JP4843283B2 - Method for producing antiglare sheet - Google Patents

Description

The present invention relates to a liquid crystal display (LCD), a flat panel display (FPD), organic EL, a display device such as a PDP, an antiglare with fine fine surface unevenness structure for suppressing the visibility deterioration of the screen of the display device The present invention relates to a method for producing a conductive sheet.

Conventionally, a display device such as a liquid crystal display (LCD), when light from an externally bright light source is incident on the surface of the display device, is reflected on the screen due to the reflection of the light source or the shadow of a person or the like. Is significantly hindered.
Therefore, for the purpose of improving the visibility of the screen, the display device surface diffuses reflected light from the display device surface, suppresses regular reflection of incident light, and prevents reflection (has antiglare properties). ) An antiglare layer having a fine surface uneven structure is formed.

As a method of forming such an antiglare layer having a fine surface concavo-convex structure on the surface of the display device, the surface concavo-convex structure can be easily miniaturized and the antiglare layer can be easily formed on the display device surface. A method in which fine particles are dispersed in a cured resin is applied to the surface of a display device and the resin is cured (for example, Patent Document 1).
In this method, for example, inorganic fine particles (for example, calcium carbonate particles, titanium oxide particles, silica particles, etc.) and organic fine particles (acrylic polymer particles, silicone polymer particles, etc.) are contained in a curable resin such as an ultraviolet curable resin. An antiglare layer having a fine surface uneven structure is formed on the surface of the display device by applying the dispersed paint to the surface of the display device and curing it.

However, in a display device having an antiglare layer formed by the above method, the antiglare layer does not exhibit sufficient antiglare property due to poor dispersion of the fine particles in the curable resin or the like. The transparency of the glare layer may decrease, and problems such as poor appearance may occur.
Furthermore, the fine particles dispersed in the cured resin with the passage of time have floated to the surface of the antiglare layer and the antiglare performance of the antiglare layer formed on the surface of the display device has deteriorated, or has also floated to the surface. In some cases, the fine particles themselves may cause poor appearance (for example, surface contamination).

In addition, a method of forming an antiglare film having a fine surface uneven structure used by being laminated on the surface of a display device by using a transfer method has been proposed (for example, Patent Document 2).
This method uses an shaping film having a concavo-convex shape formed on the surface, casts a cured resin into the shaping film, cures the cured resin, and copies it to the cured resin. An adhesive film is formed.
However, the cured resin adheres to the shaped film, and the uneven shape cannot be copied and the desired anti-glare property cannot be obtained, or the used film can be used many times. There is a problem that the uneven shape of the surface of the shaping film is changed, and furthermore, the workability is complicated.

Therefore, without using an inorganic or organic fine particles, a method which can easily produce an antiglare sheet having a fine fine uneven surface structure is desired.

Japanese Patent Laid-Open No. 9-127312 International Publication No. 95/31737 Pamphlet

In view of the above problems, without using an inorganic or organic fine particles, it is an object to provide a process for conveniently producing an antiglare sheet having a fine fine uneven surface structure.

As a result of intensive studies to solve the above problems, the present inventors applied a coating liquid in which an organic resin material and a material incompatible with the organic resin material were mixed, and a phase separation structure After the coating film is formed and cured, the anti-glare sheet having a fine surface uneven structure can be produced by removing the incompatible material from the cured coating film by a predetermined method. As a result, the present invention has been completed.

That is, the present invention relates to an organic resin material comprising an acrylic ultraviolet curable resin having two or more functional groups that can be polymerized by ultraviolet irradiation in one molecule, and an alkyl which is an incompatible material with the organic resin material. A coating having a phase separation structure in which (meth) acrylate is mixed to prepare a coating liquid, and the coating liquid is applied, and the organic resin material and the incompatible material are phase-separated. A second step of forming a film, and a curing treatment as an ultraviolet irradiation treatment is performed on the coating film, the organic resin material is cured to fix the phase separation structure, and then the coating film is subjected to the curing treatment. And a third step of forming a cured resin layer having a surface uneven structure by removing the incompatible material, and providing a method for producing an antiglare sheet.
In such a manufacturing method, a coating liquid containing an organic resin material and a material incompatible with the organic resin material is applied to form a coating film having a phase separation structure, and is cured and cured. By removing the incompatible material from the coating film, a fine surface uneven structure can be formed in the cured resin layer.

The present invention also provides an organic resin material comprising an acrylic ultraviolet curable resin having two or more functional groups that can be polymerized by ultraviolet irradiation in one molecule, and an alkyl which is a material incompatible with the organic resin material. A phase separation structure in which (meth) acrylate and a solvent are mixed to prepare a coating liquid, and the coating liquid is applied, and the organic resin material and the incompatible material are phase-separated. A second step of forming a coating film having, a solvent removal step of removing the solvent from the coating film after the second step, and a curing treatment in which the coating film from which the solvent has been removed by the solvent removal step is subjected to ultraviolet irradiation treatment The organic resin material is cured to fix the phase separation structure, and then the incompatible material is removed from the coating film that has been subjected to a curing treatment to obtain a cured resin layer having a surface uneven structure. Including a third step of forming To provide a method of manufacturing the anti-glare sheet, characterized in that.
In such a manufacturing method, a coating liquid containing an organic resin material, a material incompatible with the organic resin material and a solvent is applied, and a coating film having a phase separation structure is formed by removing the solvent. ,
By removing the incompatible material from the cured coating film, a fine surface uneven structure can be formed on the cured resin layer.

