is the largest. And light will permeate | transmit also in the direction where the angle shifted | deviated from this normal line direction, when irradiated light is scattered by an anti-glare film. This scattered light is scattered light (transmitted scattered light). In the antiglare film of the present invention, the scattered light intensity with respect to this scattering angle preferably has no maximum value. When the scattered light has a maximum value, the scattered light is collected at a specific angle, which may cause light interference. The occurrence of light interference is not preferable because it may cause a decrease in the sharpness of an image transmitted through the antiglare film.

  The antiglare film of the present invention may further have a low refractive index layer. The low refractive index layer is made of a low refractive index resin. By laminating the low refractive index layer on at least one surface of the antiglare layer, when the low refractive index layer is disposed on the outermost surface of an optical member or the like, light from the outside (external light source etc. ) Can be effectively prevented from reflecting on the surface of the antiglare film. Moreover, the haze of an anti-glare film can be further lowered by disposing the low refractive index layer so as to be the outermost surface. Anti-glare obtained by arranging the low refractive index layer to be the outermost surface, that is, by forming an anti-glare layer on the transparent substrate, and further forming a low refractive index layer on the anti-glare layer The haze of the film can be further reduced.

  The refractive index of the low refractive index resin is, for example, about 1.35 to 1.39, preferably about 1.36 to 1.39, and more preferably about 1.38 to 1.39.

  The thickness of the low refractive index layer is, for example, 0.05 to 2 μm, preferably 0.1 to 1 μm (for example, 0.1 to 0.5 μm), and more preferably about 0.1 to 0.3 μm.

  Examples of the low refractive index resin include fluorine resins such as methylpentene resin, diethylene glycol bis (allyl carbonate) resin, polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF). The low refractive index layer usually preferably contains a fluorine-containing compound. By using a fluorine-containing compound, the refractive index of the low refractive index layer can be reduced as desired.

  The fluorine-containing compound has a fluorine atom and a functional group (such as a curable group such as a crosslinkable group or a polymerizable group) that reacts with heat or active energy rays (such as ultraviolet rays or electron beams). Examples thereof include fluorine-containing resin precursors that can be cured or crosslinked by active energy rays or the like to form a fluorine-containing resin (particularly a cured or crosslinked resin). Examples of such fluorine-containing resin precursors include fluorine atom-containing thermosetting compounds or resins [with fluorine atoms, reactive groups (epoxy groups, isocyanate groups, carboxyl groups, hydroxyl groups, etc.), polymerizable groups (vinyl). Group, allyl group, (meth) acryloyl group, etc.)], fluorine atom-containing photocurable compound or resin (photocurable fluorine-containing monomer or oligomer, etc.) curable by actinic rays (such as ultraviolet rays) And ultraviolet curable compounds).

  As the fluorine atom-containing thermosetting compound or resin, for example, a low molecular weight resin obtained by using at least a fluorine-containing monomer, for example, a fluorine-containing polyol (particularly a diol) instead of part or all of the polyol component as a constituent monomer Epoxy-based fluorine-containing resin obtained by using a fluorine-containing resin; Similarly, it is obtained by using a fluorine-atom-containing polyol and / or a fluorine-atom-containing polycarboxylic acid component instead of part or all of the polyol and / or the polycarboxylic acid component. Unsaturated polyester-based fluorine-containing resins; urethane-based fluorine-containing resins obtained by using fluorine atom-containing polyols and / or polyisocyanate components in place of some or all of the polyol and / or polyisocyanate components can be exemplified. These thermosetting compounds or resins can be used alone or in combination of two or more.

  Fluorine atom-containing photocurable compounds include, for example, monomers and oligomers (or resins, particularly low molecular weight resins), and examples of monomers include monofunctionality exemplified in the section of the antiglare layer. Fluorine atom-containing monomers corresponding to monomers and polyfunctional monomers [fluorine-containing (meth) acrylic monomers such as fluorinated alkyl esters of (meth) acrylic acid, vinyl such as fluoroolefins A monofunctional monomer such as a monomer; a di (meth) acrylate of a fluorinated alkylene glycol such as 1-fluoro-1,2-di (meth) acryloyloxyethylene]. Moreover, as an oligomer or resin, the fluorine atom containing oligomer or resin corresponding to the oligomer or resin illustrated by the term of the said glare-proof layer can be used. These photocurable compounds can be used alone or in combination of two or more.

