WO2006106822A1 - Light diffusion film - Google Patents

Light diffusion film Download PDF

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Publication number
WO2006106822A1
WO2006106822A1 PCT/JP2006/306655 JP2006306655W WO2006106822A1 WO 2006106822 A1 WO2006106822 A1 WO 2006106822A1 JP 2006306655 W JP2006306655 W JP 2006306655W WO 2006106822 A1 WO2006106822 A1 WO 2006106822A1
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WO
WIPO (PCT)
Prior art keywords
light diffusion
mass
parts
diffusion layer
acrylic
Prior art date
Application number
PCT/JP2006/306655
Other languages
French (fr)
Japanese (ja)
Inventor
Satoshi Hayakawa
Masanao Takashima
Satoshi Nakagawa
Yoshinosuke Shimamura
Original Assignee
Dainippon Ink And Chemicals, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dainippon Ink And Chemicals, Inc. filed Critical Dainippon Ink And Chemicals, Inc.
Publication of WO2006106822A1 publication Critical patent/WO2006106822A1/en

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0268—Diffusing elements; Afocal elements characterized by the fabrication or manufacturing method
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • G02B6/0033—Means for improving the coupling-out of light from the light guide
    • G02B6/005—Means for improving the coupling-out of light from the light guide provided by one optical element, or plurality thereof, placed on the light output side of the light guide
    • G02B6/0051—Diffusing sheet or layer
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • G02B6/0065—Manufacturing aspects; Material aspects
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices 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
    • G02F1/01—Devices 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 
    • G02F1/13—Devices 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
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336—Illuminating devices
    • G02F1/133602—Direct backlight
    • G02F1/133606—Direct backlight including a specially adapted diffusing, scattering or light controlling members
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance

Definitions

  • the present invention relates to a light diffusing film, and more particularly to a light diffusing film used as a component of a knocklight unit of a liquid crystal display device.
  • a light diffusing film is used for diffusing the light of a point light source or a linear light source, or adjusting the angle of emitted light to obtain a uniform surface illumination with high front luminance.
  • This light diffusing film is widely used in, for example, liquid crystal displays and liquid crystal televisions equipped in mobile phones and digital cameras.
  • Fig. 1 shows an example of the general configuration of a liquid crystal display device that has conventionally been installed in computers, mobile phones, digital cameras, and the like.
  • the light diffusing film 7 is usually used as one of the components of the knock light unit 2.
  • the light diffusing film 7 is disposed between the light guide plate 5 and the prism sheet 8, and its function is to deflect the outgoing light from the light guide plate 5 toward the prism sheet 8 and to retroreflect the prism sheet 8.
  • the purpose is to diffuse the emitted light for reuse.
  • FIG. 2 shows an example of a cross-sectional configuration of a general light diffusion film.
  • the light diffusion film 7 includes a transparent sheet-like base material 10, a light diffusion layer 11 formed on one surface of the base material 10, and a back surface for preventing sticking on the other surface of the base material 10.
  • Layer 12 is provided.
  • the light diffusion layer 11 contains a light diffusion material 13 and a resin binder 14.
  • a light diffusion layer composed of a synthetic resin layer in which transparent resin beads are mixed as a light diffusion material is formed on the surface of a transparent substrate.
  • transparent acrylic resin beads for example, see Patent Document 1
  • polystyrene spherical particles for example, see Patent Document 2
  • synthetic resin layer a synthetic resin layer made of a two-component curable binder prepared using a polyol resin such as acrylic polyol or polyester polyol and isocyanate is used (for example, see Patent Document 3).
  • the resin beads are synthesized.
  • the beads are preferably partially projected from the synthetic resin layer (see, for example, Patent Document 1).
  • this light diffusing film for example, when incorporated as a backlight unit of a liquid crystal display device, it gives a good diffusing effect and condensing effect to the light with the power of a knock light source, and makes a bright and uniform liquid crystal display surface. It is described that it can be preferably formed.
  • the liquid crystal display screen will be defective and the quality will be deteriorated. Punched products with missing or omissions are excluded by visual inspection; they are discarded. Accordingly, insufficient scratch resistance and detachment resistance of the resin particles have been the cause of lowering the yield of the light diffusion film and lowering the productivity.
  • the presence of beads partially protruding from the synthetic resin layer as described above is more likely to drop off because the contact area between the beads and the synthetic resin layer holding the beads is reduced.
  • it is often designed by increasing the protruding surface area of the beads to nearly half of the total surface area. Due to this problem that the fat particles easily fall off, if the light diffusion film is soiled, it is damaged, which causes a reduction in production efficiency.
  • Patent Document 1 Japanese Utility Model Publication No. 5-073602
  • Patent Document 2 Utility Model Registration No. 3010871
  • Patent Document 3 Japanese Patent Laid-Open No. 2002-357703
  • An object of the present invention is to provide a satisfactory light transmittance and light diffusibility, high scratch resistance, and the resin particles do not easily fall off from the light diffusion layer, and have a light diffusion layer.
  • the object is to provide a light diffusing film having processability.
  • the present inventor has improved the scratch resistance of the surface of the light diffusion layer by using a specific resin binder and resin particles, so that the light diffusion layer can be removed from the light diffusion layer. It was found that the fat particles did not easily fall off and a light diffusion film could be formed.
  • the present invention is a light diffusing film in which a light diffusing layer in which rosin particles are dispersed in a rosin binder is provided on at least one surface of a transparent sheet-like base material,
  • An acrylic polyol or a polyester polyol is a copolymer crosslinked with a polyisocyanate, and the resin particles contain a curing catalyst that serves as a catalyst for a crosslinking reaction with the polyisocyanate in the resin binder.
  • a light diffusing film characterized by being an acrylic urethane resin particle.
  • the reason why the light diffusion film of the present invention has good scratch resistance and the resin particles are difficult to fall off from the light diffusion layer are not necessarily clear. Since both the resin particles and the synthetic resin layer constituting the light diffusion layer are made of a copolymer prepared by polyisocyanate and polyol resin, they are extremely difficult to be damaged by themselves. There is something to do. Furthermore, since the resin particles contain a polyol resin and polyisocyanate curing catalyst, the curing reaction proceeds very quickly at the interface between the resin particles and the synthetic resin, and there is no distortion around the resin particles. This is considered to form a synthetic resin layer to hold the resin particles.
  • the light diffusion film of the present invention is used as a light diffusion material in a resin binder of a light diffusion layer.
  • a diffusion layer can be provided.
  • the acrylic urethane resin particles themselves have better scratch resistance than conventional acrylic resin particles, styrene resin particles, etc., and as a resin binder, it is easy to obtain coating film hardness, polyisocyanate crosslinking Therefore, the surface of the light diffusing layer is hardly damaged.
  • FIG. 1 is a general configuration diagram of a liquid crystal display device.
  • FIG. 2 is a cross-sectional view showing an embodiment of the light diffusion film of the present invention. It is sectional drawing which shows
  • the light diffusion film of the present invention comprises at least a transparent sheet-like substrate and a light diffusion layer formed on at least one surface of the substrate. Further, if necessary, a back layer having at least one of a sticking prevention function, an antistatic function, a scratch prevention function, a second light diffusion layer function, and the like is provided on the other surface of the base material.
  • the material for the transparent sheet-like substrate in the present invention is not particularly limited, but a polyethylene terephthalate (PET) film is preferably used from the viewpoint of surface smoothness and mechanical strength.
  • the thickness of the substrate is preferably 10 to 300 m. If it is thinner than 10 m, it becomes difficult to handle and curling due to heat shrinkage occurs, resulting in a significant decrease in workability. If it is thicker than 300 m, the visible light transmittance of the substrate itself tends to decrease, and the front brightness of the knocklight unit tends to decrease.
  • An easy-adhesion treatment layer can be provided on the surface of the transparent sheet-like base material in order to improve the adhesion between the base material surface and the light diffusion layer or a back layer formed as necessary. Examples of the easy adhesion treatment include applying and forming a resin that improves the adhesion between the two, or applying a corona treatment to the surface of the base material.
  • the light diffusion layer in the light diffusion film of the present invention contains at least a light diffusion material and a resin binder.
  • the resin particles used as the light diffusing material of the present invention are acrylic urethane resin particles.
  • Acrylic urethane resin fine particles have a high-density cross-linked structure, so they are particularly excellent in heat resistance and solvent resistance, and also have high transparency, which is a characteristic of acrylic resin.
  • the inventor when using acrylic urethane resin fine particles as a light diffusing material, is generally used as a conventional light diffusing material while maintaining the haze and transmittance required as a light diffusing film.
  • the present inventors have found that the light diffusing layer does not leave scratches more than the fine particles of poly (methyl methacrylate) (PMMA), polystyrene, silicone, and the like.
  • poly (methyl methacrylate) which is generally used as a light diffusing material in the past, has acrylic urethane resin fine particles having a high-density crosslinked structure. This is thought to be due to the fact that it has a characteristic that it is more easily plastically deformed than fine particles of resin such as polystyrene and silicone.
  • the light diffusion layer in which the acrylic urethane resin fine particles are dispersed in the resin binder is easily deformed due to the plasticity of the acrylic urethane resin fine particles, while the surface of the light diffusion layer is made of polyisopropylene.
  • the structure is protected by a hard resin binder that is three-dimensionally cross-linked with cyanate.
  • the acrylic urethane resin fine particles if the resin fine particles having hydroxyl groups on the surface are used, the hydroxyl groups on the surface of the resin fine particles are used in the cross-linking reaction of the resin binder, and the excess polyisocyanate in the resin binder.
  • Cross-linking reaction promotes the effect of the resin binder around the light diffusing material, and also forms a cross-linked structure between the light diffusing material and the resin binder. Is further increased and preferable.
  • acrylic urethane resin fine particles can be granulated through a known production process such as a polymerization process such as suspension polymerization or emulsion polymerization, or an emulsion process of a resin dissolved in an organic solvent in an aqueous medium. .
  • a polymerization process such as suspension polymerization or emulsion polymerization
  • an emulsion process of a resin dissolved in an organic solvent in an aqueous medium By adding an appropriate amount of the curing catalyst to the raw material before the granulation step, it is possible to obtain a curing catalyst that exists at least on the surface of the resin particles.
  • the surface of acrylic urethane resin particles can be surface-treated with the solvent containing the curing catalyst, but the paint that forms the light diffusion layer is stable without the risk of gelation.
  • the curing catalyst for catalyzing the crosslinking reaction by the polyisocyanate in the resin binder used in the present invention is for accelerating the crosslinking reaction at the interface between the resin binder and the resin particles. Therefore, it is not always necessary to relate to the polymerization reaction and the crosslinking reaction when forming the resin particles. However, since these curing catalysts can be used so as to exert a catalytic effect even when the resin particles are formed, the added catalyst is effective in both the resin particles and the synthetic resin layer. Preferred to use to function as.
  • acrylic urethane resin particles using a curing catalyst for example, a monomer having a hydroxyl group and a diisocyanate or a polyisocyanate are used in the presence of a curing catalyst. After prepolymer having a urethane bond by copolymerization with acrylonitrile, suspension polymerization is carried out together with an acrylic component and a polymerization initiator, so that the curing resin is contained in the resin particles and the curing catalyst action is expressed on the surface of the resin particles. It is possible to produce rosin particles that can be produced.
  • Examples of the hydroxyl group-containing monomer include diols such as polyester diol, polyether diol, polyester amide diol, and polycarbonate diol, latatane polyester polyol obtained by ring-opening polymerization of a cyclic ester monomer, polyether polyol, poly Polyols such as ether ester polyols and polycarbonate polyols, or polyalkylene glycols having a bur group in the molecule
  • diisocyanates examples include hexamethylene diisocyanate and isophorone diisocyanate.
  • polyisocyanates include polyhydric alcohols based on HDI (hexamethylene diisocyanate) and XDI (xylene diisocyanate) aliphatic isocyanates that are difficult to yellow. Adduct type, isocyanurate type trimmed based on HDI, or piuret type based on HDI.
  • Curing catalysts include triethylenediamine, N-methylpiperazine, N, N'-dimethylpentylamine, N, N'-dimethyldensylamine, which are commonly used as urethane curing catalysts.
  • N, N, ⁇ ', ⁇ monotetramethylethylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ , —tetramethylhexamethylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl 1
  • Amines such as 3-diaminobutane, tributyltin chloride, tetrabutyltin, dibutyltin dilaurate, dioctyltin dilaurate, potassium oleate, 2-ethylhexyl titanate, zinc naphthenate, sulfonic acid, phosphorus Acids such as acid esters and carboxylic acids can be used.
  • dibutyltin dilaurate and dioctyltin dilaurate are preferable because they have an excellent catalytic effect on aliphatic isocyanate groups.
  • the amount of curing catalyst contained in the resin particles is preferably 0.0001-0. 5% by mass, more preferably 0.001-0. 1% by mass.
  • the tin content attributable to the curing catalyst in the resin particles measured by ICP emission spectrometry or X-ray fluorescence analysis is 1 to 300 ppm.
  • the acrylic component to be radically polymerized with the prepolymer having a urethane bond include, for example, (meth) acrylic acid ester, nitrile derivatives and organic acid vinyl ester copolymerizable with (meth) acrylate. Examples thereof include saturated acid esters and benzene derivative monomers.
  • polymerization initiator examples include organic peroxides such as benzoyl peroxide, t-butylperoxybivalate, t-butylperoxy-2-ethylhexanate, and 2,2-azobis, as long as they generate radicals during polymerization. (Cyclohexane-1carbo nitrile) and other azo compounds.
  • suspension stabilizer used in the suspension polymerization examples include cellulose-based water-soluble resin such as methyl cellulose, hydroxy cellulose, and carboxymethyl cellulose, polybutyl alcohol, polyethylene glycol, polybutylpyrrolidone, and polyacrylic acid. Examples include salts.
  • the amount and type of suspension stabilizer to be used can be arbitrarily determined according to the stability of the suspension system. Generally, the larger the amount of suspension stabilizer, the smaller the particle size obtained with increased stability. Tend to be.
  • the shape of the acrylic urethane resin particles is preferably spherical.
  • the resin particles preferably have an average particle size in the range of 1 to 30 / ⁇ ⁇ . If the average particle diameter is smaller than 1, the light transmitted through the light diffusion layer is transmitted without being diffused, and the light diffusion effect tends to be reduced. When the average particle diameter exceeds 30 m, coarse resin particles are likely to fall off, which causes defects and tends to easily cause defects in the appearance of the coating film and the uniformity of foreign matter.
  • the light diffusing material As a part of the light diffusing material, other resin particles, inorganic particles, or inorganic mono-organic hybrid particles that do not contain a curing catalyst are mixed with the resin particles containing a curing catalyst. It is also possible to do. In that case, it is less than the addition amount of the acrylic urethane resin particles containing the curing catalyst dispersed in the resin binder as long as the various properties of the light diffusion film are not hindered. This is preferred because it increases the effect of preventing particles from falling off.
  • an average is preferably used in order to fill the gaps between the coarse particles that are easily formed to protrude on the surface of the light diffusing layer, to smooth the surface shape of the light diffusing layer, and to improve the appearance.
  • the Norder resin used in the light diffusion layer of the light diffusion film of the present invention is a copolymer in which acrylic polyol or polyester polyol is crosslinked with polyisocyanate.
  • the acrylic polyol in the present invention is an acrylic resin obtained by polymerizing a monomer component containing an unsaturated monomer having a hydroxyl group and having a (meth) acryl unit as a constituent element.
  • a copolymer containing 1 to 50% by mass of an acrylic monomer unit having a hydroxyl group which is a constituent element of the acrylic polyol in the copolymer is preferable.
  • Examples of the unsaturated monomer having a hydroxyl group include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropino methacrylate, and acrylic monomers having a selected hydroxyl group.
  • Hydroxyl-containing unsaturated monomers such as alkenyl alcohol and crotonyl alcohol.
  • a hydroxyl group obtained by a reaction of a dihydric alcohol or epoxy compound such as ethylene glycol, propylene glycol, or phenylglycidyl ether with an unsaturated carboxylic acid such as acrylic acid, maleic acid, or fumaric acid. Examples thereof include unsaturated monomers.
  • An acrylic polyol can be produced by selecting and polymerizing at least one of the above hydroxyl group-containing unsaturated monomers so as to contain a (meth) acrylic unit.
  • Acrylic polyol can be produced by polymerization with the unsaturated monomer.
  • the monomer component ratio in the copolymer is 1 to 50% for the acrylic monomer component having a hydroxyl group, and 5 to 80% for the other monomer components.
  • the hydroxyl value of the acrylic polyol is preferably 25 to 500. When the hydroxyl value is less than 25, the crosslinking density is too low, so the hardness of the light diffusion layer tends to decrease the solvent resistance. If the hydroxyl group value is greater than 500, the crosslink density is too high and it becomes brittle and the light diffusion layer cracks.
  • the hydroxyl value generally means the number of milligrams of potassium hydroxide required to neutralize acetic acid generated when acetylating a sample lg.
  • the hydroxyl value is a value converted into a hydroxyl value per lg of the solid content of the sample.
  • the above-mentioned copolymer may be used in accordance with the need for jetyl maleate, dibutyl maleate, bis (2-ethylhexyl) maleate, dibutinorefumarate, bis (2-ethylhexyl) fumarate. It is also possible to copolymerize with one or more types of resin modifiers, such as KN-phenolmaleimide.
  • the ratio of the resin modifier component in the copolymer is preferably 50% or less.
  • acrylic polyol used in the present invention examples include “Ataridic A-801-P”, “Ataridic 56-719”, “Ataridic AU-1042”, “Ataridic WDU — 938 ”,“ Ataridic A-817 ”,“ Ataridic A-823 ”,“ Ataridate A-829 ”(manufactured by Dainippon Ink & Chemicals, Inc.).
  • any resin can be used without particular limitation as long as it has transparency when formed into a coating film.
  • Polyester polyols are usually excellent in weather resistance, scratch resistance, processability, etc., and these characteristics are further improved by crosslinking with polyisocyanate.
  • the transparency is high and the fine filler is easily dispersed in the needle. For this reason, the use of the resin can increase the total light transmittance of the light diffusion film and reduce yellowing, deterioration, etc. due to ultraviolet rays.
  • the coating film of the light diffusing layer used in the present invention has a function that the elastic coating film surface absorbs the load caused by abrasion as an elastic deformation of the coating film, and alleviates the occurrence of permanent scratches on the coating film surface. It is preferable that it is a coating film which has a self-restoring property.