  In the present invention, it is preferable to remove the incompatible material in the third step by solvent extraction.

  Furthermore, in the present invention, the solvent used for solvent extraction is preferably liquefied carbon dioxide or carbon dioxide in a supercritical state.

  In the present invention, the solvent used for solvent extraction is preferably an organic solvent that selectively dissolves incompatible materials.

In the method for producing an antiglare sheet according to the present invention, since inorganic or organic fine particles are not used, problems such as a decrease in the antiglare performance of the antiglare layer due to poor dispersion of the fine particles or a poor appearance due to nonuniform dispersion of fine particles. Can be prevented, and workability is also good.
Further, in the method for producing an antiglare sheet according to the present invention, since fine particles such as inorganic or organic fine particles are not used, there is no scattering caused by the fine particles, and characteristic design such as antiglare performance is facilitated.

Hereinafter, the manufacturing method of the anti-glare sheet | seat of this invention is demonstrated .
The method for producing an antiglare sheet according to the present invention includes an organic resin material composed of an acrylic ultraviolet curable resin having two or more functional groups polymerizable by ultraviolet irradiation in one molecule, and non-organic resin material. A first step of mixing a compatible material alkyl (meth) acrylate to prepare a coating liquid, and applying the coating liquid, the organic resin material and the incompatible material were phase-separated. A second step of forming a coating film having a phase separation structure, and a curing treatment such as an ultraviolet irradiation treatment is performed on the coating film, the organic resin material is cured to fix the phase separation structure, and then a curing treatment is performed. A third step of removing the incompatible material from the coated film and forming a cured resin layer having a surface uneven structure.

First, in the coating liquid prepared in the first step in the present invention, an organic resin material composed of an acrylic ultraviolet curable resin having two or more functional groups polymerizable by ultraviolet irradiation in one molecule and the organic resin Alkyl (meth) acrylate which is a material incompatible with the material is mixed.
Examples of the organic resin material, when cured the organic resin material, it is possible to have use those having sufficient strength and transparency as a film.
Ultraviolet curing resin, it is possible to perform the curing treatment by irradiation with ultraviolet rays, the operation is easy, and can be formed efficiently cured resin layer.

Examples of the ultraviolet curable resin include various types such as polyester, acrylic, urethane, amide, silicone, and epoxy. The ultraviolet curable resin includes ultraviolet curable monomers, oligomers, polymers, and the like.
These have functional groups that can be polymerized by irradiation with ultraviolet rays, preferably two or more of the functional groups in one molecule, in particular, an acrylic type having 3 to 6 functional groups in one molecule. These monomers and oligomers are preferred.

In the present invention, the material that is incompatible with the organic resin material is a mixture that is not compatible even when mixed with the organic resin material, and phase-separates over time even when mixed and stirred. It has a ratio area.
Such an incompatible material may be any material that can be removed by a method such as solvent extraction after phase separation and immobilization of the phase separation structure when mixed with the organic resin material. It said incompatible material is an organic equipment cost.

Examples of the incompatible materials, which are appropriately selected depending on the organic resin material to be used is A alkyl (meth) acrylate.

The molecular weight of the incompatible material is not particularly limited, but is preferably 10,000 or less (for example, 100 to 10,000) as the weight average molecular weight because the subsequent removal operation becomes easy, and more preferably. Is about 200 to 3,000.
The weight average molecular weight is measured by the method described in the examples.

The combination of organic resin material and said incompatible material is a combination of acrylic UV-curable resin (having two or more polymerizable functional groups) and alkyl (meth) acrylate.
Specifically, as an organic resin material, urethane acrylic ultraviolet curable resin, poly (meth) acrylate of polyhydric alcohol such as pentaerythritol triacrylate and dipentaerythritol hexaacrylate, and tris (2-hydroxyethyl) isocyanate A combination of one or more of the rate triacrylates and an alkyl (meth) acrylate may be used as the incompatible material.

The mixing amount of the organic resin material and the incompatible material is 10 to 400 parts by weight of the incompatible material with respect to 100 parts by weight of the organic resin material, and preferably the incompatible material 20 -200 parts by weight.
By mixing incompatible materials in the range of 10 to 400 parts by weight with respect to 100 parts by weight of the organic resin material, the haze value, average crest and valley distance (Sm), and centerline average surface of the antiglare sheet formed The roughness (Ra) can be easily adjusted to a desired range.
When the mixing amount of incompatible materials exceeds 400 parts by weight, the phase separation structure becomes too large, and the average peak-to-valley spacing (Sm) and the centerline average surface roughness (Ra) become too large. Have
Further, when the mixing amount of the incompatible material is less than 10 parts by weight, the phase separation structure becomes too fine, and it is difficult to obtain a desired average crest / valley spacing (Sm) and centerline average surface roughness (Ra). Have a problem.