  The curable precursor of the fluorine-containing resin can be obtained, for example, in the form of a solution (coating liquid), and such a coating liquid is, for example, “TT1006A” and “JN7215” manufactured by Nippon Synthetic Rubber Co., Ltd. It can be obtained as “Defenser TR-330” manufactured by Nippon Ink Chemical Co., Ltd.

  The antiglare film of the present invention may be composed of an antiglare layer and a low refractive index layer using a low refractive index layer as a transparent substrate. The antiglare film of the present invention may also be composed of a transparent substrate and an antiglare layer and a low refractive index layer that are sequentially formed on the transparent substrate.

Antiglare and antireflection film of the polarizing plate present invention can be used in the polarizing plate of the liquid crystal display device (liquid crystal display). FIG. 4 shows a schematic cross-sectional view of a polarizing plate using the antiglare film of the present invention. A polarizing plate 10 illustrated in FIG. 4 has a configuration in which the antiglare film 1 is provided on one surface (upper surface side in FIG. 4) of a polarizing layer (polarizing element) 12.

  The polarizing layer 12 is laminated between two transparent substrates 5 and 14. A TAC film can be used as the transparent substrates 5 and 14. The polarizing layer 12 has a three-layer structure. The first layer and the third layer are made of a film obtained by adding iodine to polyvinyl alcohol (PVA), and the second layer in the middle is made of a PVA film. This antiglare film 1 has a configuration in which an antiglare layer 3 is laminated on a transparent substrate 5.

  When a TAC film is used as the transparent substrate provided on both outer sides of the polarizing layer 12, since there is no birefringence and polarization is not disturbed, polarization is disturbed even when laminated with PVA and PVA + iodine films serving as polarizing elements. Not. Therefore, a liquid crystal display device with excellent display quality can be obtained using such a polarizing plate 10.

  As the polarizing element constituting the polarizing layer 12 in the polarizing plate 10 as described above, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer system, a PVA film dyed with iodine or a dye and stretched. Film.

  In addition, when laminating each film which comprises the polarizing layer 12, it is good to perform a saponification process to the said transparent base material for the increase in adhesiveness and electrostatic prevention.

Liquid crystal display device The antiglare antireflection film of the present invention can be used in a liquid crystal display device (liquid crystal display). FIG. 5 is a schematic cross-sectional view of a transmissive display device using the antiglare film of the present invention.

  A liquid crystal display device 20 shown in FIG. 5 includes a polarizing plate 22 similar to the polarizing plate 10, a liquid crystal panel 24, and a polarizing plate 26 stacked in this order, and a backlight on the back side of the polarizing plate 26. This is a transparent liquid crystal display device in which 28 is arranged.

  Examples of the liquid crystal mode used in the liquid crystal panel 24 in the liquid crystal display device 20 include a twist nematic type (TN), a super twist nematic type (STN), a phase transition type (PC), and a polymer dispersion type (PDLC). It may be.

  The driving mode of the liquid crystal may be either a simple matrix type or an active matrix type. In the case of the active matrix type, a driving method such as TFT or MIM is adopted. The liquid crystal panel 24 may be either a color type or a monochrome type.

  The antiglare antireflection film of the present invention can be used for an image display device such as a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display (CRT) in addition to a liquid crystal display device. it can. When using the anti-glare film of this invention for a liquid crystal display device, it can arrange | position to the outermost surface of a display by providing an adhesion layer on the transparent base material surface in which the anti-glare layer is not provided. An antireflection treatment or the like may be further performed on the antiglare layer of the antiglare film according to the present invention.