  • Polyester polyols used in the present invention include, for example, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and 1,3-butanediol. 1,4 butanediol, 1,5 pentanediol, neopentyl glycol, hexamethylene glycol, decamethylene glycol, 2, 2, 4 trimethyl-1,3 pentane diol, trimethylolpropane, hexanetriol, glycerin, penta Polyhydric alcohols such as erythritol, cyclohexanediol, hydrogenated bisphenol A, bis (hydroxymethyl) cyclohexinrate, xylylene glycol, and the like, for example, maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, It can be produced by reacting azelaic acid, trimetic acid, terephthalic acid, phthalic acid, is
  • the number average molecular weight of the polyester polyol obtained under the conditions of excessive hydroxyl groups is 500 to 300,000, preferably ⁇ 2000 to 100,000.
  • the hydroxyl group value is 5 or more and 300 or less, preferably 10 or more and 200 or less.
  • the number of hydroxyl groups in the polyester polyol is not particularly limited as long as it is 2 or more per molecule, but if the hydroxyl value in the solid content is 10 or less, the number of crosslinking points is reduced, and the solvent resistance and water resistance are reduced. , Film properties such as heat resistance and surface hardness tend to decrease.
  • Specific examples of polyester polyols that can be used for the resin obtained by crosslinking the polyester polyol used in the present invention with polyisocyanate include “Bernock D6—43 9”, “Bernock D—115—80”, “ Barnock D7-885, Barnock DS-1000, Barnock D-161 (Dainippon Ink and Chemicals).
  • the resin binder used in the present invention is more preferably a copolymer obtained by crosslinking an acrylic polyol with a polyisocyanate in terms of coating film hardness and transparency.
  • a polyester polyol cross-linked with a polyisocyanate in accordance with the preferred use.
  • the polyisocyanate used in the present invention is based on an aliphatic isocyanate such as HDI or XDI, which can be crosslinked with the hydroxyl group of acrylic polyol or polyester polyol, and TDI. Some of these are based on aromatic isocyanates such as MDI, HDI (hexamethylene diisocyanate), XDI (xylene diisocyanate). Polyisocyanates based on aliphatic isocyanates are preferred because they are easily yellowed by UV rays and have no weakness.
  • isocyanates are modified with polyisocyanates, such as HDI, XDI and other aliphatic isocyanates with adducts of polyhydric alcohol, HDI-based isocyanurates, or HDI-based isocyanurates.
  • polyisocyanates such as HDI, XDI and other aliphatic isocyanates with adducts of polyhydric alcohol, HDI-based isocyanurates, or HDI-based isocyanurates.
  • the piuret type that was made.
  • adduct-type polyisocyanates prepared by adding polyhydric alcohol to HDI are particularly preferred because they can provide extremely advantageous mechanical properties in the light diffusion film processing process.
  • the equivalent ratio of the isocyanate in the polyisocyanate to the hydroxyl group in the acrylic polyol or polyester polyol is preferably 0.7 to 3.0.
  • the equivalent ratio is greater than 3.0, crosslinking between polyisocyanate molecules proceeds and the light diffusion layer tends to become brittle.
  • the equivalent ratio of isocyanate to hydroxyl group (NCOZOH) is generally determined by the following formula 1.
  • Iw parts by mass in terms of solid content of polyisocyanate
  • Aw Mass parts in terms of solid content of acrylic polyol or polyester polyol
  • Ao Solid content hydroxyl value in acrylic polyol or polyester polyol
  • the blending amount of the resin particles with respect to the resin binder cannot be generally stated because the average particle diameter of the resin particles used varies depending on the film thickness of the light diffusion layer. However, it is 5 to 400 parts by weight, preferably 10 to 250 parts by weight, based on 100 parts by weight of the solid content of the resin binder. If the resin particles are less than 5 parts by mass with respect to 100 parts by mass of the resin binder, good light diffusion performance tends to be difficult to obtain. On the other hand, when the amount exceeds 400 parts by mass, the light transmittance tends to be low and it is difficult to use a sufficient amount of light.
  • resin particles containing a curing catalyst are used as a light diffusing material, and acrylic polyol or polyester polyol is crosslinked with polyisocyanate as a resin binder. Therefore, the cross-linking reaction of the resin binder at the interface between the resin particles and the resin binder proceeds preferentially and quickly, and the resin binder works as a light diffusion layer in which the resin particles are difficult to fall off. Can be provided.
  • a dispersant for example, a plasticizer, an antistatic agent, a deterioration preventing agent and the like are blended within a range that does not impair various properties of the light diffusing film. May be.
  • the film thickness of the light diffusing layer cannot be generally described because it varies depending on the blended amount of the resin particles, but the average particle diameter of the resin particles used is preferably about 5 to 50 / ⁇ ⁇ , more preferably 8 ⁇ 40 ⁇ m.
  • the back layer may be omitted.
  • a back layer is provided for the purpose of preventing stagnation.
  • the back layer of the light diffusion film of the present invention contains at least a resin binder. If necessary, a lubricant for preventing sticking, an antistatic agent for suppressing electrostatic charge on the light diffusing film, an ultraviolet absorber, an ultraviolet shielding agent, a light diffusing material and the like can be contained.
  • the resin binder contained in the back layer of the light diffusing film of the present invention is not particularly limited as long as it does not inhibit the transparency of the light diffusing film.
  • Thermoplastic methacrylic resin, thermoplastic resin It is preferable if a metataryl styrene copolymer resin, a polyester resin, or an acrylic resin is crosslinked with a polyisocyanate.
  • the light diffusion layer of the present invention can be preferably used.
  • the back layer has a function as a second light diffusion layer
  • the light diffusion layer of the present invention can be preferably used.
  • the back layer has a function as the second light diffusion layer, 5 to 50 / ⁇ ⁇ , particularly 8 to 40 / ⁇ ⁇ is preferable. Used for.
  • a light diffusing layer is formed by applying a coating material for a light diffusing layer to at least one surface of a transparent sheet-like substrate.
  • a back layer is formed by applying a back layer coating if necessary.
  • a general coating method can be used.
  • coating methods such as blade, knife, casting, dipping, impregnation machine, screen, spin, reverse roll, air doctor, gravure, spray, curtain, extrusion, fountain, kiss, rod, squeeze, forward roll, kiss roll, etc. Is available.
  • a general drying method can be used to dry the coating film.
  • drying methods such as hot air, infrared rays, microphone mouth wave, induction heating can be used. After drying, heat aging treatment is performed at a predetermined temperature and time as necessary.
  • the light diffusing film of the present invention produced as described above is a force S that is particularly useful for use as a light diffusing film constituting a backlight unit for a liquid crystal display device, and is limited to this application. It can be applied to various uses that require diffused light.
  • a reaction vessel equipped with a dried stirrer, thermometer, cooler, and nitrogen gas inlet tube is equipped with 42 parts by mass of poly-force prolataton triol (Platacel 308, manufactured by Daicel Engineering Co., Ltd.), hexamethylene diisocyanate Abbreviated as HDI.) 50 parts by mass and 0.1 part by mass of dibutyltin dilaurate were charged and reacted under stirring in a nitrogen atmosphere at 120 ° C. for 10 hours. Thereafter, unreacted HDI was removed under reduced pressure, and toluene was added to obtain a prepolymer (1) having a nonvolatile content of 90% by mass.
  • poly-force prolataton triol Platinum 308, manufactured by Daicel Engineering Co., Ltd.
  • HDI. hexamethylene diisocyanate Abbreviated as dibutyltin dilaurate
  • a separable flask equipped with a stirrer was charged with 700 parts by weight of 3% methylcellulose water, and while stirring, the prepolymer (2) 128 parts by weight, 75 parts by weight of methyl methacrylate, 25 parts by weight of n-butyl methacrylate, and t-butinolepa
  • a suspension is prepared by adding 3 parts by weight of a solution of 2 parts of xytin hexole hexanate (Strength 0, manufactured by Kayaku Akuzo).
  • the suspension was heated to 60 ° C under stirring and allowed to react for 5 hours, then heated to 100 ° C over 1 hour to separate toluene azeotropically, cooled, and then solid-liquid After separation 'washing' and drying, classification was carried out to obtain acrylic urethane resin particles ( ⁇ ). These particles had an average particle size of 6 ⁇ m and a curing catalyst content of about 0.05% by mass.
  • a separable flask equipped with a stirrer was charged with 1000 parts by mass of 3% methylcellulose water, and while stirring, 150 parts by mass of prepolymer (3), 150 parts by mass of methyl methacrylate, 3 parts by mass of t-butyl peroxybivalate (perbutyl PV) Add a solution with 20 parts by mass of toluene to make a suspension.
  • the suspension was heated to 55 ° C under stirring and allowed to react for 5 hours, then heated to 100 ° C over 1 hour to separate toluene azeotropically, cooled and then solidified. Liquid separation and washing * After drying, classification was carried out to obtain acrylic urethane resin particles (III). This grain The average particle size of the children was 6 / zm, and the content of the curing catalyst was about 0.04% by mass.
  • a separable flask equipped with a stirrer was charged with 1000 parts by weight of 3% methylcellulose water. While stirring, the prepolymer (4) 150 parts by weight, methyl metatalylate 180 parts by mass, n-butyl metatalylate 15 parts by mass, t-butyl pero Add a solution consisting of 4 parts by mass of xibivalate (perbutyl PV) to make a suspension. The suspension was heated to 55 ° C under stirring and allowed to react for 5 hours, then heated to 100 ° C over 1 hour to separate toluene azeotropically, cooled, and then solid-liquid Separation 'washing ⁇ drying and classification were carried out to obtain acrylic urethane resin particles (IV). These particles had an average particle size of 6 m and a curing catalyst content of about 0.03% by mass.
  • Synthesis Example 1 without adding dibutyltin dilaurate, the mixture was allowed to react with stirring at 120 ° C. for 24 hours in a nitrogen atmosphere. After cooling, toluene was added to obtain a prepolymer (5) having a nonvolatile content of 90% by mass.
  • Acrylic urethane resin particles (V) were obtained in the same manner as in Synthesis Example 1 except that. The average particle size of these particles was 16 ⁇ m.
  • a polyethylene terephthalate (PET) film with a thickness of 100 m as the base material apply the light diffusion layer coating material a on one side so that the dry film thickness is about 30 m, and dry with hot air.
  • a dry coating film of the light diffusion layer was obtained.
  • a light diffusing film was prepared by thermal aging treatment in a constant temperature room at 40 ° C for 48 hours.
  • Acrylic urethane resin particles (II) 125 parts by mass
  • Example 2 In the same manner as in Example 1, except that the light diffusion layer coating b was used in place of the light diffusion layer coating a in Example 1, a dry coating film was formed on the substrate to produce a light diffusion film. did
  • Acrylic urethane resin particles (III) 150 parts by mass
  • Example 2 Dried on the substrate in the same manner as in Example 1, except that the light diffusing layer coating c was used instead of the light diffusing layer coating a in Example 1 and the dry film thickness was about 15 m. A coating film was formed to produce a light diffusion film.
  • Acrylic resin particles "MBX-15" 125 parts by mass
  • Example 2 In the same manner as in Example 1, except that the light diffusion layer coating material d was used instead of the light diffusion layer coating material a in Example 1, and the dry film thickness was about 29 m. A coating film was formed to produce a light diffusion film.
  • Example 2 In the same manner as in Example 1, except that the light diffusion layer coating e was used instead of the light diffusion layer coating a in Example 1 and the dry film thickness was about 15 m. A coating film was formed to produce a light diffusion film.
  • Example 2 In the same manner as in Example 1, except that the light diffusion layer coating material f was used in place of the light diffusion layer coating material a in Example 1 and the dry film thickness was about 15 m, dry coating was performed on the substrate. A film was formed to produce a light diffusion film.
  • Example 1 instead of acrylic urethane resin particles (I), acrylic urethane resin particles Except for the use of (V), a dry coating film was formed on the substrate in the same manner as in Example 1 to produce a light diffusion film.
  • the light diffusion film was fixed so that the surfaces of the light diffusion layer were rubbed with each other, and the light diffusion surface was rubbed 1000 times with a load of 18N. After rubbing, the light diffusing film rubbed on the lower side was cut into 10 mm squares, and the falling state of the resin particles on the surface of the light diffusing layer was observed with a microscope. The following criteria were used for the evaluation of the detachment properties of the resin particles.
  • Examples 1 to 3 using acrylic urethane resin particles having a curing catalyst have good scratch resistance and drop-off resistance. It can be seen that the resin particles of Comparative Example 1 to Comparative Example 3 have lower scratch resistance and significantly lower drop resistance than Examples 1 to 3. It can be seen that even when a curing catalyst is added to the paint as in Comparative Example 3, the drop-off resistance is not improved. Further, Comparative Example 4 using acrylic urethane resin particles having no curing catalyst was more resistant to scratches than Examples 1 to 3 using acrylic urethane resin particles having a curing catalyst. It can be seen that the drop-off resistance is lowered.
  • the above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material g.
  • the equivalent ratio of isocyanate to hydroxyl group was 1.9, and the blending amount of the light diffusing material (acrylic urethane resin particles) with respect to 100 parts by mass of the solid content of the resin binder (acrylic polyol + polyisocyanate) was 150 parts by mass. .
  • Antistatic agent Power Ziegen ES—L 9 0.5 parts by mass
  • the light diffusion layer coating g Using a polyethylene terephthalate (PET) film with a thickness of 100 m as the base material, apply the light diffusion layer coating g on one side to a dry film thickness of 16 m and dry with hot air. A dry coating film of the light diffusion layer was obtained. On the other side, the back layer coating material h was applied to a dry film thickness of 2 m and dried with hot air to obtain a dry coating film for the back layer. After the coating process for light diffusion layer coating g and back coating h, the light diffusion film was prepared by storing in a constant temperature room at 40 ° C for 48 hours to accelerate the curing reaction.
  • PET polyethylene terephthalate
  • Acrylic urethane resin particles (IV) 181 parts by mass
  • the above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material i.
  • the equivalent ratio of isocyanate to hydroxyl group was 2.8, and the blending amount of light diffusing material (acrylic urethane resin particles) with respect to 100 parts by mass of the solid content of the resin binder (acrylic polyol + polyisocyanate) was 150 parts by mass. .
  • Example 4 a dry coating film was formed on the substrate in the same manner as in Example 1 except that the light diffusion layer coating i was used in place of the light diffusion layer coating g in Example 4. A film was produced.
  • Acrylic urethane resin particles (IV) 91 parts by mass
  • the above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material j.
  • the equivalent ratio of isocyanate to hydroxyl group was 0.5
  • the blending amount of the light diffusing material (acrylic urethane resin particles) with respect to 100 parts by mass of the solid content of the resin binder (acrylic polyol + polyisocyanate) was 150 parts by mass. .
  • Example 4 a dry coating film was formed on the substrate in the same manner as in Example 4 except that the light diffusion layer coating material j was used instead of the light diffusion layer coating material g in Example 4. A film was produced.
  • the above was stirred and mixed with a dispersion stirrer to obtain a k-coating material for the light diffusion layer.
  • the equivalent ratio of isocyanate to the hydroxyl group was 1.9, and the blending amount of the light diffusing material (acrylic resin particles) with respect to 100 parts by mass of the solid content of the resin binder (acrylic polyol + polyisocyanate) was 150 parts by mass.
  • Example 4 a dry coating film was formed on the substrate in the same manner as in Example 4 except that the light diffusion layer coating material k was used instead of the light diffusion layer coating material g in Example 4. A film was produced.
  • Silicone resin particles "KMP-701" 137 parts by mass
  • the above was stirred and mixed with a dispersion stirrer to obtain a coating material 1 for a light diffusion layer.
  • the equivalent ratio of isocyanate to hydroxyl group was 1.9, and the amount of the light diffusing material (silicone resin particles) to 100 parts by mass of the solid content of the resin binder (acrylic polyol + polyisocyanate) was 150 parts by mass. .
  • Example 4 a dry coating film was formed on the substrate in the same manner as in Example 4 except that the light diffusion layer coating 1 was used instead of the light diffusion layer coating g in Example 4, and the light diffusion was performed. Film Produced.
  • the above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material m.
  • the equivalent ratio of isocyanate to hydroxyl group was 1.9, and the blending amount of the light diffusing material (styrene resin particles) with respect to 100 parts by mass of the solid content of the resin binder (acrylic polyol + polyisocyanate) was 150 parts by mass. It was.
  • Example 4 a dry coating film was formed on the substrate in the same manner as in Example 4 except that the light diffusion layer coating m was used instead of the light diffusion layer coating g in Example 4, and the light diffusion was performed. A film was produced.
  • Acrylic urethane resin particles (IV) 120 parts by mass
  • the total amount of acrylic resin and 400 parts by weight of toluene were sufficiently dissolved by stirring with a dispersion stirrer, and then the remaining materials were added and stirred and mixed with a dispersion stirrer to produce a coating material for a light diffusion layer. got n.
  • the blending amount of the light diffusing material (acrylic urethane resin particles) with respect to 100 parts by mass of the solid content of the resin binder (acrylic resin) was 120 parts by mass.
  • Example 4 a dry coating film was formed on the substrate in the same manner as in Example 4 except that the light diffusion layer coating n was used instead of the light diffusion layer coating g in Example 4, and the light diffusion was performed. the film was made.
  • a predetermined number of times as shown in Table 2, the following criteria were used for visual evaluation.
  • Example 4 Acrylic urethane 1.9 o ⁇ o ⁇ o Example 5
  • Styrene 1.9 X ⁇ oo X Comparative Example 8 Acrylic Urethane 0.0 ⁇ XXXX
  • acrylic urethane resin particles have both scratch resistance, solvent resistance, and detachment resistance in the composition of the resin binder of the light diffusion layer when they do not contain isocyanate. It can be seen that the solvent resistance and dropout resistance are particularly markedly reduced. Furthermore, it can be seen that the solvent resistance and the drop-off resistance are more preferable when the ratio of isocyanate to hydroxyl group is in the appropriate range of 0.7 to 3.0 as in Example 4 and Example 5. Further, even if the ratio is within the proper range, it is understood that both the silicone resistance particles and the styrenic resin particles are low in both scratch resistance and dropout resistance.
  • the light diffusing film using a polyester polyol cross-linked with a polyisocyanate as a binder resin is examined for scratch resistance, drop-off resistance, etc.