In mixing the organic resin material and the incompatible material, an organic solvent can be further mixed. By mixing the organic solvent, the viscosity of the coating solution can be reduced, coating becomes easy, and coating unevenness is less likely to occur.
The organic solvent may be one that does not dissolve at least one of the organic resin material and the incompatible material, or one that dissolves both of them. It is appropriately selected depending on the compatible material.
Even if the organic solvent dissolves both, the organic resin material and the incompatible material are phase-separated by removing the organic solvent.
Examples of the organic solvent include aromatic hydrocarbons such as xylene and toluene, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as methyl ethyl ketone, and esters such as methyl acetate and ethyl acetate.
As the organic solvent, xylene, toluene, ethyl acetate and the like are preferable.

The mixing amount of the organic solvent is appropriately determined depending on the liquid viscosity of the mixture of the organic resin material and the incompatible material, and is usually 10 to 500 parts by weight with respect to 100 parts by weight of the organic resin material. The amount is preferably 10 to 300 parts by weight, more preferably 30 to 200 parts by weight.
When the mixing amount of the organic solvent exceeds 500 parts by weight, the viscosity of the coating liquid becomes low, so that the coating film becomes too thin and the thickness of the resulting sheet becomes extremely thin.
Further, when the amount of the organic solvent mixed is less than 10 parts by weight, there is a problem that the viscosity of the coating liquid becomes high and uneven coating tends to occur.

Moreover, the polymerization initiator which hardens the said organic resin material may be mixed with the said coating liquid. A well-known thing can be used as said polymerization initiator.
Specific examples of the polymerization initiator used for the thermosetting resin include, for example, organic peroxides such as dibenzoyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, lauroyl peroxide, and 2,2′- An azo compound such as azobisisobutyronitrile, 2,2′-azobisisovaleronitrile, and the like can be given.
Specific examples of the polymerization initiator used for the ultraviolet curable resin include, for example, acetophenones, benzophenones, diacetyls, benzyls, benzoins, benzoin ethers, benzyldimethyl ketals, benzoylbenzoates, hydroxyphenyl ketones. And the like.
The mixing amount of the polymerization initiator is 0.01 to 10 parts by weight, preferably 0.05 to 10 parts by weight of the polymerization initiator with respect to 100 parts by weight of the organic resin material. .

Further, the coating liquid is mixed with a leveling agent, thixotropic agent, antistatic agent, antioxidant, ultraviolet absorber, light stabilizer, filler, colorant and the like to the extent that the object of the present invention is not impaired. Also good.
These may be used alone or in combination.

Moreover, when the said organic resin material is hardened as needed, the said coating liquid may be mixed with the crosslinking agent which accelerates | stimulates bridge | crosslinking of the said organic resin material.
Examples of preferable types of the crosslinking agent include polyisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate, polyepoxy, various metal salts, chelate compounds, and the like.
The amount of the crosslinking agent to be mixed is not particularly limited as long as it does not impair the object of the present invention, but is preferably 20 parts by weight or less with respect to 100 parts by weight of the organic resin material, and can be appropriately adjusted within this range. . In addition, even if these crosslinking agents are used individually or in combination of 2 or more types, there is no problem.
Moreover, you may add a chain transfer agent and a plasticizer as needed.

In the present invention, the substrate to which the coating liquid is applied may be transparent (transparent substrate) or opaque (opaque substrate) as long as it has a smooth surface. Examples of the transparent substrate include glass and various transparent plastic material films.
Moreover, as an opaque base material, metal plates, such as stainless steel, etc. can be mentioned. As the substrate, the transparent substrate is preferable.

When the substrate is a transparent plastic material film, examples of the film include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, polycarbonate polymers, and polymethyl methacrylate. An acrylic polymer film such as
In addition, styrene polymers such as polystyrene and acrylonitrile-styrene copolymers, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, olefin polymers such as ethylene-propylene copolymers, vinyl chloride polymers, nylon and aromatic polyamides. Examples thereof include amide polymer films.
Furthermore, imide polymers, sulfone polymers, polyether sulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene And polymer films such as polymer-based polymers, epoxy-based polymers, and blends of the aforementioned polymers.
In the present invention, one type of the film may be a single layer, or two or more of the same type or different types of films may be laminated.
The film is preferably as colorless and transparent as possible, and preferably has a transmittance in the wavelength region of 400 to 800 nm of 80% or more, more preferably 90% or more.

The transparent plastic material film may be stretched, and in that case, may be uniaxially stretched, biaxially stretched, or Z-axis stretched.
The stretching means and the stretching ratio are not particularly limited, but it is preferable to make the same magnification in both the width direction (MD direction) and the longitudinal direction (TD direction).
The draw ratio is 0.5 to 3 times, preferably 1 to 2 times.
In general, a plastic material film develops birefringence by being subjected to a stretching treatment. Therefore, when used as an optical application, a non-stretched film that does not disturb the polarization state of a liquid crystal cell that has already been set. Is preferably used.