  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 silicone acrylic block copolymer VPS-1001N (azo group-containing polysiloxane compound, manufactured by Wako Pure Chemical Industries, Ltd., molecular weight of polysiloxane chain 10,000, solid content 50%) 243.9 g and cyclohexyl methacrylate A mixture consisting of 144.0 g, 43.7 g styrene, 52.3 g hydroxylethyl methacrylate and 343.3 g butyl acetate was mixed. This mixed solution was added to 270.0 g of butyl acetate heated to 120 ° C. under a nitrogen atmosphere at a constant rate over 3 hours in a 1000 ml reaction vessel equipped with a stirring blade, a nitrogen introducing tube, a cooling tube and a dropping funnel. The mixture was added dropwise and then mixed at 120 ° C. for 30 minutes to be reacted. A 15.0 g solution of butyl acetate containing 0.60 g of tertiary butyl peroxy-2-ethylhexanoate was dropped at a constant rate over 30 minutes, and then mixed and reacted at 120 ° C. for 1 hour to obtain a number average. A silicone acrylic block copolymer having a molecular weight of 34,000 and a weight average molecular weight of 125,000 was obtained. This resin had an Sp value of 10.8, Tg of 69 ° C., and a surface tension of 16 dyn / cm.

Preparation Example 2 Preparation of unsaturated double bond-containing silicone acrylic block copolymer VPS-1001N (azo group-containing polysiloxane compound, manufactured by Wako Pure Chemical Industries, Ltd., molecular weight of polysiloxane chain 10,000, solid content 50%) 243 0.9 g was mixed with a mixture consisting of 68.2 g cyclohexyl methacrylate, 103.9 g styrene, 44.3 g glycidyl methacrylate and 343.3 g butyl acetate. This mixed solution was added to 270.0 g of butyl acetate heated to 120 ° C. in a 1000 ml reaction vessel equipped with a stirring blade, a nitrogen introduction tube, a cooling tube and a dropping funnel at a constant rate over 3 hours. The solution was added dropwise, and then reacted at 120 ° C. for 30 minutes. A solution of 15.0 g of butyl acetate containing 0.60 g of tertiary butyl peroxy-2-ethylhexanoate was added dropwise at a constant rate over 30 minutes, and further reacted at 120 ° C. for 1 hour. To this reaction solution, 10 g of butyl acetate containing 3.12 g of tertiary butylammonium bromide and 0.2 g of hydroquinone was added dropwise, and 23.6 g of acrylic acid was added dropwise at 120 ° C. over 5 hours while bubbling air. The reaction was further carried out at 120 ° C. for 1 hour to obtain an unsaturated double bond-containing silicone acrylic block copolymer having a number average molecular weight of 19,000 and a weight average molecular weight of 83,000. This resin had an Sp value of 10.6, a Tg of 76 ° C., and a surface tension of 18 dyn / cm.

Preparation Example 3 Preparation of Acrylic Copolymer A mixture consisting of 280.8 g of isobornyl methacrylate, 4.2 g of methyl methacrylate, 15.0 g of methacrylic acid and 340.0 g of propylene glycol monomethyl ether was mixed. This mixed solution was added to 200 g of propylene glycol monomethyl ether heated at 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 a constant rate over 3 hours. The solution was added dropwise, and then reacted at 110 ° C. for 30 minutes. A solution of 120 g of propylene glycol monomethyl ether containing 3.0 g of tertiary butyl peroxy-2-ethylhexanoate was dropped at a constant rate over 30 minutes, and then tertiary butyl peroxy-2-ethylhexanoate 0. A 25.5 g solution of propylene glycol monomethyl ether containing 3 g was added dropwise for 30 minutes to obtain an acrylic copolymer having a number average molecular weight of 6,400 and a weight average molecular weight of 14,800. This resin had an Sp value of 9.9, Tg of 113 ° C., and a surface tension of 29 dyn / cm.