  • Acrylic urethane resin particles (I) 385 parts by mass
  • a polyethylene terephthalate (PET) film with a thickness of 100 m as the base material apply the above light diffusion layer coating material o on one side to a dry film thickness of about 27 m and dry with hot air.
  • a dry coating film of the light diffusion layer was obtained.
  • a light diffusing film was produced by thermal aging for 48 hours in a 40 ° C constant temperature room.
  • Acrylic urethane resin particles (II) 385 parts by mass
  • Example 7 In the same manner as in Example 7, except that the light diffusion layer coating material p was used instead of the light diffusion layer coating material o in Example 7, a dry coating film was formed on the substrate to produce a light diffusion film. did.
  • Acrylic urethane resin particles (III) 235 parts by mass
  • Example 7 In the same manner as in Example 7, except that the light diffusion layer coating material q was used in place of the light diffusion layer coating material o in Example 7, and the dry film thickness was about 13 m. A coating film was formed to produce a light diffusion film.
  • Styrene resin particles "SBX-12" 275 parts by mass
  • Polyester resin "ELITEL UE3600J 125 parts by mass
  • Example 7 In the same manner as in Example 7, except that the light diffusion layer coating!: Was used instead of the light diffusion layer coating! In Example 7 and the dry film thickness was about 24 m. A coating film was formed to produce a light diffusion film.
  • the light diffusion layer coating material s was used in place of the light diffusion layer coating material o in Example 7, and dried.
  • a light-diffusing film was produced by forming a dry coating film on the substrate in the same manner as in Example 7 except that the film thickness was about 13 m.
  • Example 7 In the same manner as in Example 7, except that the light diffusion layer coating material t was used in place of the light diffusion layer coating material o in Example 7 and the dry film thickness was about 30 m, dry coating was performed on the substrate. A film was formed to produce a light diffusion film.
  • Acrylic resin particles "MBX-20" 385 parts by mass
  • Example 7 In place of the light diffusion layer coating material o in Example 7, the light diffusion layer coating material u was used and dried. A light-diffusing film was produced by forming a dry coating film on the substrate in the same manner as in Example 7, except that the dry film thickness was about 30 m.
  • Example 7 except that acrylic urethane resin particles (V) were used instead of acrylic urethane resin particles (I), a dry coating film was formed on the substrate in the same manner as in Example 7, A light diffusing film was produced.
  • Example 8 Acrylic urethane 16 0.05 Polyisole polyol and resin 'O 96 99
  • Example 9 Acrylic urethane 6 0.04 Polyester polyol- 'Lyisocyanate o ⁇ 95 99 Comparative Example 9 Styrene resin 1 2-E' Riselle resin and X ⁇ 96 98
  • Examples 7 to 9 using acrylic urethane resin particles having a curing catalyst have not only good haze and transmittance but also scratch resistance and shedding resistance. Yes.
  • the scratch resistance is lower than that of the acrylic urethane resin particles. Since the fat particles do not contain a curing catalyst, the drop-off resistance decreases. As shown in Comparative Example 11, even when a curing catalyst is added to the paint, the drop-off resistance is not improved.
  • the light diffusing film of the present invention uses, as a light diffusing material, acrylic urethane resin particles containing a curing catalyst that serves as a catalyst for the crosslinking reaction with the polyisocyanate in the resin binder of the light diffusing layer.
  • a copolymer in which acrylic polyol or polyester polyol is crosslinked with polyisocyanate as a resin binder
  • the crosslinking reaction of the resin binder at the interface between the resin particles and the resin binder has priority. It is possible to provide a light diffusing layer that progresses smoothly and quickly and is difficult for the resin particles to fall off due to the power of the resin binder.
  • the acrylic urethane resin particles themselves have better scratch resistance than conventional acrylic resin particles, styrene resin particles, etc., and as a resin binder, it is easy to obtain coating film hardness, polyisocyanate crosslinking Therefore, the surface of the light diffusing layer is hardly damaged.

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Abstract

Disclosed is a light diffusion film comprising a light diffusion layer which has adequate light transmitting properties and light diffusion properties while exhibiting high abrasion resistance. In this light diffusion film, resin particles are hardly separated from the light diffusion layer. Specifically disclosed is a light diffusion film wherein a light diffusion layer, which is obtained by dispersing acrylic urethane resin particles in a resin binder, is arranged on at least one side of a transparent sheet-like base. Preferably, the resin binder is an acrylic copolymer containing 1-50% by mass of an acrylic monomer unit having a hydroxyl group and crosslinked by a polyisocyanate, and the resin particles contain a curing catalyst which serves as a catalyst for a crosslinking reaction between an acrylic polyol and a polyisocyanate.

Description

明 細 書  Specification
光拡散フィルム  Light diffusion film
技術分野  Technical field
[0001] 本発明は光拡散性を有するフィルム、特に、液晶ディスプレイ装置のノックライトュ- ットの構成部品として用いられる光拡散フィルムに関する。  TECHNICAL FIELD [0001] The present invention relates to a light diffusing film, and more particularly to a light diffusing film used as a component of a knocklight unit of a liquid crystal display device.
背景技術  Background art
[0002] 光拡散フィルムは、点状光源または線状光源の光を拡散し、あるいは出射光の角 度を調整し、均一で、正面輝度が高い面照明を得るために用いられている。この光 拡散フィルムは、例えば、携帯電話、デジタルカメラ等に装備されている液晶ディス プレイ、液晶テレビなどに広く使用されている。  A light diffusing film is used for diffusing the light of a point light source or a linear light source, or adjusting the angle of emitted light to obtain a uniform surface illumination with high front luminance. This light diffusing film is widely used in, for example, liquid crystal displays and liquid crystal televisions equipped in mobile phones and digital cameras.
従来、コンピュータ、携帯電話、デジタルカメラ等に装備されている液晶ディスプレ ィ装置の、一般的な構成の一例を図 1に示す。光拡散フィルム 7は、通常、ノ ックライ トユニット 2の構成部品の一つとして使用されている。一般に光拡散フィルム 7は導光 板 5とプリズムシート 8との間に配置され、その働きは、導光板 5からの出射光をプリズ ムシート 8側へ偏角させ、また、プリズムシート 8から再帰反射された光を再利用のた め拡散させることにある。  Fig. 1 shows an example of the general configuration of a liquid crystal display device that has conventionally been installed in computers, mobile phones, digital cameras, and the like. The light diffusing film 7 is usually used as one of the components of the knock light unit 2. In general, the light diffusing film 7 is disposed between the light guide plate 5 and the prism sheet 8, and its function is to deflect the outgoing light from the light guide plate 5 toward the prism sheet 8 and to retroreflect the prism sheet 8. The purpose is to diffuse the emitted light for reuse.
[0003] また、一般的な光拡散フィルムの断面構成の一例を図 2に示す。一般的に、光拡散 フィルム 7は、透明なシート状基材 10、基材 10の一方の面に形成された光拡散層 11 、基材 10の他方の面に、ステイツキング防止のための背面層 12が設けられている。 光拡散層 11には、光拡散材 13および榭脂バインダー 14を含有する。  [0003] FIG. 2 shows an example of a cross-sectional configuration of a general light diffusion film. In general, the light diffusion film 7 includes a transparent sheet-like base material 10, a light diffusion layer 11 formed on one surface of the base material 10, and a back surface for preventing sticking on the other surface of the base material 10. Layer 12 is provided. The light diffusion layer 11 contains a light diffusion material 13 and a resin binder 14.
[0004] 従来の光拡散フィルムとしては、透明な基材の表面に、光拡散材として透明榭脂製 ビーズが混入された合成樹脂層から構成される光拡散層が形成され、榭脂製ビーズ としては、透明アクリル榭脂製ビーズ (例えば、特許文献 1参照）、ポリスチレン製真球 状粒子 (例えば、特許文献 2参照)等を含有するものが知られている。また合成樹脂 層としては、アクリルポリオール、ポリエステルポリオール等のポリオール樹脂とイソシ ァネートを用いて調整される 2液硬化型バインダーよりなる合成樹脂層が用いられて いる（例えば特許文献 3参照)。光拡散フィルムとしては、前記榭脂製ビーズが合成 榭脂層内に埋設されたビーズば力りでなぐこれに加えて合成樹脂層より部分的に突 設したビーズとから構成されていることが好ましく（例えば特許文献 1参照）、このよう な構成の光拡散フィルムを用いることにより、例えば液晶ディスプレイ装置のバックラ イトユニットとして組み込まれたとき、ノ ックライト光源力もの光に良好な拡散効果と集 光効果を与えて、明るく一様な液晶ディスプレイ面を形成することができ好まし 、こと が記載されている。 [0004] As a conventional light diffusion film, a light diffusion layer composed of a synthetic resin layer in which transparent resin beads are mixed as a light diffusion material is formed on the surface of a transparent substrate. Examples of known materials include transparent acrylic resin beads (for example, see Patent Document 1), polystyrene spherical particles (for example, see Patent Document 2), and the like. As the synthetic resin layer, a synthetic resin layer made of a two-component curable binder prepared using a polyol resin such as acrylic polyol or polyester polyol and isocyanate is used (for example, see Patent Document 3). As the light diffusing film, the resin beads are synthesized. In addition to the beads embedded in the resin layer, the beads are preferably partially projected from the synthetic resin layer (see, for example, Patent Document 1). By using this light diffusing film, for example, when incorporated as a backlight unit of a liquid crystal display device, it gives a good diffusing effect and condensing effect to the light with the power of a knock light source, and makes a bright and uniform liquid crystal display surface. It is described that it can be preferably formed.
[0005] し力しながら、従来の光拡散フィルムは、耐擦傷性の向上ゃ榭脂粒子の脱落防止 に関する検討が光学的特性の検討ほどには行われておらず、光拡散フィルムの耐擦 傷性ゃ榭脂粒子の脱落防止に対する処置が不十分であり、加工工程でフィルム面 に傷がつくことがあった。特にバックライトユニットの設計に従った形状に切り抜く工程 において、光拡散面が傷つき、また榭脂粒子が脱落してしまうという問題が起きやす かった。さらにこのような合成樹脂層力 の脱落した榭脂粒子が原因で、光拡散フィ ルム面に新たな傷や欠点を生じることもある。  However, conventional light diffusing films have improved scratch resistance, and studies on prevention of falling off of resin particles have not been performed as much as optical characteristics. Insufficient measures were taken to prevent the removal of fragile resin particles, and the film surface could be damaged during the processing. In particular, in the process of cutting out into a shape according to the design of the backlight unit, problems such as damage to the light diffusing surface and dropping of the resin particles were likely to occur. Furthermore, new scratches and defects may occur on the surface of the light diffusing film due to the resin particles that have lost the synthetic resin layer force.
傷ゃ榭脂粒子の脱落を有する光拡散フィルムがノ ックライトユニットに装着されると 、液晶ディスプレイ画面に欠点を生じさせ品質を低下させてしまうことから、光拡散フ イルムの加工工程において、傷や脱落の発生した打ち抜き加工品は、外観検査によ り除外さ；^棄される。従って、耐擦傷性や、榭脂粒子の耐脱落性が不十分であるこ とが、光拡散フィルムの収率を引き下げ、生産性を低下させる原因となっていた。  If a light diffusing film with detachment of the resin particles is attached to the knocklight unit, the liquid crystal display screen will be defective and the quality will be deteriorated. Punched products with missing or omissions are excluded by visual inspection; they are discarded. Accordingly, insufficient scratch resistance and detachment resistance of the resin particles have been the cause of lowering the yield of the light diffusion film and lowering the productivity.
[0006] このような傷や欠点を防ぐためには榭脂粒子や合成樹脂層の表面硬度を向上させ ることも大切であるが、それだけでは榭脂粒子の脱落や、脱落に起因する傷発生の 低減も含めた全体的な加工適性を向上させることは困難であった。 [0006] In order to prevent such scratches and defects, it is also important to improve the surface hardness of the resin particles and the synthetic resin layer, but that alone will cause the particles of the resin particles to drop off and cause scratches due to the dropping. It has been difficult to improve the overall processability including the reduction.
特に前述のように合成樹脂層より部分的に突設しているビーズの存在は、ビーズと それを保持している合成樹脂層との接触面積を小さくするためより脱落が起きやすい 。光拡散シートに要求される光学的特性によっては、ビーズの突出表面積を全表面 積の半分近くにまで増加させて設計することも多ぐ光拡散フィルムの製造工程中に 、その合成樹脂層より榭脂粒子が脱落し易ぐこの問題が原因で光拡散フィルムに汚 れゃ傷がつき、生産効率を落とす要因となっていた。  In particular, the presence of beads partially protruding from the synthetic resin layer as described above is more likely to drop off because the contact area between the beads and the synthetic resin layer holding the beads is reduced. Depending on the optical properties required for the light diffusing sheet, it is often designed by increasing the protruding surface area of the beads to nearly half of the total surface area. Due to this problem that the fat particles easily fall off, if the light diffusion film is soiled, it is damaged, which causes a reduction in production efficiency.
特許文献 1 :実開平 5— 073602号公報 特許文献 2：実用新案登録 3010871号 Patent Document 1: Japanese Utility Model Publication No. 5-073602 Patent Document 2: Utility Model Registration No. 3010871
特許文献 3：特開 2002— 357703号公報  Patent Document 3: Japanese Patent Laid-Open No. 2002-357703
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0007] 本発明の目的は、十分な光透過性と光拡散性を有し、耐擦傷性が高ぐ且つ、光 拡散層から樹脂粒子が脱落し難 、光拡散層を有し、良好な加工適性を有する光拡 散フィルムを提供することにある。 [0007] An object of the present invention is to provide a satisfactory light transmittance and light diffusibility, high scratch resistance, and the resin particles do not easily fall off from the light diffusion layer, and have a light diffusion layer. The object is to provide a light diffusing film having processability.
課題を解決するための手段  Means for solving the problem
[0008] 本発明者は、上記目的を達成すべく鋭意研究を重ねた結果、特定の榭脂バインダ 一と榭脂粒子を用いることにより光拡散層面の耐擦傷性を高め、光拡散層から榭脂 粒子が脱落し難 、光拡散フィルムを形成できることを見 、だした。 [0008] As a result of intensive studies to achieve the above object, the present inventor has improved the scratch resistance of the surface of the light diffusion layer by using a specific resin binder and resin particles, so that the light diffusion layer can be removed from the light diffusion layer. It was found that the fat particles did not easily fall off and a light diffusion film could be formed.
すなわち本発明は、透明なシート状基材の少なくとも一方の面に、榭脂バインダー 中に榭脂粒子を分散させた光拡散層を設けた光拡散フィルムであって、前記榭脂バ インダ一はアクリルポリオールまたはポリエステルポリオールがポリイソシァネートで架 橋された共重合体であり、かつ前記榭脂粒子が、前記榭脂バインダーにおいて前記 ポリイソシァネートによる架橋反応の触媒となる硬化触媒を含有しているアクリルウレ タン榭脂粒子である事を特徴とする光拡散フィルムを提供する。  That is, the present invention is a light diffusing film in which a light diffusing layer in which rosin particles are dispersed in a rosin binder is provided on at least one surface of a transparent sheet-like base material, An acrylic polyol or a polyester polyol is a copolymer crosslinked with a polyisocyanate, and the resin particles contain a curing catalyst that serves as a catalyst for a crosslinking reaction with the polyisocyanate in the resin binder. Provided is a light diffusing film characterized by being an acrylic urethane resin particle.
本発明の光拡散フィルムが良好な耐擦傷性を有し、榭脂粒子が光拡散層から脱落 し難い理由は、必ずしも全て明確というわけではない。榭脂粒子と光拡散層を構成す る合成樹脂層がともにポリイソシァネートとポリオール榭脂によって調整された共重合 体によって構成されて ヽるため、それ自体として極めて傷付き難!ヽものであることがあ げられる。さらに榭脂粒子がポリオール樹脂とポリイソシァネートの硬化触媒を含有し ているため、榭脂粒子と合成樹脂の界面で極めて速やかに硬化反応が進行し、まず 榭脂粒子の周囲に歪みの無い合成樹脂層を形成して榭脂粒子を保持するためと考 えられる。  The reasons why the light diffusion film of the present invention has good scratch resistance and the resin particles are difficult to fall off from the light diffusion layer are not necessarily clear. Since both the resin particles and the synthetic resin layer constituting the light diffusion layer are made of a copolymer prepared by polyisocyanate and polyol resin, they are extremely difficult to be damaged by themselves. There is something to do. Furthermore, since the resin particles contain a polyol resin and polyisocyanate curing catalyst, the curing reaction proceeds very quickly at the interface between the resin particles and the synthetic resin, and there is no distortion around the resin particles. This is considered to form a synthetic resin layer to hold the resin particles.
発明の効果  The invention's effect
[0009] 本発明の光拡散フィルムは、光拡散材として、光拡散層の榭脂バインダーにおいて 前記ポリイソシァネートによる架橋反応の触媒となる硬化触媒を含有しているアクリル ウレタン榭脂粒子を用い、榭脂バインダーとしてアクリルポリオールまたはポリエステ ルポリオールがポリイソシァネートで架橋された共重合体を用いて 、るために、榭脂 粒子と榭脂バインダーとの界面における榭脂バインダーの架橋反応が優先的かつ速 やかに進行し、榭脂バインダー力ゝら榭脂粒子が脱落し難 ヽ光拡散層を提供する事が できる。さらにアクリルウレタン榭脂粒子自体が従来のアクリル榭脂粒子、スチレン榭 脂粒子等に比べて耐擦傷性が良好であり、また、榭脂バインダーとして、塗膜硬度の 得やす 、ポリイソシァネート架橋による共重合体を用いて 、るために光拡散層面が 傷つき難い。一方、硬化触媒量は光学特性を阻害する程度まで添加する必要はなく 、従来の光拡散フィルムと同様の光透過性と光拡散性を維持することが可能である。 図面の簡単な説明 [0009] The light diffusion film of the present invention is used as a light diffusion material in a resin binder of a light diffusion layer. A copolymer obtained by crosslinking acrylic polyol or polyester polyol with polyisocyanate as a resin binder using acrylic urethane resin particles containing a curing catalyst to be a catalyst for a crosslinking reaction with the polyisocyanate. Therefore, the cross-linking reaction of the resin binder at the interface between the resin particles and the resin binder proceeds preferentially and quickly, and the resin particles hardly fall off due to the power of the resin binder. A diffusion layer can be provided. Furthermore, the acrylic urethane resin particles themselves have better scratch resistance than conventional acrylic resin particles, styrene resin particles, etc., and as a resin binder, it is easy to obtain coating film hardness, polyisocyanate crosslinking Therefore, the surface of the light diffusing layer is hardly damaged. On the other hand, it is not necessary to add the curing catalyst amount to the extent that the optical properties are hindered, and it is possible to maintain the same light transmittance and light diffusibility as those of conventional light diffusion films. Brief Description of Drawings
[図 1]液晶ディスプレイ装置の一般的な構成図である。 FIG. 1 is a general configuration diagram of a liquid crystal display device.