When the substrate is the transparent plastic material film, at least one surface may be subjected to various surface treatments such as corona treatment, UV treatment, and EB (electron beam) treatment.
By performing the surface treatment on the surface of the film, adhesion between the cured resin layer obtained by applying and curing the coating liquid and the film can be improved.

  The thickness of the substrate is appropriately set according to the purpose, but is generally 10 to 500 μm, preferably 20 to 300 μm, from the viewpoints of workability such as strength, handleability, and thin film properties. More preferably, it is 30-200 micrometers.

Next, the manufacturing method of the anti-glare sheet of this invention is demonstrated along each process.
First, in a first step, serving the material incompatible with polymerizable functional groups to the organic resin material and the organic resin material made of an acrylic UV-curable resin having at least two by irradiation of ultraviolet rays in a molecule Alkyl (meth) acrylate is mixed without a solvent, or the organic resin material and a material incompatible with the organic resin material are mixed using an organic solvent to prepare a coating liquid.
It is preferable that the coating liquid thus obtained is slightly clouded visually.
As a mixing method for preparing the coating liquid, it is not necessary to adopt any special method, and for example, a general mixing method such as stirring and ultrasonic irradiation can be used.
The prepared coating liquid preferably has a level at which the liquid turbidity after mixing and stirring sufficiently becomes slightly cloudy visually.

  Next, in a 2nd process, the coating liquid obtained as mentioned above is apply | coated to the said base material, for example, and the coating film which has a phase-separation structure is formed.

As a method for forming a coating film on the substrate, for example, an appropriate method such as phanten, phanten metalling, die coater, casting, spin coating, or gravure method can be used.
In the case where the coating solution contains an organic solvent, generally, after forming a coating film on the substrate using the above method, the organic solvent is removed by heating, reduced pressure removal, etc. in a solvent removal step. Remove using conventional methods.

  Next, in the third step, the coating film is cured, the organic resin material is cured to fix the phase separation structure, and then the incompatible material is removed from the coating film subjected to the curing process. It is removed and a cured resin layer having a surface uneven structure is formed on the substrate.

Before the curing treatment, the organic resin material and the incompatible material are in a liquid phase-separated state, but the phase separation is promoted by performing the curing treatment, and the cured resin layer of the organic resin material And a liquid layer of the incompatible material, and an uneven structure is formed at the interface portion.
In the first step, the concavo-convex structure is formed if the liquid turbidity after mixing the organic resin material and the incompatible material and stirring sufficiently is a level that is slightly cloudy visually. Achieved.

For the curing treatment, a curing treatment method corresponding to the curable resin material used as the organic resin material is appropriately employed.
That is, the order organic resin material is an ultraviolet curing resin, Ru by irradiating ultraviolet rays to cure the organic resin material in the coating film.
The resin obtained by curing the organic resin material is preferably as colorless and transparent as possible, and preferably has a transmittance in the wavelength region of 400 to 800 nm of 80% or more, more preferably 90% or more. .

The method for removing the incompatible material from the cured coating can be performed by extraction with a solvent.
By removing the incompatible material from the cured coating film, the portion of the phase separation structure in the coating film occupied by the incompatible material is removed, and the surface has a concavo-convex structure. A cured resin layer is formed.

The extraction solvent for removing the incompatible material from the cured coating film is a good solvent for the incompatible material used in the present invention, and the organic solvent used in the present invention. There is no particular limitation as long as it does not dissolve the cured resin material.
As long as it has such properties, it can be used by appropriately selecting from common solvents, and is not particularly limited, but from the viewpoint of removal efficiency and harmlessness, liquefied carbon dioxide and super Carbon dioxide in a critical state (supercritical carbon dioxide) is used.

  The apparatus for removing incompatible materials in the cured coating film with liquefied carbon dioxide or carbon dioxide in a supercritical state (supercritical carbon dioxide) is not particularly limited as long as it is a pressure vessel. Any type of pressure vessel may be used as long as it is a batch type pressure vessel or a pressure vessel equipped with a sheet feeding and winding device.

A specific method in the case of using liquefied carbon dioxide or carbon dioxide in a supercritical state (supercritical carbon dioxide) as an extraction solvent will be described.
The coating film subjected to the curing treatment is put into a pressure vessel, carbon dioxide is injected, and liquefied carbon dioxide or supercritical carbon dioxide is allowed to permeate the coating film.
After sufficiently infiltrating the carbon dioxide, evacuation and injection of carbon dioxide are repeated continuously or intermittently, and the incompatible material in the coating film subjected to the curing treatment is liquefied carbon dioxide or supercritical state. Insoluble carbon dioxide (supercritical carbon dioxide) is extracted (dissolved) to remove the incompatible material from the coating film.