Preparation Example 4 Preparation of Unsaturated Double Bond-Containing Acrylic Copolymer A mixture consisting of 187.2 g of isobornyl methacrylate, 2.8 g of methyl methacrylate, 10.0 g of methacrylic acid and 160.0 g of propylene glycol monomethyl ether was mixed. This mixed solution was added to 200.0 g of propylene glycol monomethyl ether heated to 100 ° 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 2-ethylhexanoate, and then allowed to react at 100 ° C. for 1 hour. Thereafter, a propylene glycol monomethyl ether solution containing 0.2 g of tertiary butyl peroxy-2-ethylhexanoate was added dropwise and reacted at 100 ° C. for 1 hour. Add 5.0 g of propylene glycol monomethyl ether solution containing 1.5 g of tetrabutylammonium bromide and 0.2 g of hydroquinone to the reaction solution, and further add a solution of 17.3 g of glycidyl methacrylate and 5 g of propylene glycol monomethyl ether while bubbling air. 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 8,800 and a weight average molecular weight of 18,000 was obtained. This resin had an Sp value of 9.8, a Tg of 113 ° C., and a surface tension of 31 dyn / cm.

Preparation Example 5 Preparation of unsaturated double bond-containing acrylic copolymer Isoboronyl methacrylate 147.2 g, methyl methacrylate 2.8 g, ethyl hydroxyacrylate 4.0 g, methylacrylic acid 10.0 g and propylene glycol monomethyl ether 160.0 g A mixture consisting of This mixed liquid was mixed with 200.0 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, and tert-butylperoxy 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 2 g of 2-ethylhexanoate, and then reacted at 110 ° C. for 30 minutes. Thereafter, a solution of 17 g of propylene glycol monomethyl ether containing 0.2 g of tertiary butyl peroxy-2-ethylhexanoate was dropped and reacted at 110 ° C. for 30 minutes. To the reaction solution, 5.0 g of propylene glycol monomethyl ether solution containing 1.5 g of tetrabutylammonium bromide and 0.1 g of hydroquinone was added, and 17.3 g of glycidyl methacrylate and 5 g of propylene glycol monomethyl ether were added while air bubbling. The solution was added dropwise over a period of time, and then further reacted over 5 hours. An unsaturated double bond-containing acrylic copolymer having a number average molecular weight of 8,800 and a weight average molecular weight of 18,000 was obtained. This resin had an Sp value of 9.9, a Tg of 55 ° C., and a surface tension of 27 dyn / cm.

Preparation Example 6 Preparation of Unsaturated Double Bond-Containing Acrylic Copolymer A mixture consisting of 171.6 g of isobornyl methacrylate, 2.6 g of methyl methacrylate, and 9.2 g of methyl acrylic acid was mixed. This mixed solution was added to 330.0 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. A solution of 80.0 g of propylene glycol monomethyl ether containing 1.8 g of 2-ethylhexanoate was added dropwise at a constant rate over 3 hours and then reacted at 110 ° C. for 30 minutes. Thereafter, 0.2 g of tertiary butyl peroxy-2-ethylhexanoate was added dropwise to a solution of 17.0 g of propylene glycol monomethyl ether, and 5.0 g of propylene glycol containing 1.4 g of tetrabutylammonium bromide and 0.1 g of hydroquinone. A monomethyl ether solution was added, and a solution of 22.4 g of 4-hydroxybutyl acrylate glycidyl ether and 5.0 g of propylene glycol monomethyl ether was added dropwise over 2 hours with air bubbling, followed by further reaction over 5 hours. An unsaturated double 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 an Sp value of 10.0, a Tg of 92 ° C., and a surface tension of 31 dyn / cm.

Example 1
32 parts by weight of the silicone acrylic block copolymer of Preparation Example 1 (Sp value of this resin: 10.8, Tg: 69 ° C.), 48 parts by weight of the acrylic copolymer of Preparation Example 3 (Sp value of this resin: 9. 9, Tg: 113 ° C.), 20 parts by weight of a melamine curing agent as a thermosetting agent, 6 parts by weight of paratoluenesulfonic acid as a thermosetting catalyst, and 0.1 part by weight of a perfluoroalkyl group-containing oligomer are solvents. A solution was prepared by mixing with anisole (Sp value: 9.5) so that the nonvolatile content was 23% by weight. The obtained solution was coated on a triacetyl cellulose film substrate at an environmental temperature of 23 ° C. with a spin coater at a rotation speed of 800 rpm for 10 seconds. A coating film having a thickness of 5 μm was heat-cured at 100 ° C. for 10 minutes to obtain an antiglare film.