[図 2]本発明の光拡散フィルムの一実施例を示す断面図である。を示す断面図であ  FIG. 2 is a cross-sectional view showing an embodiment of the light diffusion film of the present invention. It is sectional drawing which shows
符号の説明 Explanation of symbols
1. 液晶ユニット  1. LCD unit
2 ノ ックライトユニット  2 Knocklight unit
3. 光源  3. Light source
4. 反射フィルム  4. Reflective film
5 導光板  5 Light guide plate
6. 反射シート  6. Reflective sheet
7 光拡散フィルム  7 Light diffusion film
8 プリズムシート  8 Prism sheet
9. 保護フィルム  9. Protective film
10 透明なシート状基材  10 Transparent sheet base material
11 光拡散層  11 Light diffusion layer
12 背面層  12 Back layer
13 光拡散材 14 榭脂バインダー 13 Light diffusing material 14 Oil binder
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0012] まず、本発明の光拡散フィルムの構造について説明する。本発明の光拡散フィル ムは、少なくとも、透明なシート状基材、および基材の少なくとも一方の面に形成され た光拡散層から構成される。また、必要に応じ、基材の他方の面に、ステイツキング防 止機能、帯電防止機能、傷つき防止機能、第二の光拡散層機能などのうち一つ以上 を有する背面層が設けられて 、てもよ 、。  [0012] First, the structure of the light diffusion film of the present invention will be described. The light diffusion film of the present invention comprises at least a transparent sheet-like substrate and a light diffusion layer formed on at least one surface of the substrate. Further, if necessary, a back layer having at least one of a sticking prevention function, an antistatic function, a scratch prevention function, a second light diffusion layer function, and the like is provided on the other surface of the base material. Anyway.
[0013] 本発明における透明なシート状基材には、特にその材料について限定されないが 、表面の平滑性や機械的強度から、ポリエチレンテレフタレート（PET)フィルムを使 用することが好ましい。基材の厚さは、 10〜300 mであることが好ましい。 10 m り薄い場合、取り扱いが困難となるばかりでなぐ熱収縮に起因するカールが発生し て作業性を著しく低下するなど、加工性が低下する。 300 mより厚い場合、基材そ のものの可視光透過率が低下し、ノ ックライトユニットの正面輝度が低下する傾向が ある。透明なシート状基材の表面には、基材表面と光拡散層あるいは必要に応じて 形成される背面層との密着性を向上させるため、易接着処理層を設ける事ができる。 易接着処理としては、両者の密着性を向上させる榭脂を塗布形成する、あるいは基 材表面にコロナ処理を施すなどが挙げられる。  [0013] The material for the transparent sheet-like substrate in the present invention is not particularly limited, but a polyethylene terephthalate (PET) film is preferably used from the viewpoint of surface smoothness and mechanical strength. The thickness of the substrate is preferably 10 to 300 m. If it is thinner than 10 m, it becomes difficult to handle and curling due to heat shrinkage occurs, resulting in a significant decrease in workability. If it is thicker than 300 m, the visible light transmittance of the substrate itself tends to decrease, and the front brightness of the knocklight unit tends to decrease. An easy-adhesion treatment layer can be provided on the surface of the transparent sheet-like base material in order to improve the adhesion between the base material surface and the light diffusion layer or a back layer formed as necessary. Examples of the easy adhesion treatment include applying and forming a resin that improves the adhesion between the two, or applying a corona treatment to the surface of the base material.
[0014] 本発明の光拡散フィルムにおける光拡散層は、少なくとも光拡散材及び樹脂バイン ダーを含有する。本発明の光拡散材として用いられる榭脂粒子は、アクリルウレタン 榭脂粒子である。  [0014] The light diffusion layer in the light diffusion film of the present invention contains at least a light diffusion material and a resin binder. The resin particles used as the light diffusing material of the present invention are acrylic urethane resin particles.
アクリルウレタン榭脂微粒子は、高密度の架橋構造をもつことにより、特に耐熱性と 耐溶剤性に優れており、かつ、アクリル榭脂の特徴である高い透明性も有している。 発明者は、アクリルウレタン榭脂微粒子を光拡散材として用いた場合、光拡散フィル ムとして必要なヘイズ、透過率を維持しつつ、かつ、従来光拡散材として一般的に用 いられている、ポリメチルメタタリレート（PMMA)、ポリスチレン、シリコーン等の榭脂 微粒子に比べて、光拡散層により擦過傷が残りにく 、と 、う特徴を見出した。  Acrylic urethane resin fine particles have a high-density cross-linked structure, so they are particularly excellent in heat resistance and solvent resistance, and also have high transparency, which is a characteristic of acrylic resin. The inventor, when using acrylic urethane resin fine particles as a light diffusing material, is generally used as a conventional light diffusing material while maintaining the haze and transmittance required as a light diffusing film. The present inventors have found that the light diffusing layer does not leave scratches more than the fine particles of poly (methyl methacrylate) (PMMA), polystyrene, silicone, and the like.
[0015] この理由について、発明者らは、アクリルウレタン榭脂微粒子が、高密度の架橋構 造をもちながら、従来光拡散材として一般的に用いられているポリメチルメタタリレート 、ポリスチレン、シリコーンなどの榭脂微粒子に比べて塑性変形しやすいという特徴を 持つことに起因すると考えている。すなわち、アクリルウレタン榭脂微粒子が榭脂バイ ンダー中に分散した光拡散層は、内部がアクリルウレタン榭脂微粒子の塑性のため に変形しやすくなつており、一方その表面はアクリル榭脂がポリイソシァネートにより 三次元架橋された硬い榭脂バインダーで保護された構造となるため、外部力もの応 力により破損しにく 、特性を持つことができたと思われる。 [0015] For this reason, the inventors of the present invention have disclosed that poly (methyl methacrylate), which is generally used as a light diffusing material in the past, has acrylic urethane resin fine particles having a high-density crosslinked structure. This is thought to be due to the fact that it has a characteristic that it is more easily plastically deformed than fine particles of resin such as polystyrene and silicone. In other words, the light diffusion layer in which the acrylic urethane resin fine particles are dispersed in the resin binder is easily deformed due to the plasticity of the acrylic urethane resin fine particles, while the surface of the light diffusion layer is made of polyisopropylene. The structure is protected by a hard resin binder that is three-dimensionally cross-linked with cyanate.
アクリルウレタン榭脂微粒子としては、表面に水酸基を有する榭脂微粒子を用いる と、榭脂バインダーの架橋反応において、榭脂微粒子表面の水酸基が、榭脂バイン ダ一中の過剰分のポリイソシァネートと架橋反応することにより、光拡散材の周囲の 榭脂バインダーの効果が促進されるとともに、光拡散材と榭脂バインダーとの間でも 架橋構造が形成されるため、光拡散層としての架橋密度がさらに高められ好ましい。  As the acrylic urethane resin fine particles, if the resin fine particles having hydroxyl groups on the surface are used, the hydroxyl groups on the surface of the resin fine particles are used in the cross-linking reaction of the resin binder, and the excess polyisocyanate in the resin binder. Cross-linking reaction promotes the effect of the resin binder around the light diffusing material, and also forms a cross-linked structure between the light diffusing material and the resin binder. Is further increased and preferable.
[0016] これらアクリルウレタン榭脂微粒子は懸濁重合、乳化重合等の重合プロセスや、有 機溶剤に溶解した榭脂の水性媒体中への乳化プロセス等公知の製造過程を通じて 造粒することができる。そして硬化触媒はこれら造粒工程前の原料に適量添加して おくことで、少なくとも樹脂粒子表面に硬化触媒が存在しているものを得ることができ る。  [0016] These acrylic urethane resin fine particles can be granulated through a known production process such as a polymerization process such as suspension polymerization or emulsion polymerization, or an emulsion process of a resin dissolved in an organic solvent in an aqueous medium. . By adding an appropriate amount of the curing catalyst to the raw material before the granulation step, it is possible to obtain a curing catalyst that exists at least on the surface of the resin particles.
これら硬化触媒を含まな!/ヽアクリルウレタン榭脂粒子の表面を、前記硬化触媒を含 有する溶剤を用いて表面処理することもできるが、光拡散層を形成する塗料がゲル 化のおそれなく安定して塗布できるためには、榭脂粒子の製造段階で添加されその まま榭脂粒子表面に残留して 、る硬化触媒を用いることが好ま 、。  These curing catalysts are not included! / The surface of acrylic urethane resin particles can be surface-treated with the solvent containing the curing catalyst, but the paint that forms the light diffusion layer is stable without the risk of gelation. In order to be able to be applied, it is preferable to use a curing catalyst which is added at the production stage of the resin particles and remains on the surface of the resin particles as it is.
[0017] 本発明において使用される榭脂バイダーにおいてポリイソシァネートによる架橋反 応を触媒する硬化触媒は、榭脂バインダーと榭脂粒子との界面にぉ 、て架橋反応を 促進するためのものであるので、必ずしも榭脂粒子形成時の重合反応、架橋反応に 係わるものである必要はない。しかし、これら硬化触媒は榭脂粒子形成時においても 触媒効果を発揮するように使用しうるものであるため、添加した触媒が榭脂粒子と合 成榭脂層の双方にぉ 、て有効に触媒として機能するように用いることが好ま 、。 硬化触媒を用いたアクリルウレタン榭脂粒子の製造方法としては、例えば、水酸基を 有するモノマーとジイソシァネート類あるいはポリイソシァネート類を硬化触媒存在下 で共重合させてウレタン結合を有するプレボリマーとした後、アクリル成分と重合開始 剤と共に懸濁重合することで榭脂粒子中に硬化触媒を含有し、榭脂粒子表面にお いて硬化触媒作用を発現させる事のできる榭脂粒子を作製することができる。 [0017] The curing catalyst for catalyzing the crosslinking reaction by the polyisocyanate in the resin binder used in the present invention is for accelerating the crosslinking reaction at the interface between the resin binder and the resin particles. Therefore, it is not always necessary to relate to the polymerization reaction and the crosslinking reaction when forming the resin particles. However, since these curing catalysts can be used so as to exert a catalytic effect even when the resin particles are formed, the added catalyst is effective in both the resin particles and the synthetic resin layer. Preferred to use to function as. As a method for producing acrylic urethane resin particles using a curing catalyst, for example, a monomer having a hydroxyl group and a diisocyanate or a polyisocyanate are used in the presence of a curing catalyst. After prepolymer having a urethane bond by copolymerization with acrylonitrile, suspension polymerization is carried out together with an acrylic component and a polymerization initiator, so that the curing resin is contained in the resin particles and the curing catalyst action is expressed on the surface of the resin particles. It is possible to produce rosin particles that can be produced.
[0018] 前記水酸基を有するモノマーとしては例えば、ポリエステルジオール、ポリエーテル ジオール、ポリエステルアミドジオール、ポリカーボネートジオール等のジオール類、 環状エステルモノマーの開環重合により得られるラタトン系ポリエステルポリオール、 ポリエーテルポリオール、ポリエーテル ·エステルポリオール、ポリカーボネートポリオ ール等のポリオール類あるいは分子中にビュル基を有するポリアルキレングリコール [0018] Examples of the hydroxyl group-containing monomer include diols such as polyester diol, polyether diol, polyester amide diol, and polycarbonate diol, latatane polyester polyol obtained by ring-opening polymerization of a cyclic ester monomer, polyether polyol, poly Polyols such as ether ester polyols and polycarbonate polyols, or polyalkylene glycols having a bur group in the molecule
(メタ)アタリレート類が挙げられる。 (Meth) atarylates are mentioned.
ジイソシァネート類としては例えば、へキサメチレンジイソシァネート、イソホロンジイソ シァネート等が挙げられる。ポリイソシァネート類としては例えば、黄変し難い HDI ( へキサメチレンジイソシァネート）系、 XDI (キシレンジイソシァネート）系の脂肪族イソ シァネートをベースに多価アルコールを付カ卩したァダクト型、 HDIをベースに三量ィ匕 したイソシァヌレート型、または HDIをベースにしたピウレット型などが挙げられる。  Examples of diisocyanates include hexamethylene diisocyanate and isophorone diisocyanate. Examples of polyisocyanates include polyhydric alcohols based on HDI (hexamethylene diisocyanate) and XDI (xylene diisocyanate) aliphatic isocyanates that are difficult to yellow. Adduct type, isocyanurate type trimmed based on HDI, or piuret type based on HDI.
[0019] 硬化触媒の種類としては、ウレタン硬化触媒として一般的に使用されているトリエチレ ンジァミン、 N—メチルピペラジン、 N, N'—ジメチルペンジルァミン、 N, N'—ジメチ ルドデンシルァミン、 N, N, Ν' , Ν，一テトラメチルエチレンジァミン、 Ν, Ν, Ν' , Ν， —テトラメチルへキサメチレンジァミン、 Ν, Ν, Ν' , Ν'—テトラメチル 1, 3—ジァミノ ブタンなどのアミン類、塩化トリブチル錫、テトラブチル錫、ジブチル錫ジラウレート、 ジォクチル錫ジラウレート、ォレイン酸カリウム、チタン酸 2—ェチルへキシル、ナフテ ン酸亜鉛などの金属化合物、スルホン酸、リン酸エステル、カルボン酸などの酸が使 用可能である。特に、ジブチル錫ジラウレート、ジォクチル錫ジラウレートが、脂肪族 イソシァネート基に対しても優れた触媒効果を有するため好適である。榭脂粒子に含 有される硬化触媒量は、 0. 0001-0. 5質量％が好ましぐ 0. 001-0. 1質量％が さらに好ましい。 [0019] Curing catalysts include triethylenediamine, N-methylpiperazine, N, N'-dimethylpentylamine, N, N'-dimethyldensylamine, which are commonly used as urethane curing catalysts. , N, N, Ν ', Ν, monotetramethylethylenediamine, Ν, Ν, Ν', Ν, —tetramethylhexamethylenediamine, Ν, Ν, Ν ', Ν'-tetramethyl 1 , Amines such as 3-diaminobutane, tributyltin chloride, tetrabutyltin, dibutyltin dilaurate, dioctyltin dilaurate, potassium oleate, 2-ethylhexyl titanate, zinc naphthenate, sulfonic acid, phosphorus Acids such as acid esters and carboxylic acids can be used. In particular, dibutyltin dilaurate and dioctyltin dilaurate are preferable because they have an excellent catalytic effect on aliphatic isocyanate groups. The amount of curing catalyst contained in the resin particles is preferably 0.0001-0. 5% by mass, more preferably 0.001-0. 1% by mass.
特に錫を含有する硬化触媒を使用する場合には、 ICP発光分光分析法または蛍 光 X線分析法で測定した榭脂粒子中の硬化触媒起因の錫含有量が l〜300ppmで あることが好ましい。 [0020] 前記ウレタン結合を有するプレボリマーとラジカル重合させるアクリル成分としては例 えば、（メタ）アクリル酸のエステルイ匕物、二トリル誘導体および (メタ）アタリレートと共 重合しうる有機酸ビニルエステル、不飽和酸エステル、ベンゼン誘導体系モノマー等 が挙げられる。 In particular, when a curing catalyst containing tin is used, it is preferable that the tin content attributable to the curing catalyst in the resin particles measured by ICP emission spectrometry or X-ray fluorescence analysis is 1 to 300 ppm. . [0020] Examples of the acrylic component to be radically polymerized with the prepolymer having a urethane bond include, for example, (meth) acrylic acid ester, nitrile derivatives and organic acid vinyl ester copolymerizable with (meth) acrylate. Examples thereof include saturated acid esters and benzene derivative monomers.
重合開始剤としては例えば、重合時にラジカルを発生するものであればよぐベンゾ ィルパーオキサイド、 t ブチルパーォキシビバレート、 t ブチルパーォキシ 2— ェチルへキサネート等の有機過酸化物や 2, 2ァゾビス（シクロへキサン— 1 カルボ 二トリル)等のァゾィ匕合物等が挙げられる。  Examples of the polymerization initiator are organic peroxides such as benzoyl peroxide, t-butylperoxybivalate, t-butylperoxy-2-ethylhexanate, and 2,2-azobis, as long as they generate radicals during polymerization. (Cyclohexane-1carbo nitrile) and other azo compounds.
また、懸濁重合で使用される懸濁安定剤としては例えば、メチルセルロース、ヒドロキ シェチルセルロース、カルボキシメチルセルロース等のセルロース系水溶性榭脂、ポ リビュルアルコール、ポリエチレングリコール、ポリビュルピロリドン、ポリアクリル酸塩 類等が挙げられる。使用する懸濁安定剤の量や種類は、懸濁系の安定性に応じて 任意に決める事ができ、一般に懸濁安定剤の量が多くなると安定性が増して得られ る粒径が小さくなる傾向がある。  Examples of the suspension stabilizer used in the suspension polymerization include cellulose-based water-soluble resin such as methyl cellulose, hydroxy cellulose, and carboxymethyl cellulose, polybutyl alcohol, polyethylene glycol, polybutylpyrrolidone, and polyacrylic acid. Examples include salts. The amount and type of suspension stabilizer to be used can be arbitrarily determined according to the stability of the suspension system. Generally, the larger the amount of suspension stabilizer, the smaller the particle size obtained with increased stability. Tend to be.
[0021] アクリルウレタン榭脂粒子の形状としては、真球状であることが好ま 、。該榭脂粒 子は、平均粒子径が 1〜30 /ζ πιの範囲にあることが好ましい。平均粒子径が 1より小 さいと、光拡散層を透過する光が拡散されずに透過するようになり、光拡散効果が低 下する傾向にある。平均粒子径が 30 mを超えると、粗大榭脂粒子が脱落しやすく なるため欠点を生ずる原因となり易ぐ塗膜外観上も異物感のある均一性を欠いたも のとなりやすい傾向にある。  [0021] The shape of the acrylic urethane resin particles is preferably spherical. The resin particles preferably have an average particle size in the range of 1 to 30 / ζ πι. If the average particle diameter is smaller than 1, the light transmitted through the light diffusion layer is transmitted without being diffused, and the light diffusion effect tends to be reduced. When the average particle diameter exceeds 30 m, coarse resin particles are likely to fall off, which causes defects and tends to easily cause defects in the appearance of the coating film and the uniformity of foreign matter.