As extraction (dissolution) conditions, for example, in the case of extracting and removing an incompatible material with carbon dioxide in a supercritical state (supercritical carbon dioxide), the temperature is 32 ° C. and the pressure is 7.3 MPa or more.
In the supercritical state, the incompatible material can be efficiently removed from the inside of the coating film by promoting the swelling of the cured organic resin material and improving the diffusion coefficient of the incompatible material.
In the case of liquefied carbon dioxide, the diffusion coefficient is reduced, but the permeability to the cured organic resin material is improved. Can be efficiently removed.

When extracting (dissolving) the incompatible material from the cured film, an organic solvent that dissolves the incompatible material without dissolving the cured product of the organic resin material may be used. it can.
By using the organic solvent, the incompatible material can be removed under atmospheric pressure, and deformation of the substrate can be suppressed as compared with the case where the organic solvent is removed under pressure.
Moreover, extraction time can also be shortened by selecting an organic solvent.
Furthermore, it is also possible to continuously perform the step of removing the incompatible material from the coating film by passing the cured coating film sequentially in an organic solvent.

The organic solvent is not particularly limited, and examples include generally used solvents such as toluene, ethanol, ethyl acetate, and heptane.
These organic solvents may be used alone or in admixture of two or more, but are preferably extracted with toluene or ethanol from the viewpoint of the removal efficiency of incompatible materials.

The method for removing the incompatible material using the organic solvent is not particularly limited. For example, the method for removing the incompatible material by impregnating the cured film with the organic solvent or the organic Examples thereof include a method of removing an incompatible material by showering a solvent-applied coating film from a spray nozzle or the like.
From the viewpoint of efficient removal, a method of removing an incompatible material by impregnating the cured coating film with an organic solvent is preferable.
For example, the incompatible material can be removed by immersing in a 200 ml organic solvent for 10 minutes with respect to a coating film (length 10 cm × width 15 cm × thickness 4 μm) subjected to a curing treatment at a temperature of 25 ° C. .
Moreover, the said incompatible material can be efficiently removed by extracting while changing an organic solvent over several times, or stirring an organic solvent.

The surface uneven structure of the antiglare sheet in the present invention can be appropriately prepared depending on the combination or blending amount of an incompatible material and an organic resin material.
By preparing a combination or blending amount of an incompatible material and an organic resin material,
Can be the desired ones haze value of the antiglare sheet as antiglare sheet.

The average peak-valley spacing (Sm) of the antiglare sheet produced by the production method of the present invention is 80 to 400 μm, preferably 80 to 300 μm.
When the average peak-valley interval (Sm) is less than 80 μm, there is a problem that the optical characteristics may be almost the same as when there is no unevenness.
In addition, when the average peak-valley interval (Sm) exceeds 400 μm, there is a problem that glare or roughness increases.
In addition, an average mountain valley space | interval (Sm) is measured by the method of an Example description.

The centerline average surface roughness (Ra) of the antiglare sheet produced by the production method of the present invention is 50 to 1500 nm, preferably 50 to 1000 nm.
When the center line average surface roughness (Ra) is within the above range, the antiglare property functions sufficiently.
The centerline average surface roughness (Ra) is measured by the method described in the examples.

The haze value of the antiglare sheet manufactured by the manufacturing method of the present invention is set to 80 to 400 μm and the center line average surface roughness (Ra) is set to 50 to 1500 nm. It can be controlled within a range of 5 to 50% and can exhibit antiglare properties.
The haze value is preferably 50% or less, more preferably 40% or less from the viewpoint of image clarity.
The haze value is measured by the method described in the examples.

Although the thickness in particular of an anti-glare sheet is not restrict | limited, It is 0.5-30 micrometers, Preferably it is 3-20 micrometers.
When the thickness of the antiglare sheet is within the above range, the handling properties are good.
In addition, the thickness of the film used as a base material is not included in the thickness of the anti-glare sheet.

A low refractive index layer having an antireflection function can be separately provided on the surface of the antiglare sheet having an uneven structure. The material for the low refractive index layer is not particularly limited as long as it has a lower refractive index than the material constituting the cured resin layer. Examples of the method for forming the low refractive index layer include a wet coating method and a vacuum deposition method.

The anti-glare sheet produced by the production method of the present invention can be formed on at least one side of a transparent substrate. Various optical elements can be attached to the other surface of the transparent base material of the antiglare sheet.
In addition, as a transparent base material, the transparent plastic material film described above can be used suitably.
Examples of the optical element include a polarizing plate. The polarizing plate is not particularly limited, and various types can be used.

  In addition, in order to widen the viewing angle so that the image can be seen clearly even when the screen of the liquid crystal display device is viewed from a slightly oblique direction rather than perpendicular to the screen on a polarizing plate with an antiglare sheet attached. The viewing angle compensating retardation plate may be combined, or a brightness enhancement film for improving the brightness may be combined.

  When the optical element is attached to the antiglare sheet, an adhesive or a pressure-sensitive adhesive can be used. The type of adhesive or pressure-sensitive adhesive is not particularly limited, and various types can be used. In particular, an acrylic pressure-sensitive adhesive that exhibits adhesive properties such as optical transparency, appropriate wettability, and cohesiveness, and is excellent in weather resistance, heat resistance, and the like is preferably used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples.