  Evaluation of the obtained antiglare film and evaluation of unevenness on the surface of the antiglare layer were carried out as described below. The results obtained by these evaluation methods are shown in Table 2.

Ten-point average roughness (R z JIS94 )
The ten-point average roughness (R z JIS94 ) of irregularities 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 JIS94 value was obtained.

Maximum height roughness of the roughness curve (R z JIS )
The maximum height roughness (R z JIS ) of the roughness curve of the unevenness on the surface was measured in accordance with JIS-B0601 using an ultra-deep shape measuring microscope manufactured by Keyence, and an R z JIS value was obtained. The maximum height roughness (R z JIS ) of this roughness curve was measured only in Examples 4 and 5.

Using a total light transmittance 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 are measured. Was used to calculate the total light transmittance (T t (%)).

Providing a visually cloudiness external light is diffused and reflected by the surface irregularities of the white blur antiglare layer (white blur) was judged visually. The case where there was no cloudiness by visual judgment was evaluated as ◯, the case where there was a slight cloudiness, Δ, and the case where the cloudiness could be clearly confirmed visually was evaluated as ×.

Average length of surface roughness curve element (Sm)
The average length (Sm) of the surface roughness curve element was measured based on JIS-B0633 using an ultra-deep shape measuring microscope manufactured by Keyence, and an Sm value was obtained.

Haze
Using a haze meter (manufactured by Suga Test Instruments Co., Ltd.), the diffuse light 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 (%)

  The three-dimensional image obtained by the ultra-deep shape measuring microscope in the uneven state on the surface of the antiglare layer showed a sea-island structure as shown in FIG. The obtained anti-glare film was excellent in anti-glare property without reflection of a fluorescent lamp under a fluorescent lamp.

Example 2
40 parts by weight of unsaturated double bond-containing silicone acrylic block copolymer of Preparation Example 2 (Sp value of this resin: 10.6, Tg: 76 ° C.), unsaturated double bond-containing acrylic copolymer of Preparation Example 4 (Sp value of this resin: 9.8, Tg: 113 ° C.) 60 parts by weight, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 5 parts by weight as a photoinitiator, 0.1 perfluoroalkyl group-containing oligomer A part by weight was mixed with anisole as a solvent to prepare a solution so that the nonvolatile fraction was 20% by weight. This solution was applied to a triacetyl cellulose film substrate at an environmental temperature of 23 ° C. with a spin coater at a rotation speed of 1000 rpm for 10 seconds, and then heated at 120 ° C. for 10 minutes to volatilize the solvent to a film thickness of 8 μm. did. The film film was exposed to ultraviolet light with an ultrahigh pressure mercury lamp so that the ultraviolet energy was 1 J / cm 2 . The unevenness of the obtained antiglare film and antiglare layer surface was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

  The three-dimensional image obtained by measuring the uneven state of the antiglare layer surface with an ultra-deep shape measurement microscope showed a sea-island structure as shown in FIG. The obtained antiglare film was excellent in antiglare property without reflection of fluorescent light under a fluorescent light.

Example 3
75 parts by weight of dipentaerythritol hexaacrylate (Sp value of this monomer: 12.1) which is a polyfunctional unsaturated double bond-containing monomer and the unsaturated double bond-containing acrylic copolymer of Preparation Example 5 (of this resin) Sp value: 9.9, Tg: 55 ° C.), 2,4,6-trimethylbenzoyldiphenylphosphine oxide 5 parts by weight as a photoinitiator, 0.1 part by weight of perfluoroalkyl group-containing oligomer, propylene glycol monomethyl Ether (SP value: 10.1) was used as a solvent and the non-volatile fraction was adjusted to 23% by weight. This solution was bar coated on a triacetyl cellulose film substrate with a bar coater (No. 18) at an environmental temperature of 23 ° C., and heated at 50 ° C. for 10 minutes to remove the solvent to a film thickness of 6 μm. did. Thereafter, this film was exposed with an ultra-high pressure mercury lamp so that ultraviolet rays had an energy of 1 J / cm 2 to form an antiglare layer. The unevenness of the obtained antiglare film and antiglare layer surface was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

  The three-dimensional image obtained by the ultra-deep shape measuring microscope in the uneven state on the surface of the antiglare layer showed a sea-island structure as shown in FIG. The obtained anti-glare film was excellent in anti-glare property without reflection of a fluorescent lamp under a fluorescent lamp.