[0022] また、光拡散材の一部に、硬化触媒を含有していない他の榭脂粒子、無機粒子、 または無機一有機ハイブリッド粒子を、硬化触媒を含有した榭脂粒子と混合して使用 する事も可能である。その場合、光拡散フィルムの諸特性を阻害しない範囲で、榭脂 ノインダ一に分散させる硬化触媒を含有したアクリルウレタン榭脂粒子の添加量より も少な!/ヽ添加量とする事が、榭脂粒子の脱落防止効果を高める点から好ま ヽ。 さらに、光拡散層表面に突出して形成されやすい粗大粒子どうしの隙間を穴埋めし 、光拡散層表面形状をなめらかにし、外観を向上させるために、光拡散材の一部とし て、好ましくは、平均粒子径力^〜 5 mの真球状榭脂微粒子を含有することができ る。 [0022] In addition, as a part of the light diffusing material, other resin particles, inorganic particles, or inorganic mono-organic hybrid particles that do not contain a curing catalyst are mixed with the resin particles containing a curing catalyst. It is also possible to do. In that case, it is less than the addition amount of the acrylic urethane resin particles containing the curing catalyst dispersed in the resin binder as long as the various properties of the light diffusion film are not hindered. This is preferred because it increases the effect of preventing particles from falling off. Further, as a part of the light diffusing material, an average is preferably used in order to fill the gaps between the coarse particles that are easily formed to protrude on the surface of the light diffusing layer, to smooth the surface shape of the light diffusing layer, and to improve the appearance. Can contain spherical spherical resin fine particles with particle diameter ^ ~ 5 m The
[0023] 本発明の光拡散フィルムの光拡散層に用いられるノインダー榭脂は、アクリルポリ オールまたはポリエステルポリオールがポリイソシァネートで架橋された共重合体で ある。  [0023] The Norder resin used in the light diffusion layer of the light diffusion film of the present invention is a copolymer in which acrylic polyol or polyester polyol is crosslinked with polyisocyanate.
本発明でアクリルポリオールとは、水酸基を有する不飽和モノマーを含むモノマー成 分を重合して得られ、かつ (メタ)アクリル単位を構成要素として有するアクリル系榭脂 である。  The acrylic polyol in the present invention is an acrylic resin obtained by polymerizing a monomer component containing an unsaturated monomer having a hydroxyl group and having a (meth) acryl unit as a constituent element.
アクリルポリオールがポリイソシァネートで架橋された共重合体としては、共重合体 中にアクリルポリオールの構成要素である水酸基を有するアクリルモノマー単位を 1 〜50質量％含有する共重合体が好ま 、。  As the copolymer obtained by crosslinking the acrylic polyol with polyisocyanate, a copolymer containing 1 to 50% by mass of an acrylic monomer unit having a hydroxyl group which is a constituent element of the acrylic polyol in the copolymer is preferable.
[0024] 水酸基を有する不飽和モノマーとしては、ヒドロキシェチルアタリレート、ヒドロキシェ チノレメタタリレート、ヒドロキシプロピルアタリレート、ヒドロキシプロピノレメタタリレートな ど力 選ばれる水酸基を有するアクリルモノマーゃァリルアルコール、ケィヒアルコー ル、クロトニルアルコール等の水酸基含有不飽和モノマー。あるいは例えばエチレン グリコール、プロプレングリコール、フエ-ルグリシジルエーテル等の 2価アルコールま たはエポキシ化合物と、例えばアクリル酸、マレイン酸、フマル酸等の不飽和カルボ ン酸等との反応で得られる水酸基含有不飽和モノマー等が挙げることができる。（メタ )アクリル単位を含むように上記水酸基含有不飽和モノマー等力 少なくとも 1つ以上 を選択し重合させアクリルポリオールを製造することができる。 [0024] Examples of the unsaturated monomer having a hydroxyl group include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropino methacrylate, and acrylic monomers having a selected hydroxyl group. Hydroxyl-containing unsaturated monomers such as alkenyl alcohol and crotonyl alcohol. Alternatively, for example, a hydroxyl group obtained by a reaction of a dihydric alcohol or epoxy compound such as ethylene glycol, propylene glycol, or phenylglycidyl ether with an unsaturated carboxylic acid such as acrylic acid, maleic acid, or fumaric acid. Examples thereof include unsaturated monomers. An acrylic polyol can be produced by selecting and polymerizing at least one of the above hydroxyl group-containing unsaturated monomers so as to contain a (meth) acrylic unit.
またメチルメタタリレート、ブチルメタタリレート、ラウリルメタタリレート、メチルアタリレ ート、ェチルアタリレート、ブチルアタリレート、イソブチルアタリレート、 2—ェチルへキ シルアタリレート、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、 N—メチロ ールアクリルアミド、グリシジルアタリレート、グリシジルメタタリレートなどのアクリルモノ マー、およびスチレン、アクリロニトリルなどカゝら選ばれる 1種類または 2種類以上のェ チレン性不飽和モノマーを上記水酸基含有不飽和モノマーと重合してアクリルポリオ ールを製造することができる。  Also, methyl methacrylate, butyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethyl hexyl acrylate, acrylic acid, methacrylic acid, acrylamide, One or more ethylenically unsaturated monomers selected from acrylic monomers such as methacrylamide, N-methylolacrylamide, glycidyl acrylate, glycidyl methacrylate, and styrene, acrylonitrile, etc. Acrylic polyol can be produced by polymerization with the unsaturated monomer.
共重合体中のモノマー成分比率としては、水酸基を有するアクリルモノマー成分が 1〜50%、その他のモノマー成分が 5〜80%である。 [0025] アクリルポリオールの水酸基価は 25〜500が好ましい。水酸基価が 25より小さい場 合、架橋密度が低すぎるために、光拡散層の硬度ゃ耐溶剤性が低下しやすい。水 酸基価が 500より大きい場合、架橋密度が高すぎるために脆くなり、光拡散層の割れThe monomer component ratio in the copolymer is 1 to 50% for the acrylic monomer component having a hydroxyl group, and 5 to 80% for the other monomer components. [0025] The hydroxyl value of the acrylic polyol is preferably 25 to 500. When the hydroxyl value is less than 25, the crosslinking density is too low, so the hardness of the light diffusion layer tends to decrease the solvent resistance. If the hydroxyl group value is greater than 500, the crosslink density is too high and it becomes brittle and the light diffusion layer cracks.
、欠けが生じやすくなり、加工時における作業性を低下させる傾向にある。 , Chipping tends to occur, and workability during processing tends to be reduced.
ここで、水酸基価とは、一般に、試料 lgをァセチル化する時生ずる酢酸を中和する のに要する水酸ィ匕カリウムのミリグラム数をいう。水酸基価は、試料であるアクリルポリ オール力 Sワニス (溶液)の場合には、試料の固形分 lg当たりの水酸基価に換算した数 値である。 Here, the hydroxyl value generally means the number of milligrams of potassium hydroxide required to neutralize acetic acid generated when acetylating a sample lg. In the case of acrylic polyol force S varnish (solution) as a sample, the hydroxyl value is a value converted into a hydroxyl value per lg of the solid content of the sample.
[0026] また、上記共重合体は、必要に応じてジェチルマレエート、ジブチルマレエート、ビ ス（2—ェチルへキシル）マレエート、ジブチノレフマレート、ビス（2—ェチルへキシル） フマレー K N—フエ-ルマレイミドなど力も選ばれる 1種類または 2種類以上の榭脂 改質剤と共重合させる事も可能である。共重合体中の榭脂改質剤成分比率としては 、 50%以下とすることが好ましい。  [0026] In addition, the above-mentioned copolymer may be used in accordance with the need for jetyl maleate, dibutyl maleate, bis (2-ethylhexyl) maleate, dibutinorefumarate, bis (2-ethylhexyl) fumarate. It is also possible to copolymerize with one or more types of resin modifiers, such as KN-phenolmaleimide. The ratio of the resin modifier component in the copolymer is preferably 50% or less.
[0027] 本発明で用いられるアクリルポリオールを具体的に挙げるとすれば、「アタリディック A— 801— P」、「アタリディック 56— 719」、「アタリディック AU— 1042」、「アタリディ ック WDU— 938」、 「アタリディック A— 817」、 「アタリディック A— 823」、 「アタリデイツ ク A— 829」（大日本インキ化学工業社製)などである。  [0027] Specific examples of the acrylic polyol used in the present invention include "Ataridic A-801-P", "Ataridic 56-719", "Ataridic AU-1042", "Ataridic WDU — 938 ”,“ Ataridic A-817 ”,“ Ataridic A-823 ”,“ Ataridate A-829 ”(manufactured by Dainippon Ink & Chemicals, Inc.).
[0028] 本発明で用いられるポリエステルポリオールをポリイソシァネートで架橋した榭脂と しては、塗膜としたときに透明性があるものであれば特に制限無く使用可能である。 通常ポリエステルポリオールは耐候性ゃ耐擦傷性、加工性などに優れ、これら特性 はポリイソシァネートとの架橋によってさらに向上する。さらに透明性が高ぐまたカロえ てノ インダー中への微少充填材の分散が容易である。このため該榭脂を用いること により光拡散フィルムの全光線透過率を高め、紫外線による黄変、劣化等を低減す ることができる。本発明で用いる光拡散層の塗膜は、弾力性を有する塗膜表面が擦 過による負荷を塗膜の弾性変形として吸収し、塗膜表面に永久的な擦過傷が生じる 事を緩和する機能を有する、自己修復性を有する塗膜であることが好ましい。  [0028] As a resin obtained by crosslinking the polyester polyol used in the present invention with a polyisocyanate, any resin can be used without particular limitation as long as it has transparency when formed into a coating film. Polyester polyols are usually excellent in weather resistance, scratch resistance, processability, etc., and these characteristics are further improved by crosslinking with polyisocyanate. Furthermore, the transparency is high and the fine filler is easily dispersed in the needle. For this reason, the use of the resin can increase the total light transmittance of the light diffusion film and reduce yellowing, deterioration, etc. due to ultraviolet rays. The coating film of the light diffusing layer used in the present invention has a function that the elastic coating film surface absorbs the load caused by abrasion as an elastic deformation of the coating film, and alleviates the occurrence of permanent scratches on the coating film surface. It is preferable that it is a coating film which has a self-restoring property.
[0029] 本発明で使用するポリエステルポリオールは、例えばエチレングリコール、ジェチレ ングリコール、プロピレングリコール、ジプロピレングリコール、 1, 3—ブタンジォーノレ 、 1, 4 ブタンジオール、 1, 5 ペンタンジオール、ネオペンチルグリコール、へキ サメチレングリコール、デカメチレングリコール、 2, 2, 4 トリメチルー 1, 3 ペンタン ジオール、トリメチロールプロパン、へキサントリオール、グリセリン、ペンタエリスリトー ル、シクロへキサンジオール、水添ビスフエノール A、ビス（ヒドロキシメチル）シクロへ シヌレート、キシリレングリコール等の多価アルコールと、例えばマレイン酸、フマル酸 、コハク酸、アジピン酸、セバチン酸、ァゼライン酸、トリメット酸、テレフタル酸、フタル 酸、イソフタル酸等の多塩基酸とを、多価アルコール中の水酸基数が前記多塩基酸 のカルボキシル基数よりも多い条件で反応させて製造することができる。 [0029] Polyester polyols used in the present invention include, for example, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and 1,3-butanediol. 1,4 butanediol, 1,5 pentanediol, neopentyl glycol, hexamethylene glycol, decamethylene glycol, 2, 2, 4 trimethyl-1,3 pentane diol, trimethylolpropane, hexanetriol, glycerin, penta Polyhydric alcohols such as erythritol, cyclohexanediol, hydrogenated bisphenol A, bis (hydroxymethyl) cyclohexinrate, xylylene glycol, and the like, for example, maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, It can be produced by reacting azelaic acid, trimetic acid, terephthalic acid, phthalic acid, isophthalic acid and other polybasic acids under conditions where the number of hydroxyl groups in the polyhydric alcohol is greater than the number of carboxyl groups in the polybasic acid. .
[0030] 力かる水酸基過剰の条件で得られるポリエステルポリオールの数平均分子量は 50 0以上 300000以下であり、好まし <は 2000以上 100000以下である。また、その水 酸基価は 5以上 300以下、好ましくは 10以上 200以下である。  [0030] The number average molecular weight of the polyester polyol obtained under the conditions of excessive hydroxyl groups is 500 to 300,000, preferably <2000 to 100,000. The hydroxyl group value is 5 or more and 300 or less, preferably 10 or more and 200 or less.
なお、上記ポリエステルポリオール中の水酸基の個数は、 1分子当たり 2個以上で あれば特に限定されないが、固形分中の水酸基価が 10以下であると架橋点数が減 少し、耐溶剤性、耐水性、耐熱性、表面硬度等の被膜物性が低下する傾向がある。 本発明で用いられるポリエステルポリオールをポリイソシァネートで架橋した榭脂に 使用可能なポリエステルポリオールを具体的に挙げるとすれば、「バーノック D6— 43 9」、 「バーノック D— 115— 80」、 「バーノック D7— 885」、 「バーノック DS— 1000」「 バーノック D— 161」（大日本インキ化学工業社製)などである。  The number of hydroxyl groups in the polyester polyol is not particularly limited as long as it is 2 or more per molecule, but if the hydroxyl value in the solid content is 10 or less, the number of crosslinking points is reduced, and the solvent resistance and water resistance are reduced. , Film properties such as heat resistance and surface hardness tend to decrease. Specific examples of polyester polyols that can be used for the resin obtained by crosslinking the polyester polyol used in the present invention with polyisocyanate include “Bernock D6—43 9”, “Bernock D—115—80”, “ Barnock D7-885, Barnock DS-1000, Barnock D-161 (Dainippon Ink and Chemicals).
[0031] なお本発明で使用する榭脂バインダーとしては、塗膜硬さや透明性の点でアクリル ポリオールがポリイソシァネートで架橋された共重合体を用いることがより好ましいが、 光拡散フィルム表面の耐擦傷性の一層の向上のためにはポリエステルポリオールが ポリイソシァネートで架橋された共重合体が好ましぐ用途に応じてこれらを使い分け ることがでさる。  [0031] The resin binder used in the present invention is more preferably a copolymer obtained by crosslinking an acrylic polyol with a polyisocyanate in terms of coating film hardness and transparency. In order to further improve the scratch resistance, it is possible to use a polyester polyol cross-linked with a polyisocyanate in accordance with the preferred use.
[0032] 本発明で用いるポリイソシァネートとしては、アクリルポリオールまたはポリエステルポ リオールの水酸基と架橋することが可能な、 HDI系、 XDI系などの脂肪族イソシァネ ートをベースにしたもの、 TDI系、 MDI系などの芳香族イソシァネートをベースにした ものがあるが、 HDI (へキサメチレンジイソシァネート）系、 XDI (キシレンジイソシァネ ート）系の脂肪族イソシァネートをベースにしたポリイソシァネートは紫外線によって 黄変しやす ヽと 、う弱点が無く好ま U、。これらのイソシァネートをポリイソシァネート とする変性の型としては、 HDI、 XDIなどの脂肪族イソシァネートに多価アルコール を付カ卩したァダクト型、 HDIをベースに三量化したイソシァヌレート型、または HDIを ベースにしたピウレット型などが挙げられる。なかでも、 HDIに多価アルコールを付カロ したァダクト型のポリイソシァネートが、光拡散フィルムの加工工程において極めて有 利な機械物性を得られやす!ヽ点から、特に好ま ヽ。 [0032] The polyisocyanate used in the present invention is based on an aliphatic isocyanate such as HDI or XDI, which can be crosslinked with the hydroxyl group of acrylic polyol or polyester polyol, and TDI. Some of these are based on aromatic isocyanates such as MDI, HDI (hexamethylene diisocyanate), XDI (xylene diisocyanate). Polyisocyanates based on aliphatic isocyanates are preferred because they are easily yellowed by UV rays and have no weakness. These isocyanates are modified with polyisocyanates, such as HDI, XDI and other aliphatic isocyanates with adducts of polyhydric alcohol, HDI-based isocyanurates, or HDI-based isocyanurates. The piuret type that was made. Of these, adduct-type polyisocyanates prepared by adding polyhydric alcohol to HDI are particularly preferred because they can provide extremely advantageous mechanical properties in the light diffusion film processing process.
[0033] ポリイソシァネート中のイソシァネートの、アクリルポリオールまたはポリエステルポリ オール中の水酸基に対する当量比は、 0. 7〜3. 0とする事が好ましい。当量比が 0. 7より小さい場合、架橋密度が低くなりやすぐ光拡散層の耐擦過性および耐溶剤性 が不十分となる事に加えて、榭脂粒子の脱落が起きやすくなる傾向にある。当量比 が 3. 0より大きい場合、ポリイソシァネート分子間の架橋が進行し、光拡散層が脆くな りやすい。 [0033] The equivalent ratio of the isocyanate in the polyisocyanate to the hydroxyl group in the acrylic polyol or polyester polyol is preferably 0.7 to 3.0. When the equivalence ratio is less than 0.7, the crosslinking density becomes low, and the light diffusion layer tends to have insufficient scratch resistance and solvent resistance. . When the equivalent ratio is greater than 3.0, crosslinking between polyisocyanate molecules proceeds and the light diffusion layer tends to become brittle.
[0034] ここで、イソシァネートの水酸基に対する当量比（NCOZOH)は、下記の数式 1に よって一般的に求められる。  [0034] Here, the equivalent ratio of isocyanate to hydroxyl group (NCOZOH) is generally determined by the following formula 1.