(Measurement method of weight average molecular weight)
The weight average molecular weight is a value converted by standard polystyrene by the GPC method.
As the GPC main body, model name: “HLC-8120GPC” manufactured by Tosoh Corporation was used, the column temperature was 40 ° C., the pump flow rate was 0.5 ml / min, and the detector RI was used. Data processing is performed using standard polystyrene calibration curves with known molecular weights in advance (molecular weights of 20.6 million, 8.42 million, 4.48 million, 1.11 million, 707,000, 354,000, 188,000, 98,000, 372,000, 171,000, 9830, 5870, A calibration curve was prepared using standard polystyrenes of 2500, 1050 and 500), and the molecular weight was determined from the converted molecular weight.
Column used: Trade name "TSKgel GMH-H (S)" x 2 (Tosoh Corporation)
Mobile phase: Tetrahydrofuran Injection volume: 100 μl
Sample concentration: 1.0 g / l (tetrahydrofuran solution)

(Measurement method of total light transmittance)
Using “Suga Test Instruments Co., Ltd .: Haze meter, model name: HGM-2DP”, the total light was measured when light (400 nm to 700 nm) was transmitted from the surface uneven surface side of the antiglare sheet. .
For the total light transmittance (Tt), the ratio of the incident light quantity (T1) and the total light quantity (T2) that passed through the test piece was obtained by the following formula. (Formula): Tt = T2 / T1 (%)
In addition, the measured value in Table 2 is a measured value at 550 nm.

(Measuring method of mean interval between valleys (Sm))
According to JIS B 0601 (1994), the shape of the surface uneven structure of the antiglare sheet is 8 mm, and the stylus type surface roughness measuring instrument (manufactured by Kosaka Laboratory, model name: high precision fine shape measuring instrument). Using a surf coder ET4000), the measurement was performed at a stylus speed of 500 μm / s.

(Measurement method of centerline average surface roughness (Ra))
According to JIS B 0601 (1994), the shape of the surface uneven structure of the antiglare sheet is 8 mm, and the stylus type surface roughness measuring instrument (manufactured by Kosaka Laboratory, model name: high precision fine shape measuring instrument). Using a surf coder ET4000), the measurement was performed in the same manner as the above-described method for measuring the average crevice interval (Sm).

(Haze value measurement method)
In accordance with JIS K 7105-1981, using “Suga Test Instruments Co., Ltd., model name: Digital Variable Glossmeter UGV-5DP”, make the surface of the anti-glare sheet surface uneven structure face the light source. Measured.

(Glossiness measurement method)
The 60 ° gloss was measured according to JIS K 7105-1981 using “Suga Test Instruments Co., Ltd., model name: Digital Variable Glossmeter UGV-5DP”.

(Total reflectance measurement method)
A black acrylic plate is bonded to the base material surface of the antiglare sheet on which the surface uneven structure is not formed with an adhesive to eliminate reflection on the back surface. “Murakami Color Research Laboratory, model name: GL-3D Glossmeter GM-3D Was used to measure 60 ° gloss.

Example 1
Urethane acrylic ultraviolet curable resin (Dainippon Ink Chemical Co., Ltd., trade name: Unidic) 100 parts by weight, lauryl methacrylate (Nippon Yushi Co., Ltd.) 100 parts by weight, benzophenone photopolymerization initiator (Ciba Specialty Chemicals, trade name: Irgacure 907) 4 parts by weight and 106 parts by weight of toluene were mixed to prepare a coating solution.
The obtained coating liquid was cloudy because the urethane acrylic ultraviolet curable resin and lauryl methacrylate were incompatible.
The coating solution is applied to a polyethylene terephthalate (PET) film (thickness 50 μm), dried at 25 ° C. for 2 minutes, and then irradiated with ultraviolet rays (365 nm, ultraviolet intensity 300 mJ / cm ² ) to form a cured coating on the PET film. A laminated sheet having a thickness of about 4.1 μm was produced.
Cutting the laminated sheet into strips, putting it in a pressure vessel, pressurizing it to 40 ° C. and 25 MPa, maintaining the pressure, and injecting and exhausting carbon dioxide at a gas flow rate of 5 liters / min. The operation was performed for 2 hours to extract lauryl methacrylate.
The laminated sheet after performing the extraction operation had a fine surface uneven structure showing good antiglare properties.
The amount of each reagent and the extraction conditions are shown in Table 1.
Further, the optical properties and surface roughness of the laminated sheet after the extraction operation were measured, and the results are shown in Table 2.

(Example 2)
A coating solution similar to that in Example 1 was prepared, and the same operation as in Example 1 was performed except that the coating solution was applied to a triacetylcellulose (TAC) film (thickness 50 μm), and a cured coating film was formed on the TAC film. A laminated sheet having a thickness of about 4 μm was obtained.
The laminated sheet after the extraction operation had a fine surface uneven structure showing good antiglare properties.
Table 1 shows the blending amounts and extraction conditions of each reagent, and the optical properties and surface roughness of the laminated sheet after the extraction operation were measured. The results are shown in Table 2.