Example 4
20 parts by weight of an unsaturated double bond-containing acrylic copolymer of Preparation Example 6 (Sp value of this resin: 10.0, Tg: 92 ° C.) and pentaerythritol triacrylate which is a polyfunctional unsaturated double bond-containing monomer (Sp value of this monomer: 12.7) 90 parts by weight, and 7 parts by weight of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photoinitiator as a solvent It mixed with a certain isobutyl alcohol (SP value: 11.3), and the solution was created so that a non volatile fraction might be 40 weight%. This solution was applied to a triacetylcellulose film substrate with a bar coater (No. 12) at an environmental temperature of 23 ° C., and heated at 60 ° C. for 1 minute to remove the solvent and dried to a film thickness of 6 μm. Then, an antiglare layer was formed. Thereafter, this film was exposed to an ultraviolet ray with an ultrahigh pressure mercury lamp so as to have an energy of 1 J / cm 2 and cured. The unevenness on the surface of the obtained antiglare film and antiglare layer was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

Example 5
5 parts by weight of an unsaturated double bond-containing acrylic copolymer of Preparation Example 6 (Sp value of this resin: 10.0, Tg: 92 ° C.) and pentaerythritol triacrylate which is a polyfunctional unsaturated double bond-containing monomer (Sp value of this monomer: 12.7) 50 parts by weight, 50 parts by weight of polyethylene glycol # 200 diacrylate (Sp value of this monomer: 13.6), 2-methyl-1 [4- ( Methylthio) phenyl] -2-morpholinopropan-1-one 13 parts by weight is mixed with methyl isobutyl ketone (SP value: 8.3) as a solvent to prepare a solution so that the nonvolatile content is 60% by weight. did. This solution was bar coated with a bar coater (No. 5) on a triacetyl cellulose film substrate at an environmental temperature of 23 ° C., and heated at 80 ° C. for 3 minutes to remove the solvent to a film thickness of 4 μm. did. Thereafter, this film was exposed to an ultraviolet ray with an energy of 1 J / cm 2 with an ultrahigh pressure mercury lamp to form an antiglare layer and cured. The unevenness on the surface of the obtained antiglare film and antiglare layer was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

Comparative example 1 (reference example based on patent document 1)
100 parts of UV curable resin (Nippon Kayaku PETA), 1.7 parts by weight of triacetyl cellulose (Bayer), 5 parts by weight of photocuring initiator (Ciba Geigy, Irgacure 184) and styrene beads (Soken Chemical) 20 parts by weight) were mixed. The solid content was adjusted to 40% using toluene, and applied to a triacetyl cellulose film substrate at an environmental temperature of 23 ° C. using a spin coater so as to have a dry film thickness of 3.5 μm. The solvent was dried at 80 ° C. for 10 minutes, and then an ultraviolet ray was irradiated at 200 mJ / cm (superscript: 2) to form an antiglare layer. The obtained antiglare film and antiglare layer were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

Comparative Example 2 (Reference Example Based on Patent Document 3)
A solution in which a fluorine group-introduced epoxy resin and an acrylic resin were mixed at a ratio of 2: 1 on a triacetylcellulose film substrate was applied at an environmental temperature of 23 ° C. with a spin coater. The applied resin was cured by heat treatment at a temperature of 80 ° C. for 90 minutes to form an antiglare layer having an uneven surface shape. The obtained antiglare film and antiglare layer were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2. The surface of this antiglare layer showed a sea-island structure. The obtained antiglare film was not reflected under a fluorescent lamp, but the total light transmittance was as low as 80%, and the white blur evaluation was x.