N CO 】w X In X 561  N CO】 w X In X 561
OH Aw x Ao 42 上記の数式において、 Iw、 In、 Aw、 Ao はそれぞれ下記のとおりである。 Iw:ポリイソシァネートの固形分換算質量部  OH Aw x Ao 42 In the above formula, Iw, In, Aw, and Ao are as follows. Iw: parts by mass in terms of solid content of polyisocyanate
In：ポリイソシァネートにおける固形分中の有効 NCO含量（％)  In: Effective NCO content (%) in the solid content of polyisocyanate
Aw：アクリルポリオールまたはポリエステルポリオールの固形分換算質量部  Aw: Mass parts in terms of solid content of acrylic polyol or polyester polyol
Ao：アクリルポリオールまたはポリエステルポリオールにおける固形分水酸基価  Ao: Solid content hydroxyl value in acrylic polyol or polyester polyol
[0035] 本発明の光拡散フィルムにおいて、榭脂バインダーに対する、榭脂粒子の配合量 は、使用する榭脂粒子の平均粒子径ゃ光拡散層の膜厚によって変化するために一 概に言えないが、榭脂バインダーの固形分 100質量部に対し、 5〜400質量部、好 ましくは 10〜250質量部である。榭脂粒子が榭脂バインダー 100質量部に対して 5 質量部に満たないと、良好な光拡散性能が得られ難い傾向にある。一方、 400質量 部を超えると、光透過性が低下して充分な光量が利用し難い傾向にある。 [0036] 本発明で使用される榭脂粒子においては、光拡散材として硬化触媒を含有した榭 脂粒子を用い、榭脂バインダーとしてアクリルポリオールまたはポリエステルポリオ一 ルがポリイソシァネートで架橋したものを用いて 、るために、榭脂粒子と榭脂バインダ 一界面における榭脂バインダーの架橋反応が優先的かつ速やかに進行し、榭脂バ インダ一力 榭脂粒子が脱落し難い光拡散層を提供する事ができる。 [0035] In the light diffusion film of the present invention, the blending amount of the resin particles with respect to the resin binder cannot be generally stated because the average particle diameter of the resin particles used varies depending on the film thickness of the light diffusion layer. However, it is 5 to 400 parts by weight, preferably 10 to 250 parts by weight, based on 100 parts by weight of the solid content of the resin binder. If the resin particles are less than 5 parts by mass with respect to 100 parts by mass of the resin binder, good light diffusion performance tends to be difficult to obtain. On the other hand, when the amount exceeds 400 parts by mass, the light transmittance tends to be low and it is difficult to use a sufficient amount of light. In the resin particles used in the present invention, resin particles containing a curing catalyst are used as a light diffusing material, and acrylic polyol or polyester polyol is crosslinked with polyisocyanate as a resin binder. Therefore, the cross-linking reaction of the resin binder at the interface between the resin particles and the resin binder proceeds preferentially and quickly, and the resin binder works as a light diffusion layer in which the resin particles are difficult to fall off. Can be provided.
本発明の光拡散フィルムの光拡散層には、上記の材料のほか、光拡散フィルムの 諸特性を阻害しない範囲で、例えば分散剤、可塑剤、帯電防止剤、劣化防止剤など が配合されていてもよい。  In the light diffusing layer of the light diffusing film of the present invention, in addition to the above materials, for example, a dispersant, a plasticizer, an antistatic agent, a deterioration preventing agent and the like are blended within a range that does not impair various properties of the light diffusing film. May be.
光拡散層の膜厚は、使用する榭脂粒子の平均粒径ゃ榭脂粒子の配合量によって 変化するために一概に言えないが、 5〜50 /ζ πι程度が好ましぐさらに好ましくは 8〜 40 μ mである。  The film thickness of the light diffusing layer cannot be generally described because it varies depending on the blended amount of the resin particles, but the average particle diameter of the resin particles used is preferably about 5 to 50 / ζ πι, more preferably 8 ~ 40 μm.
[0037] 本発明の光拡散フィルムにおいて、背面層は無くてもよいが、多くの場合、光拡散 フィルムの光拡散層と反対側の面への摩擦傷を防止したり、導光板とのステイツキン グを防止したりするなどの目的で、背面層が設けられる。  [0037] In the light diffusing film of the present invention, the back layer may be omitted. However, in many cases, a frictional scratch on the surface of the light diffusing film opposite to the light diffusing layer is prevented, or a state skin with the light guide plate is used. A back layer is provided for the purpose of preventing stagnation.
本発明の光拡散フィルムの背面層には、少なくとも榭脂バインダーを含有する。必 要に応じ、ステイツキング防止のための滑剤、光拡散フィルムへの静電気帯電を抑制 するための帯電防止剤、紫外線吸収剤、紫外線遮蔽剤、光拡散材などを含有させる ことができる。  The back layer of the light diffusion film of the present invention contains at least a resin binder. If necessary, a lubricant for preventing sticking, an antistatic agent for suppressing electrostatic charge on the light diffusing film, an ultraviolet absorber, an ultraviolet shielding agent, a light diffusing material and the like can be contained.
本発明の光拡散フィルムの背面層に含有される榭脂バインダーとしては、光拡散フ イルムの透明性を阻害しな ヽものであれば特に限定されな ヽが、熱可塑性メタクリル 榭脂、熱可塑性メタタリルースチレン共重合榭脂や、ポリエステル榭脂またはアクリル 榭脂をポリイソシァネートで架橋したものであれば好ましい。  The resin binder contained in the back layer of the light diffusing film of the present invention is not particularly limited as long as it does not inhibit the transparency of the light diffusing film. Thermoplastic methacrylic resin, thermoplastic resin It is preferable if a metataryl styrene copolymer resin, a polyester resin, or an acrylic resin is crosslinked with a polyisocyanate.
[0038] 背面層に第二の光拡散層としての機能を持たせる場合は、本発明の光拡散層が 好適に使用できる。光拡散フィルムの両面に光拡散層を設ける事で、ステイツキング 防止層としての機能に加えて、より高ヘイズを求められる用途に対応できるようになる 背面層の膜厚としては、 1〜15 m程度が好適に用いられるが、背面層に第二の 光拡散層としての機能を持たせる場合には、 5〜50 /ζ πι、特には 8〜40 /ζ πιが好適 に用いられる。 [0038] When the back layer has a function as a second light diffusion layer, the light diffusion layer of the present invention can be preferably used. By providing light diffusing layers on both sides of the light diffusing film, in addition to its function as an anti-sticking layer, it can be used for applications that require higher haze. However, when the back layer has a function as the second light diffusion layer, 5 to 50 / ζ πι, particularly 8 to 40 / ζ πι is preferable. Used for.
[0039] 本発明における光拡散フィルムを製造するためには、透明なシート状基材の少なく とも一方の面に、光拡散層用塗料を塗布して、光拡散層を形成させる。他方の面に は、必要に応じて背面層用塗料を塗布することにより背面層を形成させる。  [0039] In order to produce the light diffusing film in the present invention, a light diffusing layer is formed by applying a coating material for a light diffusing layer to at least one surface of a transparent sheet-like substrate. On the other side, a back layer is formed by applying a back layer coating if necessary.
塗布する方法としては、一般的な塗工方式が利用できる。例えば、ブレード、ナイフ 、キャスト、浸漬、含浸機、スクリーン、スピン、リバースロール、エアドクター、グラビア 、スプレー、カーテン、押出、フアウンテン、キス、ロッド、スクイズ、正回転ロール、キス ロールなどの塗工方式が利用できる。  As a coating method, a general coating method can be used. For example, coating methods such as blade, knife, casting, dipping, impregnation machine, screen, spin, reverse roll, air doctor, gravure, spray, curtain, extrusion, fountain, kiss, rod, squeeze, forward roll, kiss roll, etc. Is available.
塗膜の乾燥には、一般的な乾燥方式が利用できる。例えば、熱風、赤外線、マイク 口波、誘導加熱などの乾燥方式が利用できる。乾燥後、必要に応じて所定の温度お よび時間にて熱エージング処理を行う。  A general drying method can be used to dry the coating film. For example, drying methods such as hot air, infrared rays, microphone mouth wave, induction heating can be used. After drying, heat aging treatment is performed at a predetermined temperature and time as necessary.
[0040] 以上のようにして製造される本発明の光拡散フィルムは、液晶表示装置用バックラ イトユニットを構成する光拡散フィルムとして利用するのに特に有用である力 S、この用 途に限定されるものではなぐ光拡散光の必要な種々の用途に適用することができる  [0040] The light diffusing film of the present invention produced as described above is a force S that is particularly useful for use as a light diffusing film constituting a backlight unit for a liquid crystal display device, and is limited to this application. It can be applied to various uses that require diffused light.
実施例 Example
[0041] 以下に、実施例を用いて本発明を説明する。  [0041] The present invention will be described below with reference to examples.
(合成例 1)  (Synthesis Example 1)
乾燥させた攪拌機、温度計、冷却器および窒素ガス導入管を取り付けた反応容器 にポリ力プロラタトントリオール (プラタセル 308、ダイセルィ匕学社製) 42質量部、へキ サメチレンジイソシァネート（以下、 HDIと略す。） 50質量部、ジブチル錫ジラウレート 0. 1質量部を仕込み、窒素雰囲気下で 120°C、 10時間攪拌しながら反応させた。そ の後、減圧下にて未反応の HDIを除去した後、トルエンを加えて不揮発分 90質量％ のプレポリマー（1)を得た。  A reaction vessel equipped with a dried stirrer, thermometer, cooler, and nitrogen gas inlet tube is equipped with 42 parts by mass of poly-force prolataton triol (Platacel 308, manufactured by Daicel Engineering Co., Ltd.), hexamethylene diisocyanate Abbreviated as HDI.) 50 parts by mass and 0.1 part by mass of dibutyltin dilaurate were charged and reacted under stirring in a nitrogen atmosphere at 120 ° C. for 10 hours. Thereafter, unreacted HDI was removed under reduced pressure, and toluene was added to obtain a prepolymer (1) having a nonvolatile content of 90% by mass.
攪拌機付きセパラブルフラスコに 2%メチルセルロース水 670質量部を仕込み、攪 拌しながらプレポリマー（1) 102質量部、メチルメタタリレート 100質量部、トルエン 10 質量部、 t—ブチルパーォキシビバレート (パーブチル PV、 日本油脂社製） 2質量部 カゝらなる溶液を加えて懸濁液を作製する。攪拌係属下で懸濁液を 60°Cに昇温して 5 時間反応させた後、 1時間以上かけて 100°Cまで昇温してトルエンを共沸にて分離し 、冷却後、固液分離'洗浄 ·乾燥'分級してアクリルウレタン榭脂粒子 (I)を得た。この 粒子の平均粒径は 16 mで、硬化触媒含有量は約 0. 05質量％であった。 In a separable flask equipped with a stirrer, 670 parts by weight of 2% methylcellulose water was charged, and while stirring, 102 parts by weight of prepolymer (1), 100 parts by weight of methyl methacrylate, 10 parts by weight of toluene, and t-butyl peroxybivalate (Perbutyl PV, manufactured by Nippon Oil & Fats Co., Ltd.) 2 parts by mass A solution consisting of a mixture is added to prepare a suspension. Raise the suspension temperature to 60 ° C while stirring. After reacting for a period of time, the temperature was raised to 100 ° C over 1 hour, and toluene was separated azeotropically. After cooling, solid-liquid separation 'washing · drying' classification was performed to classify acrylic urethane resin particles (I) Got. These particles had an average particle size of 16 m and a curing catalyst content of about 0.05% by mass.
[0042] (合成例 2) [0042] (Synthesis Example 2)
合成例 1と同様の方法にて、ポリ力プロラタトンジオール（プラタセル 210、ダイセル 化学社製) 48質量部、 HDI42質量部、ジォクチル錫ジラウレート 0. 1質量部を反応 させ、トルエンをカ卩えて不揮発分 70質量0 /0のプレボリマー（2)を得た。 In the same manner as in Synthesis Example 1, 48 parts by mass of polyforce prolatatondiol (Platacel 210, manufactured by Daicel Chemical Industries), 42 parts by mass of HDI, and 0.1 part by mass of dioctyltin dilaurate were reacted, and toluene was added to form nonvolatile obtain min 70 mass 0/0 Pureborima (2).
攪拌機付きセパラブルフラスコに 3%メチルセルロース水 700質量部を仕込み、攪 拌しながらプレボリマー（2) 128質量部、メチルメタタリレート 75質量部、 n—ブチルメ タクリレート 25質量部、 tーブチノレパーォキシ 2 ェチノレへキサネート（力ャエステ ル 0、化薬ァクゾ社製) 3質量部カゝらなる溶液を加えて懸濁液を作製する。攪拌係属 下で懸濁液を 60°Cに昇温して 5時間反応させた後、 1時間以上かけて 100°Cまで昇 温してトルエンを共沸にて分離し、冷却後、固液分離 '洗浄'乾燥した後、分級してァ クリルウレタン榭脂粒子 (Π)を得た。この粒子の平均粒径は 6 μ mで、硬化触媒含有 量は約 0. 05質量％であった。  A separable flask equipped with a stirrer was charged with 700 parts by weight of 3% methylcellulose water, and while stirring, the prepolymer (2) 128 parts by weight, 75 parts by weight of methyl methacrylate, 25 parts by weight of n-butyl methacrylate, and t-butinolepa A suspension is prepared by adding 3 parts by weight of a solution of 2 parts of xytin hexole hexanate (Strength 0, manufactured by Kayaku Akuzo). The suspension was heated to 60 ° C under stirring and allowed to react for 5 hours, then heated to 100 ° C over 1 hour to separate toluene azeotropically, cooled, and then solid-liquid After separation 'washing' and drying, classification was carried out to obtain acrylic urethane resin particles (粒子). These particles had an average particle size of 6 μm and a curing catalyst content of about 0.05% by mass.
[0043] (合成例 3) [Synthesis Example 3]
合成例 1と同様の方法にて、ポリ力プロラタトンジオール (プラタセル L212AL、ダイ セル化学社製) 44質量部、 HDI25質量部、ジォクチル錫ジラウレート 0. 15質量部 を反応させた後、ラタトン変性 (メタ）アタリレート (プラタセル FM3、ダイセル化学社製 ) 15質量部、ポリアルキレングリコール (メタ）アタリレート（ブレンマー E、 日本油脂社 製) 81質量部およびトルエン 18質量部を添加し、 80°Cにて反応させて不揮発分 90 質量％のプレボリマー（3)を得た。  In the same way as in Synthesis Example 1, after reacting 44 parts by mass of polyprolatatondiol (Platacel L212AL, manufactured by Daicel Chemical), 25 parts by mass of HDI, and 0.15 parts by mass of dioctyltin dilaurate, Add 15 parts by weight of (meth) atalylate (Platacel FM3, manufactured by Daicel Chemical), 81 parts by weight of polyalkylene glycol (meth) atalylate (Blenmer E, manufactured by NOF Corporation) and 18 parts by weight of toluene at 80 ° C To obtain a prepolymer (3) having a nonvolatile content of 90% by mass.
攪拌機付きセパラブルフラスコに 3 %メチルセルロース水 1000質量部を仕込み、 攪拌しながらプレボリマー（3) 150質量部、メチルメタタリレート 150質量部、 t—ブチ ルパーォキシビバレート（パーブチル PV) 3質量部、トルエン 20質量部力もなる溶液 を加えて懸濁液を作製する。攪拌係属下で懸濁液を 55°Cに昇温して 5時間反応さ せた後、 1時間以上かけて 100°Cまで昇温してトルエンを共沸にて分離し、冷却後、 固液分離'洗浄 *乾燥した後、分級してアクリルウレタン榭脂粒子 (III)を得た。この粒 子の平均粒径は 6 /z mで、硬化触媒含有量は約 0. 04質量％であった。 A separable flask equipped with a stirrer was charged with 1000 parts by mass of 3% methylcellulose water, and while stirring, 150 parts by mass of prepolymer (3), 150 parts by mass of methyl methacrylate, 3 parts by mass of t-butyl peroxybivalate (perbutyl PV) Add a solution with 20 parts by mass of toluene to make a suspension. The suspension was heated to 55 ° C under stirring and allowed to react for 5 hours, then heated to 100 ° C over 1 hour to separate toluene azeotropically, cooled and then solidified. Liquid separation and washing * After drying, classification was carried out to obtain acrylic urethane resin particles (III). This grain The average particle size of the children was 6 / zm, and the content of the curing catalyst was about 0.04% by mass.
[0044] (合成例 4) [0044] (Synthesis Example 4)
合成例 1と同様の方法にて、ポリ力プロラタトンジオール（プラタセル L212AL) 15 質量部、 HDI75質量部、ジォクチル錫ジラウレート 0. 09質量部を反応させた後、ラ タトン変性 (メタ）アタリレート（プラタセル FM3) 15質量部、ポリアルキレングリコール（ メタ）アタリレート（ブレンマー E) 30質量部およびトルエン 34質量部を添カ卩し、 80°C にて反応させて不揮発分 80質量％のプレボリマー (4)を得た。  In the same manner as in Synthesis Example 1, after reacting 15 parts by mass of polyprolatatondiol (Platacel L212AL), 75 parts by mass of HDI, and 0.09 parts by mass of dioctyltin dilaurate, the rataton modified (meth) atalylate ( Platacel FM3) 15 parts by weight, 30 parts by weight of polyalkylene glycol (meth) acrylate (Bremmer E) and 34 parts by weight of toluene were added and reacted at 80 ° C to react with 80% by weight non-volatile polymer (4 )
攪拌機付きセパラブルフラスコに 3 %メチルセルロース水 1000質量部を仕込み、 攪拌しながらプレボリマー（4) 150質量部、メチルメタタリレート 180質量部、 n—ブチ ルメタタリレート 15質量部、 t—ブチルパーォキシビバレート（パーブチル PV) 4質量 部からなる溶液を加えて懸濁液を作製する。攪拌係属下で懸濁液を 55°Cに昇温し て 5時間反応させた後、 1時間以上かけて 100°Cまで昇温してトルエンを共沸にて分 離し、冷却後、固液分離'洗浄《乾燥した後、分級してアクリルウレタン榭脂粒子 (IV) を得た。この粒子の平均粒径は 6 mで、硬化触媒含有量は約 0. 03質量％であつ た。  A separable flask equipped with a stirrer was charged with 1000 parts by weight of 3% methylcellulose water. While stirring, the prepolymer (4) 150 parts by weight, methyl metatalylate 180 parts by mass, n-butyl metatalylate 15 parts by mass, t-butyl pero Add a solution consisting of 4 parts by mass of xibivalate (perbutyl PV) to make a suspension. The suspension was heated to 55 ° C under stirring and allowed to react for 5 hours, then heated to 100 ° C over 1 hour to separate toluene azeotropically, cooled, and then solid-liquid Separation 'washing << drying and classification were carried out to obtain acrylic urethane resin particles (IV). These particles had an average particle size of 6 m and a curing catalyst content of about 0.03% by mass.