(Example 3)
The same coating liquid as in Example 1 was prepared, and the coating liquid was applied to a triacetyl cellulose (TAC) film (thickness 50 μm) to form a laminated sheet having a cured coating (thickness about 4 μm) formed on the TAC film. Produced.
The laminated sheet was cut into strips of 100 mm × 150 mm and immersed in 300 cc of toluene at an ambient temperature of 25 ° C. for 10 minutes to extract lauryl methacrylate.
The laminated sheet after the extraction operation had a fine surface uneven structure showing good antiglare properties.
Table 1 shows the blending amounts and extraction conditions of each reagent, and the optical properties and surface roughness of the laminated sheet after the extraction operation were measured. The results are shown in Table 2.

Example 4
A laminated sheet in which a cured film (thickness of about 4 μm) was formed on a TAC film by performing the same operation as in Example 2 except that 100 parts by weight of lauryl acrylate (manufactured by Nippon Oil & Fats Co., Ltd.) was used instead of lauryl methacrylate. Was made.
The operation of extracting lauryl acrylate from the laminated sheet was performed in the same manner as in Example 1.
The laminated sheet after the extraction operation had a fine surface uneven structure showing good antiglare properties.
Table 1 shows the blending amounts and extraction conditions of each reagent, and the optical properties and surface roughness of the laminated sheet after the extraction operation were measured. The results are shown in Table 2.
The obtained coating solution was cloudy because the urethane acrylic ultraviolet curable resin and lauryl acrylate were incompatible.

(Example 5)
Acrylic ultraviolet curable resin (Toa Gosei Co., Ltd., pentaerythritol triacrylate) 100 parts by weight, lauryl methacrylate (Nippon Yushi Co., Ltd.) 100 parts by weight, benzophenone photopolymerization initiator (Ciba Specialty) Made by Chemicals Co., Ltd., trade name: Irgacure 907) 4 parts by weight and 106 parts by weight of toluene were mixed to prepare a coating solution, and the same operation as in Example 1 was carried out to form a cured coating (thickness 3. A laminated sheet having a thickness of 8 μm was produced.
The operation of extracting lauryl methacrylate from the laminated sheet was also performed in the same manner as in Example 1.
The laminated sheet after the extraction operation had a fine surface uneven structure showing good antiglare properties.
Table 1 shows the blending amounts and extraction conditions of each reagent, and the optical properties and surface roughness of the laminated sheet after the extraction operation were measured. The results are shown in Table 2.

(Example 6)
Acrylic ultraviolet curable resin (Toa Gosei Co., Ltd., dipentaerythritol hexaacrylate) 100 parts by weight, lauryl methacrylate (Nippon Yushi Co., Ltd.) 100 parts by weight, benzophenone photopolymerization initiator (Ciba Specialty)・ Product made by Chemicals, trade name: Irgacure 907) 4 parts by weight and 106 parts by weight of toluene were mixed to prepare a coating liquid, and the same operation as in Example 1 was carried out to form a cured coating (thickness 4) .6 μm) was produced.
The operation of extracting lauryl methacrylate from the laminated sheet was also performed in the same manner as in Example 1.
The laminated sheet after the extraction operation had a fine surface uneven structure showing good antiglare properties.
Table 1 shows the blending amounts and extraction conditions of each reagent, and the optical properties and surface roughness of the laminated sheet after the extraction operation were measured. The results are shown in Table 2.

(Example 7)
100 parts by weight of an acrylic ultraviolet curable resin (manufactured by Aldrich, tris- (2-hydroxyethyl) isocyanurate triacrylate), 100 parts by weight of lauryl acrylate (manufactured by NOF Corporation), benzophenone photopolymerization initiator (Ciba -Specialty Chemicals Co., Ltd., trade name: Irgacure 907) The same procedure as in Example 1 was carried out except that 4 parts by weight and 106 parts by weight of toluene were mixed to form a cured coating on the PET film ( A laminated sheet having a thickness of 5.1 μm was produced.
The operation of extracting lauryl methacrylate from the laminated sheet was also performed in the same manner as in Example 1.
The laminated sheet after the extraction operation had a fine surface uneven structure showing good antiglare properties.
Table 1 shows the blending amounts and extraction conditions of each reagent, and the optical properties and surface roughness of the laminated sheet after the extraction operation were measured. The results are shown in Table 2.

(Comparative Example 1)
The same procedure as in Example 1 was carried out except that 100 parts by weight of polyethylene glycol dimethyl ether (manufactured by NOF Corporation, trade name: MM500) was used instead of lauryl methacrylate used in Example 1.
In addition, since the obtained coating liquid had good compatibility with urethane acrylic type ultraviolet curable resin and polyethyleneglycol dimethyl ether, phase separation was not recognized.
As a result, the cured coating (thickness: 4.1 μm) of the laminated sheet had almost no unevenness on the surface, and the antiglare property was extremely insufficient.
Table 1 shows the blending amount and extraction conditions of each reagent, and the optical properties and surface roughness of the obtained laminated sheet were measured. The results are shown in Table 2.