  In the above examples, it is confirmed that the antiglare film formed from the coating composition of the present invention has excellent performance such as high total light transmittance and no white blur compared to the comparative example. It was done. Moreover, as shown in Examples 4 and 5, it was confirmed that the present invention can prepare an antiglare film having excellent performance such as low haze, high total light transmittance, and no white blur.

Claims (14)

  1. An antiglare coating composition that is applied on a transparent substrate to form an antiglare layer,
    The antiglare coating composition comprises a first component and a second component;
    After applying the antiglare coating composition on a substrate, the first component and the second component are phase-separated based on the difference in physical properties of the first component and the second component, and random irregularities are formed on the surface. A resin layer is formed,
    An antiglare coating composition comprising:
    The first component is an oligomer or resin which is an unsaturated double bond-containing acrylic copolymer, and the second component is a polyfunctional unsaturated double bond-containing monomer ;
    The SP value (SP 1 ) of the first component and the SP value (SP 2 ) of the second component are in a relationship satisfying SP 1 <SP 2 ;
    Antiglare coating composition.
  2. An antiglare coating composition that is applied on a transparent substrate to form an antiglare layer,
    The antiglare coating composition comprises a first component and a second component;
    After applying the antiglare coating composition on a substrate, the first component and the second component are phase-separated based on the difference in physical properties of the first component and the second component, and random irregularities are formed on the surface. A resin layer is formed,
    An antiglare coating composition comprising:
    The first component is an acrylic copolymer, said second component is a silicone-acrylic block copolymer,
    The SP value (SP 1 ) of the first component and the SP value (SP 2 ) of the second component are in a relationship satisfying SP 1 <SP 2 ;
    Antiglare coating composition.
  3. Furthermore, an antiglare coating composition containing an organic solvent,
    The SP value (SP 1 ) of the first component, the SP value (SP 2 ) of the second component, and the SP value (SP sol ) of the organic solvent are
    The difference between SP 1 and SP sol is 1.7 or less;
    The anti-glare coating composition according to claim 1 or 2, wherein
  4. The anti-glare coating composition according to any one of claims 1 to 3 , wherein a difference between the SP value (SP 1 ) of the first component and the SP value (SP 2 ) of the second component is 0.8 to 3.6. object.
  5. Furthermore, the anti-glare coating composition in any one of Claims 1-4 containing a hardening | curing agent.
  6. And wherein the free of resin particles, according to claim 1-5 antiglare coating composition according to any one.
  7. An antiglare film having a transparent base material and an antiglare layer, wherein the antiglare layer is formed from the antiglare coating composition according to any one of claims 1 to 6 .
  8. An application step of applying the antiglare coating composition according to any one of claims 1 to 6 to a transparent substrate, and a curing step of curing the obtained coating film,
    A method for producing an antiglare film.
  9. The application process which apply | coats the anti-glare coating composition in any one of Claims 1-6 to a transparent base material,
    A drying step for drying and phase-separating the obtained coating film, and a curing step for curing the dried coating film,
    A method for producing an antiglare film.
  10. An application step of applying the antiglare coating composition according to any one of claims 1 to 6 to a transparent substrate, and a light irradiation step of irradiating light to the obtained coating film to cause phase separation and curing,
    A method for producing an antiglare film.
  11. The anti-glare film obtained by the manufacturing method of the anti-glare film in any one of Claims 8-10 .
  12. A polarizing plate comprising the antiglare film according to claim 7 and a polarizing element, wherein the antiglare film surface and the polarizing element surface opposite to the antiglare layer provided on the transparent substrate face each other. The polarizing plate is laminated.
  13. A planar light-transmitting display, a light source device that irradiates the light-transmitting display from the back, and the antiglare film according to claim 7 or 11 laminated on the surface of the light-transmitting display. A transmissive display device.
  14. A liquid crystal display device in which the antiglare film according to claim 7 or 11 is used as an outermost layer of a display.
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