[0045] (合成例 5)  [0045] (Synthesis Example 5)
合成例 1において、ジブチル錫ジラウレートを添加せずに仕込み、窒素雰囲気下で 120°C、 24時間攪拌しながら反応させ、冷却後、トルエンを加えて不揮発分 90質量 %のプレボリマー（5)を得た以外は、合成例 1と同様にしてアクリルウレタン榭脂粒子 (V)を得た。この粒子の平均粒径は 16 μ mであった。  In Synthesis Example 1, without adding dibutyltin dilaurate, the mixture was allowed to react with stirring at 120 ° C. for 24 hours in a nitrogen atmosphere. After cooling, toluene was added to obtain a prepolymer (5) having a nonvolatile content of 90% by mass. Acrylic urethane resin particles (V) were obtained in the same manner as in Synthesis Example 1 except that. The average particle size of these particles was 16 μm.
[0046] (実施例 1) [Example 1]
<光拡散層用塗料 aの調製工程 >  <Preparation process of coating material a for light diffusion layer>
トルエン 250 質量部  Toluene 250 parts by weight
シクロへキサノン 40 質量部  Cyclohexanone 40 parts by mass
アクリルウレタン榭脂粒子 (I) 125 質量部  Acrylic urethane resin particles (I) 125 parts by mass
アクリルポリオール「アタリディック WDU— 938」  Acrylic polyol "Ataridic WDU- 938"
〔固形分 50%、固形分の水酸基価 50、大日本インキ化学工業社製〕  [50% solid content, hydroxyl value 50 solid content, manufactured by Dainippon Ink & Chemicals, Inc.]
100 質量部 ポリイソシァネート「コロネート HL」 15 質量部 100 parts by mass Polyisocyanate "Coronate HL" 15 parts by mass
〔固形分 75%、 HDI系、固形分中の有効 NCO含量 17%、 日本ポリウレタン工業社 製〕  (Solid content 75%, HDI, effective NCO content 17% in solid content, manufactured by Nippon Polyurethane Industry Co., Ltd.)
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 aを得た。このときイソシァネート の水酸基に対する当量比は 1. 0であった。塗料 aは温度 25°C、湿度 60%の環境に お 、て 8時間静置しても、粘度上昇は発生しな力つた。  The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material a. At this time, the equivalent ratio of isocyanate to hydroxyl group was 1.0. Paint a did not increase in viscosity even after standing for 8 hours in an environment with a temperature of 25 ° C and a humidity of 60%.
基材として、厚さ 100 mのポリエチレンテレフタレート（PET)フィルムを使用し、こ の一方の面に上記光拡散層用塗料 aを、乾燥膜厚が約 30 mになるように塗布し、 熱風乾燥させて光拡散層の乾燥塗膜を得た。塗布工程終了後、 40°C恒温室中 48 時間の熱エージング処理を行い光拡散フィルムを作製した。  Using a polyethylene terephthalate (PET) film with a thickness of 100 m as the base material, apply the light diffusion layer coating material a on one side so that the dry film thickness is about 30 m, and dry with hot air. Thus, a dry coating film of the light diffusion layer was obtained. After the coating process was completed, a light diffusing film was prepared by thermal aging treatment in a constant temperature room at 40 ° C for 48 hours.
[0047] (実施例 2) [Example 2]
<光拡散層用塗料 bの調製工程 >  <Preparation process of paint b for light diffusion layer>
トルエン 250 質量部  Toluene 250 parts by weight
シクロへキサノン  Cyclohexanone
40 質量部  40 parts by mass
アクリルウレタン榭脂粒子 (II) 125 質量部  Acrylic urethane resin particles (II) 125 parts by mass
アクリルポリオール「アタリディック WDU— 938」  Acrylic polyol "Ataridic WDU- 938"
100 質量部  100 parts by mass
ポリイソシァネート「コロネート HL」 15 質量部  Polyisocyanate "Coronate HL" 15 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 bを得た。このときイソシァネート の水酸基に対する当量比は 1. 0であった。塗布工程終了後、 40°C恒温室中で 48時 間の熱エージング処理を行つた。  The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material b. At this time, the equivalent ratio of isocyanate to hydroxyl group was 1.0. After the coating process, heat aging treatment was performed for 48 hours in a constant temperature room at 40 ° C.
実施例 1における光拡散層用塗料 aの代わりに上記光拡散層用塗料 bを用いた他 は、実施例 1と同一の方法で、基材上に乾燥塗膜を形成し光拡散フィルムを作製し た  In the same manner as in Example 1, except that the light diffusion layer coating b was used in place of the light diffusion layer coating a in Example 1, a dry coating film was formed on the substrate to produce a light diffusion film. did
[0048] (実施例 3)  [0048] (Example 3)
<光拡散層用塗料 cの調製工程 >  <Preparation process of light diffusion layer paint c>
トルエン 300 質量部 シクロへキサノン 55 質量部 300 parts by mass of toluene Cyclohexanone 55 parts by weight
アクリルウレタン榭脂粒子 (III) 150 質量部  Acrylic urethane resin particles (III) 150 parts by mass
アクリルポリオール「アタリディック WDU  Acrylic polyol "Atari Dick WDU
100 質量部  100 parts by mass
ポリイソシァネート「コロネート HL」 30 質量部  Polyisocyanate "Coronate HL" 30 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 cを得た。このときイソシァネート の水酸基に対する当量比は 2. 0であった。塗布工程終了後、 40°C恒温室中 48時間 の熱エージング処理を行った。  The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material c. At this time, the equivalent ratio of isocyanate to hydroxyl group was 2.0. After the coating process, thermal aging treatment was performed for 48 hours in a constant temperature room at 40 ° C.
実施例 1における光拡散層用塗料 aの代わりに上記光拡散層用塗料 cを用い、乾 燥膜厚を約 15 mとした他は、実施例 1と同一の方法で、基材上に乾燥塗膜を形成 し光拡散フィルムを作製した。  Dried on the substrate in the same manner as in Example 1, except that the light diffusing layer coating c was used instead of the light diffusing layer coating a in Example 1 and the dry film thickness was about 15 m. A coating film was formed to produce a light diffusion film.
[0049] (比較例 1) [0049] (Comparative Example 1)
<光拡散層用塗料 dの調製工程 >  <Preparation process of coating material d for light diffusion layer>
トルエン 250 質量部  Toluene 250 parts by weight
シクロへキサノン 40 質量部  Cyclohexanone 40 parts by mass
アクリル榭脂粒子「MBX— 15」 125 質量部  Acrylic resin particles "MBX-15" 125 parts by mass
〔平均粒子径約 13 μ m、硬化触媒含有なし、積水化成品工業社製〕  [Average particle size of about 13 μm, no curing catalyst, manufactured by Sekisui Plastics Co., Ltd.]
アクリルポリオール「アタリディック WDU— 938」  Acrylic polyol "Ataridic WDU- 938"
100 質量部  100 parts by mass
ポリイソシァネート「コロネート HL」 15 質量部  Polyisocyanate "Coronate HL" 15 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用 d塗料を得た。このときイソシァネート の水酸基に対する当量比は 1. 0であった。  The above was stirred and mixed with a dispersion stirrer to obtain d coating material for the light diffusion layer. At this time, the equivalent ratio of isocyanate to hydroxyl group was 1.0.
実施例 1における光拡散層用塗料 aの代わりに上記光拡散層用塗料 dを用い、乾 燥膜厚を約 29 mとした他は、実施例 1と同一の方法で、基材上に乾燥塗膜を形成 し光拡散フィルムを作製した。  In the same manner as in Example 1, except that the light diffusion layer coating material d was used instead of the light diffusion layer coating material a in Example 1, and the dry film thickness was about 29 m. A coating film was formed to produce a light diffusion film.
[0050] (比較例 2) [0050] (Comparative Example 2)
<光拡散層用塗料 eの調製工程 >  <Preparation process of paint for light diffusion layer e>
トルエン 300 質量部 シクロへキサノン 55 質量部 300 parts by mass of toluene Cyclohexanone 55 parts by weight
スチレン榭脂粒子「SBX 150 質量部 Styrene resin particles “SBX 150 parts by mass
〔平均粒子径約 6 μ m、硬化触媒含有なし、積水化成品工業社製〕  (Average particle size of about 6 μm, no curing catalyst, manufactured by Sekisui Plastics Co., Ltd.)
アクリルポリオール「アタリディック WDU Acrylic polyol "Atari Dick WDU
100 質量部  100 parts by mass
ポリイソシァネート「コロネート HL」 30 質量部 Polyisocyanate "Coronate HL" 30 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 eを得た。このときイソシァネート の水酸基に対する当量比は 2. 0であった。 The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material e. At this time, the equivalent ratio of isocyanate to hydroxyl group was 2.0.
実施例 1における光拡散層用塗料 aの代わりに上記光拡散層用塗料 eを用い、乾 燥膜厚を約 15 mとしたほかは、実施例 1と同一の方法で、基材上に乾燥塗膜を形 成し、光拡散フィルムを作製した。  In the same manner as in Example 1, except that the light diffusion layer coating e was used instead of the light diffusion layer coating a in Example 1 and the dry film thickness was about 15 m. A coating film was formed to produce a light diffusion film.
(比較例 3) (Comparative Example 3)
<光拡散層用塗料 fの調製工程 >  <Preparation process of paint for light diffusion layer f>
トルエン 290 質量部 Toluene 290 parts by mass
シクロへキサノン 50 質量部 Cyclohexanone 50 parts by mass
ジブチル錫ジラウレート 0. 2 質量部 Dibutyltin dilaurate 0.2 parts by mass
シリコーン榭脂粒子「トスパール 2000B」 150 質量部 Silicone oil particles “Tospearl 2000B” 150 parts by mass
〔平均粒子径約 6 m、硬化触媒含有なし、 GE東芝シリコーン社製〕  (Average particle size of about 6 m, no curing catalyst, manufactured by GE Toshiba Silicones)
アクリルポリオール「アタリディック WDU— 938」 Acrylic polyol "Ataridic WDU- 938"
100 質量部  100 parts by mass
ポリイソシァネート「コロネート HL」 15 質量部 Polyisocyanate "Coronate HL" 15 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 fを得た。このときイソシァネート の水酸基に対する当量比は 1. 0であった。 The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material f. At this time, the equivalent ratio of isocyanate to hydroxyl group was 1.0.
実施例 1における光拡散層用塗料 aの代わりに上記光拡散層用塗料 fを用い、乾燥 膜厚を約 15 mとしたほかは、実施例 1と同一の方法で、基材上に乾燥塗膜を形成 し光拡散フィルムを作製した。  In the same manner as in Example 1, except that the light diffusion layer coating material f was used in place of the light diffusion layer coating material a in Example 1 and the dry film thickness was about 15 m, dry coating was performed on the substrate. A film was formed to produce a light diffusion film.
(比較例 4) (Comparative Example 4)
実施例 1において、アクリルウレタン榭脂粒子 (I)に替えてアクリルウレタン榭脂粒子 (V)を用いたほかは、実施例 1と同一の方法で、基材上に乾燥塗膜を形成し、光拡 散フィルムを作製した。 In Example 1, instead of acrylic urethane resin particles (I), acrylic urethane resin particles Except for the use of (V), a dry coating film was formed on the substrate in the same manner as in Example 1 to produce a light diffusion film.
[0053] (榭脂粒子の脱落性の評価）  [0053] (Evaluation of detachment of sallow particles)
表面性試験機サゥザランド ·ラブテスタ (東洋精機製作所社製)を使用し、光拡散層 面同士が擦られるようにして光拡散フィルムを固定し、荷重 18Nで 1000往復、光拡 散面を摩擦した。摩擦後に、下側で摩擦された光拡散フィルムを 10mm角に切り出 し、光拡散層面の榭脂粒子の脱落状態を顕微鏡にて観察した。榭脂粒子の脱落性 の評価には、以下の基準を用いた。  Using a surface testing machine, Sutherland Love Tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the light diffusion film was fixed so that the surfaces of the light diffusion layer were rubbed with each other, and the light diffusion surface was rubbed 1000 times with a load of 18N. After rubbing, the light diffusing film rubbed on the lower side was cut into 10 mm squares, and the falling state of the resin particles on the surface of the light diffusing layer was observed with a microscope. The following criteria were used for the evaluation of the detachment properties of the resin particles.
〇 · · ·脱落箇所が観察されない。  ○ · · · No dropout is observed.
△ · · ·脱落箇所力^〜 3である。  Δ · · · Dropout force ^ ~ 3.
X · · ·脱落箇所が 4以上である。  X · · · There are 4 or more omission points.
評価結果を表 1に示した。表 1からゎカゝるように、硬化触媒を含有した榭脂粒子を使 用した場合、光拡散層面から榭脂粒子が脱落し難ぐ光拡散フィルムとして極めて優 れたものであった。一方、塗料中に硬化触媒を添加した場合は、耐擦傷性に劣る事 に加えて塗料のゲルイ匕が早まり、実使用上好ましくな ヽ結果であった。  The evaluation results are shown in Table 1. As shown in Table 1, when the resin particles containing a curing catalyst were used, the resin particles were extremely excellent as a light diffusion film in which the resin particles hardly fall off from the surface of the light diffusion layer. On the other hand, when a curing catalyst was added to the paint, in addition to inferior scratch resistance, the gel of the paint was accelerated, which was a favorable result in practical use.
[0054] (光拡散層の耐擦傷性の評価） [0054] (Evaluation of scratch resistance of light diffusion layer)
表面性試験機 HEIDON— 14D (新東科学社製）にて、ステンレス製ボール圧子（S US304、直径 4. 76mm)を使用し、 20gfの荷重をかけて移動速度 60mmZ秒で 5 0往復、光拡散面を摩擦した。摩擦後に光拡散面を上にして背面から蛍光灯の光を 当てて透過光による目視観察と、蛍光灯下で光拡散面を照らして表面反射光による 目視観察を行った。評価結果を表 1に示した。傷の評価には、以下の基準を用いて 目視で行った。  Using a stainless steel ball indenter (S US304, diameter 4.76mm) with a surface property tester HEIDON-14D (made by Shinto Kagaku Co., Ltd.), reciprocating 50 times at a moving speed of 60mmZ seconds with a load of 20gf, light The diffusion surface was rubbed. After rubbing, the light diffusing surface was turned up and the light from the fluorescent lamp was applied from the back to visually observe the transmitted light, and the light diffusing surface was illuminated under the fluorescent light and the surface reflected light was visually observed. The evaluation results are shown in Table 1. The scratch was evaluated visually using the following criteria.
〇 · · ·透過光および表面反射光による目視観察で、共に傷が確認されなかった。 ○ · · · No scratches were observed by visual observation with transmitted light and surface reflected light.
△ · · ·透過光による目視観察で傷は確認されな力つたが、表面反射光による目視 観察で、傷が確認された。 Δ ······ Flaws were confirmed by visual observation using transmitted light, but scratches were confirmed by visual observation using reflected light from the surface.
X · · ·透過光および表面反射光による目視観察で、共に傷が確認された。  X ··· Scratches were confirmed by visual observation with transmitted light and surface reflected light.
評価結果を表 1に示した。表 1からわかるように、硬化触媒を含有した榭脂粒子を使 用した場合、耐擦傷'性が最も良好となった。 [0055] (光学特性の評価） The evaluation results are shown in Table 1. As can be seen from Table 1, when the resin particles containing the curing catalyst were used, the scratch resistance was the best. [0055] (Evaluation of optical properties)
ヘイズメーター NDH2000 (日本電色社製）を使用し、光拡散フィルムの全光線透 過率とヘイズを測定した。評価結果を表 1に示した。表 1からゎカゝるように、硬化触媒 を含有した榭脂粒子を使用した場合でも、光透過性と光拡散性に違いは観られなか つた o  Using a haze meter NDH2000 (Nippon Denshoku Co., Ltd.), the total light transmittance and haze of the light diffusion film were measured. The evaluation results are shown in Table 1. As shown in Table 1, there was no difference in light transmission and light diffusibility even when using resin particles containing a curing catalyst.
[0056] [表 1]  [0056] [Table 1]
Figure imgf000023_0001
Figure imgf000023_0001
[0057] 表 1より明らかなように硬化触媒を有するアクリルウレタン榭脂粒子を用いた実施例 1 〜実施例 3は、良好な耐擦傷性と耐脱落性を有している。比較例 1〜比較例 3の榭 脂粒子は、実施例 1〜実施例 3に比べて、耐擦傷性が低下し、耐脱落性が顕著に低 下することがわかる。比較例 3のように塗料中に硬化触媒を添加しても、耐脱落性は 改良されないことがわかる。また、硬化触媒を有しないアクリルウレタン榭脂粒子を用 Vヽた比較例 4は、硬化触媒を有するアクリルウレタン榭脂粒子を用いた実施例 1〜実 施例 3に比べて、耐擦傷性と耐脱落性が低下することがわかる。 As is clear from Table 1, Examples 1 to 3 using acrylic urethane resin particles having a curing catalyst have good scratch resistance and drop-off resistance. It can be seen that the resin particles of Comparative Example 1 to Comparative Example 3 have lower scratch resistance and significantly lower drop resistance than Examples 1 to 3. It can be seen that even when a curing catalyst is added to the paint as in Comparative Example 3, the drop-off resistance is not improved. Further, Comparative Example 4 using acrylic urethane resin particles having no curing catalyst was more resistant to scratches than Examples 1 to 3 using acrylic urethane resin particles having a curing catalyst. It can be seen that the drop-off resistance is lowered.
[0058] さらに以下に、アクリルポリオールとイソシァネートを含有するバインダー榭脂の組成 について、イソシァネートの水酸基に対する当量比を変化させて光拡散層を形成し、 背面層を付加した上で耐擦傷性、及び耐脱落性等の特性を検討した。  [0058] Further below, regarding the composition of the binder resin containing acrylic polyol and isocyanate, the equivalent ratio of isocyanate to hydroxyl group is changed to form a light diffusion layer, and after adding a back layer, scratch resistance, and Characteristics such as dropout resistance were examined.