(Comparative Example 2)
The same operation as in Example 5 was performed, except that a coating solution to which lauryl methacrylate was not added was used.
In addition, since the obtained coating liquid did not form the phase-separation structure, it did not become cloudy and the phase separation was not recognized also in the ultraviolet curing process.
As a result, the cured film (thickness 4 μm) of the laminated sheet had almost no irregularities on the surface, and the antiglare property was extremely insufficient.
Table 1 shows the blending amount and extraction conditions of each reagent, and the optical properties and surface roughness of the obtained laminated sheet were measured. The results are shown in Table 2.

(Comparative Example 3)
The same operation as in Example 6 was performed except that a coating solution to which lauryl methacrylate was not added was used.
In addition, since the obtained coating liquid did not form the phase-separation structure, it did not become cloudy and the phase separation was not recognized also in the ultraviolet curing process.
As a result, the cured film (thickness 4 μm) of the laminated sheet had almost no irregularities on the surface, and the antiglare property was extremely insufficient.
Table 1 shows the blending amount and extraction conditions of each reagent, and the optical properties and surface roughness of the obtained laminated sheet were measured. The results are shown in Table 2.

(Comparative Example 4)
The same operation as in Example 7 was performed, except that a coating solution to which lauryl methacrylate was not added was used.
In addition, since the obtained coating liquid did not form the phase-separation structure, it did not become cloudy and the phase separation was not recognized also in the ultraviolet curing process.
As a result, the cured film (thickness 4 μm) of the laminated sheet had almost no irregularities on the surface, and the antiglare property was extremely insufficient.
Table 1 shows the blending amount and extraction conditions of each reagent, and the optical properties and surface roughness of the obtained laminated sheet were measured. The results are shown in Table 2.

PET：ポリエチレンテレフタレート
TAC：トリアセチルセルロース
PEGジメチルエーテル：ポリエチレングリコールジメチルエーテル
PETA：ペンタエリスリトールトリアクリレート
DPEHA：ジペンタエリスリトールヘキサアクリレート
THEIC：トリス−(２−ヒドロキシエチル)イソシアヌレートトリアクリレート

PET: Polyethylene terephthalate
TAC: Triacetylcellulose
PEG dimethyl ether: polyethylene glycol dimethyl ether
PETA: Pentaerythritol triacrylate
DPEHA: Dipentaerythritol hexaacrylate
THEIC: Tris- (2-hydroxyethyl) isocyanurate triacrylate

Antiglare sheet obtained by the production method of the anti-glare sheet of the present invention has been found to have excellent anti-glare properties.

Claims (7)

An organic resin material composed of an acrylic ultraviolet curable resin having two or more functional groups polymerizable by ultraviolet irradiation in one molecule, and an alkyl (meth) acrylate which is a material incompatible with the organic resin material A first step of mixing and preparing a coating liquid;
A second step of applying the coating liquid and forming a coating film having a phase separation structure in which the organic resin material and the incompatible material are phase separated;
The coating film is subjected to a curing treatment such as an ultraviolet irradiation treatment , the organic resin material is cured to fix the phase separation structure, and then the incompatible material is removed from the coating film subjected to the curing treatment. And a third step of forming a cured resin layer having a surface uneven structure, and a method for producing an antiglare sheet. An organic resin material comprising an acrylic ultraviolet curable resin having two or more functional groups polymerizable by ultraviolet irradiation in one molecule, an alkyl (meth) acrylate and a solvent which are incompatible with the organic resin material And a first step of preparing a coating liquid,
A second step of applying the coating liquid and forming a coating film having a phase separation structure in which the organic resin material and the incompatible material are phase separated;
A solvent removal step of removing the solvent from the coating film after the second step;
The coating film from which the solvent has been removed by the solvent removal step is subjected to a curing treatment such as an ultraviolet irradiation treatment , the organic resin material is cured to fix the phase separation structure, and then the coating film subjected to the curing treatment is used. And a third step of forming a cured resin layer having a surface uneven structure by removing the incompatible material, and a method for producing an antiglare sheet. The method for producing an antiglare sheet according to claim 1 or 2, wherein the incompatible material has a molecular weight of 200 to 3,000 . The method for producing an antiglare sheet according to any one of claims 1 to 3, wherein the incompatible material in the third step is removed by solvent extraction. The method for producing an antiglare sheet according to claim 4, wherein a solvent used for the solvent extraction is liquefied carbon dioxide or carbon dioxide in a supercritical state. The method for producing an antiglare sheet according to claim 4, wherein the solvent used for the solvent extraction is an organic solvent that selectively dissolves incompatible materials. The method for producing an antiglare sheet according to any one of claims 1 to 6, wherein the antiglare sheet has a center line average surface roughness (Ra) of from 50 to 1500 nm and an average interval between valleys (Sm) of from 80 to 400 µm.