[0059] (実施例 4)  [Example 4]
<光拡散層用塗料 gの調製工程 >  <Preparation process of coating material for light diffusion layer g>
トルエン 278 質量部 アクリルウレタン榭脂粒子 (IV) 137 質量部 Toluene 278 parts by mass Acrylic urethane resin particles (IV) 137 parts by mass
アクリルポリオール「アタリディック A— 801— P」  Acrylic polyol "Ataridic A-801-P"
〔固形分 50%、固形分の水酸基価 100、大日本インキ化学工業社製〕  [50% solid content, hydroxyl value of solid content 100, manufactured by Dainippon Ink & Chemicals, Inc.]
100 質量部  100 parts by mass
ポリイソシァネート「コロネート HL」 55 質量部  Polyisocyanate "Coronate HL" 55 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 gを得た。このときイソシァネート の水酸基に対する当量比は 1. 9、榭脂バインダー（アクリルポリオール +ポリイソシァ ネート)の固形分 100質量部に対する光拡散材 (アクリルウレタン榭脂粒子)の配合 量は 150質量部であった。  The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material g. At this time, the equivalent ratio of isocyanate to hydroxyl group was 1.9, and the blending amount of the light diffusing material (acrylic urethane resin particles) with respect to 100 parts by mass of the solid content of the resin binder (acrylic polyol + polyisocyanate) was 150 parts by mass. .
[0060] <背面層用塗料 hの調製工程 > [0060] <Preparation process of paint h for back layer>
トルエン 120 質量部  120 parts by mass of toluene
アクリル榭脂「ダイヤナール BR— 80」 10 質量部  Acrylic resin "Dianar BR-80" 10 parts by mass
〔固形分 100%、水酸基価なし、三菱レイヨン社製〕  [100% solids, no hydroxyl value, manufactured by Mitsubishi Rayon Co., Ltd.]
帯電防止剤「力チォーゲン ES— L 9」 0. 5質量部  Antistatic agent “Power Ziegen ES—L 9” 0.5 parts by mass
〔カチオン系界面活性剤、第一工業製薬社製〕  [Cationic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.]
滑剤「ケミスノー MR—10HG」 0. 2質量部  Lubricant "Chemisnow MR-10HG" 0.2 parts by mass
〔アクリル榭脂粒子、体積平均粒子径 10 m、綜研化学社製〕  [Acrylic rosin particles, volume average particle size 10 m, manufactured by Soken Chemical Co., Ltd.]
上記の材料のうち、アクリル榭脂全量とトルエン 40質量部を分散攪拌機にて攪拌し 十分に溶解させたのち、残りの材料を追加して分散攪拌機にて攪拌混合し、背面層 用塗料 hを得た。  Among the above materials, the total amount of acrylic resin and 40 parts by mass of toluene were stirred and sufficiently dissolved with a dispersion stirrer, and then the remaining materials were added and stirred and mixed with a dispersion stirrer. Obtained.
[0061] <基材への塗布 '乾燥'硬化工程 > [0061] <Applying to Substrate 'Drying' Curing Process>
基材として、厚さ 100 mのポリエチレンテレフタレート（PET)フィルムを使用し、こ の一方の面に上記光拡散層用塗料 gを、乾燥膜厚 16 mになるように塗布し、熱風 乾燥させて光拡散層の乾燥塗膜を得た。他方の面に、上記背面層用塗料 hを、乾燥 膜厚 2 mになるように塗布し、熱風乾燥させて背面層の乾燥塗膜を得た。光拡散層 用塗料 gと背面塗料 hの塗布工程終了後、硬化反応を促進させるため、 40°C恒温室 中 48時間保管して光拡散フィルムを作製した。  Using a polyethylene terephthalate (PET) film with a thickness of 100 m as the base material, apply the light diffusion layer coating g on one side to a dry film thickness of 16 m and dry with hot air. A dry coating film of the light diffusion layer was obtained. On the other side, the back layer coating material h was applied to a dry film thickness of 2 m and dried with hot air to obtain a dry coating film for the back layer. After the coating process for light diffusion layer coating g and back coating h, the light diffusion film was prepared by storing in a constant temperature room at 40 ° C for 48 hours to accelerate the curing reaction.
[0062] (実施例 5) <光拡散層用塗料 iの調製工程 > [Example 5] <Preparation process of paint i for light diffusion layer>
トルエン 393 質量部 Toluene 393 parts by mass
アクリルウレタン榭脂粒子 (IV) 181 質量部 Acrylic urethane resin particles (IV) 181 parts by mass
アクリルポリオール「ダイヤナール LR 1532」 Acrylic polyol "Dianar LR 1532"
100 質量部  100 parts by mass
ポリイソシァネート「コロネート HL」 81 質量部 Polyisocyanate "Coronate HL" 81 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 iを得た。このときイソシァネート の水酸基に対する当量比は 2. 8、榭脂バインダー（アクリルポリオール +ポリイソシァ ネート)の固形分 100質量部に対する光拡散材 (アクリルウレタン榭脂粒子)の配合 量は 150質量部であった。  The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material i. At this time, the equivalent ratio of isocyanate to hydroxyl group was 2.8, and the blending amount of light diffusing material (acrylic urethane resin particles) with respect to 100 parts by mass of the solid content of the resin binder (acrylic polyol + polyisocyanate) was 150 parts by mass. .
以下、実施例 4における光拡散層用塗料 gの代わりに上記光拡散層用塗料 iを用い たほかは、実施例 1と同一の方法で、基材上に乾燥塗膜を形成し、光拡散フィルムを 作製した。  Hereinafter, a dry coating film was formed on the substrate in the same manner as in Example 1 except that the light diffusion layer coating i was used in place of the light diffusion layer coating g in Example 4. A film was produced.
(実施例 6) (Example 6)
<光拡散層用塗料 jの調製工程 >  <Preparation process of paint j for light diffusion layer>
トルエン 175 質量部 175 parts by mass of toluene
アクリルウレタン榭脂粒子 (IV) 91 質量部 Acrylic urethane resin particles (IV) 91 parts by mass
アクリルポリオール「アタリディック A— 801— P」 Acrylic polyol "Ataridic A-801-P"
100 質量部  100 parts by mass
ポリイソシァネート「コロネート HL」 14 質量部 Polyisocyanate "Coronate HL" 14 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 jを得た。このときイソシァネート の水酸基に対する当量比は 0. 5、榭脂バインダー（アクリルポリオール +ポリイソシァ ネート)の固形分 100質量部に対する光拡散材 (アクリルウレタン榭脂粒子)の配合 量は 150質量部であった。  The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material j. At this time, the equivalent ratio of isocyanate to hydroxyl group was 0.5, and the blending amount of the light diffusing material (acrylic urethane resin particles) with respect to 100 parts by mass of the solid content of the resin binder (acrylic polyol + polyisocyanate) was 150 parts by mass. .
以下、実施例 4における光拡散層用塗料 gの代わりに上記光拡散層用塗料 jを用い たほかは、実施例 4と同一の方法で、基材上に乾燥塗膜を形成し、光拡散フィルムを 作製した。  Hereinafter, a dry coating film was formed on the substrate in the same manner as in Example 4 except that the light diffusion layer coating material j was used instead of the light diffusion layer coating material g in Example 4. A film was produced.
(比較例 5) <光拡散層用塗料 kの調製工程 > (Comparative Example 5) <Process for preparing light diffusion layer coating material k>
トルエン 278 質量部 Toluene 278 parts by mass
アクリル榭脂粒子「ケミスノー MR— 7HG」 137 質量部 Acrylic rosin particles “Chemisnow MR—7HG” 137 parts by mass
〔体積平均粒子径約 6 μ m、綜研化学社製〕 [Volume average particle size: approx. 6 μm, manufactured by Soken Chemical Co., Ltd.]
アクリルポリオール「アタリディック A— 801— P」 Acrylic polyol "Ataridic A-801-P"
100 質量部  100 parts by mass
ポリイソシァネート「コロネート HL」 55 質量部 Polyisocyanate "Coronate HL" 55 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用 k塗料を得た。このときイソシァネート の水酸基に対する当量比は 1. 9、榭脂バインダー（アクリルポリオール +ポリイソシァ ネート)の固形分 100質量部に対する光拡散材 (アクリル榭脂粒子)の配合量は 150 質量部であった。  The above was stirred and mixed with a dispersion stirrer to obtain a k-coating material for the light diffusion layer. At this time, the equivalent ratio of isocyanate to the hydroxyl group was 1.9, and the blending amount of the light diffusing material (acrylic resin particles) with respect to 100 parts by mass of the solid content of the resin binder (acrylic polyol + polyisocyanate) was 150 parts by mass.
以下、実施例 4における光拡散層用塗料 gの代わりに上記光拡散層用塗料 kを用い たほかは、実施例 4と同一の方法で、基材上に乾燥塗膜を形成し、光拡散フィルムを 作製した。 Hereinafter, a dry coating film was formed on the substrate in the same manner as in Example 4 except that the light diffusion layer coating material k was used instead of the light diffusion layer coating material g in Example 4. A film was produced.
(比較例 6) (Comparative Example 6)
<光拡散層用塗料 1の調製工程 >  <Preparation process of paint 1 for light diffusion layer>
トルエン 278 質量部 Toluene 278 parts by mass
シリコーン榭脂粒子「KMP— 701」 137 質量部 Silicone resin particles "KMP-701" 137 parts by mass
〔体積平均粒子径約 3. 5 m、信越シリコーン社製〕  (Volume average particle diameter of about 3.5 m, manufactured by Shin-Etsu Silicone)
アクリルポリオール「アタリディック A— 801— P」 Acrylic polyol "Ataridic A-801-P"
100 質量部  100 parts by mass
ポリイソシァネート「コロネート HL」 55 質量部 Polyisocyanate "Coronate HL" 55 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 1を得た。このときイソシァネート の水酸基に対する当量比は 1. 9、榭脂バインダー（アクリルポリオール +ポリイソシァ ネート)の固形分 100質量部に対する光拡散材 (シリコーン榭脂粒子)の配合量は 15 0質量部であった。  The above was stirred and mixed with a dispersion stirrer to obtain a coating material 1 for a light diffusion layer. At this time, the equivalent ratio of isocyanate to hydroxyl group was 1.9, and the amount of the light diffusing material (silicone resin particles) to 100 parts by mass of the solid content of the resin binder (acrylic polyol + polyisocyanate) was 150 parts by mass. .
以下、実施例 4における光拡散層用塗料 gの代わりに上記光拡散層用塗料 1を用い たほかは、実施例 4と同一の方法で、基材上に乾燥塗膜を形成し、光拡散フィルムを 作製した。 Hereinafter, a dry coating film was formed on the substrate in the same manner as in Example 4 except that the light diffusion layer coating 1 was used instead of the light diffusion layer coating g in Example 4, and the light diffusion was performed. Film Produced.
[0066] (比較例 7)  [0066] (Comparative Example 7)
<光拡散層用塗料 mの調製工程 >  <Process for preparing light diffusion layer coating m>
トルエン 278 質量部  Toluene 278 parts by mass
スチレン榭脂粒子「テクポリマー SBX— 6」 137 質量部  Styrene resin particles "Techpolymer SBX-6" 137 parts by mass
〔平均粒子径約 6 μ m、積水化成品工業社製〕  (Average particle size: approx. 6 μm, manufactured by Sekisui Plastics Co., Ltd.)
アクリルポリオール「アタリディック A— 801— P」  Acrylic polyol "Ataridic A-801-P"
100 質量部  100 parts by mass
ポリイソシァネート「コロネート HL」 55 質量部  Polyisocyanate "Coronate HL" 55 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 mを得た。このときイソシァネー トの水酸基に対する当量比は 1. 9、榭脂バインダー（アクリルポリオール +ポリイソシ ァネート)の固形分 100質量部に対する光拡散材 (スチレン榭脂粒子)の配合量は 1 50質量部であった。  The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material m. At this time, the equivalent ratio of isocyanate to hydroxyl group was 1.9, and the blending amount of the light diffusing material (styrene resin particles) with respect to 100 parts by mass of the solid content of the resin binder (acrylic polyol + polyisocyanate) was 150 parts by mass. It was.
以下、実施例 4における光拡散層用塗料 gの代わりに上記光拡散層用塗料 mを用 いたほかは、実施例 4と同一の方法で、基材上に乾燥塗膜を形成し、光拡散フィルム を作製した。  Hereinafter, a dry coating film was formed on the substrate in the same manner as in Example 4 except that the light diffusion layer coating m was used instead of the light diffusion layer coating g in Example 4, and the light diffusion was performed. A film was produced.
[0067] (比較例 8) [0067] (Comparative Example 8)
<光拡散層用塗料 nの調製工程 >  <Preparation process of paint n for light diffusion layer>
トルエン 840 質量部  Toluene 840 parts by mass
アクリル榭脂「ダイヤナール BR— 80」 100 質量部  Acrylic resin "Dianar BR-80" 100 parts by mass
〔固形分 100%、水酸基価なし、三菱レイヨン社製〕  [100% solids, no hydroxyl value, manufactured by Mitsubishi Rayon Co., Ltd.]
アクリルウレタン榭脂粒子 (IV) 120 質量部  Acrylic urethane resin particles (IV) 120 parts by mass
上記の材料のうち、アクリル榭脂全量とトルエン 400質量部を分散攪拌機にて攪 拌し十分に溶解させたのち、残りの材料を追加して分散攪拌機にて攪拌混合し、光 拡散層用塗料 nを得た。榭脂バインダー (アクリル榭脂)の固形分 100質量部に対す る光拡散材 (アクリルウレタン榭脂粒子)の配合量は 120質量部であった。  Among the above materials, the total amount of acrylic resin and 400 parts by weight of toluene were sufficiently dissolved by stirring with a dispersion stirrer, and then the remaining materials were added and stirred and mixed with a dispersion stirrer to produce a coating material for a light diffusion layer. got n. The blending amount of the light diffusing material (acrylic urethane resin particles) with respect to 100 parts by mass of the solid content of the resin binder (acrylic resin) was 120 parts by mass.
以下、実施例 4における光拡散層用塗料 gの代わりに上記光拡散層用塗料 nを用 いたほかは、実施例 4と同一の方法で、基材上に乾燥塗膜を形成し、光拡散フィルム を作製した。 Hereinafter, a dry coating film was formed on the substrate in the same manner as in Example 4 except that the light diffusion layer coating n was used instead of the light diffusion layer coating g in Example 4, and the light diffusion was performed. the film Was made.
[0068] (光拡散層の耐擦傷性の評価）  [0068] (Evaluation of scratch resistance of light diffusion layer)
実施例 1〜3、比較例 1〜4について行ったと同じ表面性試験機、ステンレス製ボー ル圧子を使用し、 5gfの荷重をかけて移動速度 60mmZ秒で 50往復、光拡散面を 摩擦した。傷の評価には、実施例 1〜3、比較例 1〜4について行ったと同じ基準を用 いて行った。  Using the same surface property tester and stainless steel ball indenter that were used for Examples 1 to 3 and Comparative Examples 1 to 4, the light diffusion surface was rubbed 50 strokes at a moving speed of 60 mmZ seconds with a load of 5 gf. The same criteria as those used for Examples 1 to 3 and Comparative Examples 1 to 4 were used for the evaluation of the scratches.
評価結果を表 2に示した。表 2からわ力るように、アクリルウレタン榭脂粒子を使用 した場合、耐擦傷'性が最も良好となった。  The evaluation results are shown in Table 2. As shown in Table 2, the scratch resistance was the best when acrylic urethane resin particles were used.
[0069] (光拡散層の耐溶剤性の評価） [0069] (Evaluation of solvent resistance of light diffusion layer)
トルエン:メチルェチルケトン = 1： 1の混合溶剤で湿した綿棒を用い、光拡散層を摩 擦した。表 2に示した所定の回数摩擦したとき、以下の基準を用いて目視にて評価を 行った。  The light diffusion layer was rubbed with a cotton swab moistened with a mixed solvent of toluene: methyl ethyl ketone = 1: 1. When rubbed a predetermined number of times as shown in Table 2, the following criteria were used for visual evaluation.
〇 · · ·光拡散層に変化がみられな 、。  ○ No change in the light diffusion layer.
△ · · ·光拡散層が一部溶解した痕跡が残った。  Δ · · · Traces of partial dissolution of the light diffusion layer remained.
X · · ·光拡散層が剥がれて基材面が現れた。  X ... The light diffusion layer was peeled off and the substrate surface appeared.
評価結果を表 2に示した。  The evaluation results are shown in Table 2.
[0070] (榭脂粒子の脱落性の評価） [0070] (Evaluation of detachment properties of rosin particles)
実施例 1〜3、比較例 1〜4について行ったと同様の表面性試験機を使用し、同様 の方法で光拡散層面の榭脂粒子の脱落状態を顕微鏡にて観察した。評価結果を表 The same surface property tester as that used in Examples 1 to 3 and Comparative Examples 1 to 4 was used, and the falling state of the resin particles on the surface of the light diffusion layer was observed with a microscope in the same manner. Table of evaluation results
2に示した。榭脂粒子の脱落性の評価には、実施例 1〜3、比較例 1〜4について行 つたと同様の基準を用いた。 Shown in 2. For the evaluation of the detachment properties of the resin particles, the same criteria as those used for Examples 1 to 3 and Comparative Examples 1 to 4 were used.
[0071] [表 2] 先拡散フイルムの構成 評 価 結 果 [0071] [Table 2] Composition of pre-diffusion film Evaluation results
樹脂ハインタ-組成 耐溶剤 1  Resin Hinter composition Solvent resistance 1
樹脂粒子  Resin particles
イソシァネ -ト /水酸基 耐擦傷性 擦回 耐脱落性 (光拡散材）  Isocyanate / Hydroxyl Scratch resistance Scratch resistance (light diffusing material)
(当量比） 20 40 60  (Equivalent ratio) 20 40 60
実施例 4 アクリルウレタン 1. 9 o 〇 o 〇 o 実施例 5 アクリルウレタン 2. 8 o 〇 o o o 実施例 6 アクリルウレタン 0. 5 o 0 Δ 厶 0~Δ 比較例 5 アクリル 1. 9 △ 〇 o o X 比較例 6 シリコーン 1 . 9 Δ 〇 o o X 比較例 7 スチレン 1 . 9 X 〇 o o X 比較例 8 アクリルウレタン 0. 0 厶 X X X X  Example 4 Acrylic urethane 1.9 o ○ o ○ o Example 5 Acrylic urethane 2.8 o ○ ooo Example 6 Acrylic urethane 0.5 o 0 Δ 厶 0 to Δ Comparative Example 5 Acrylic 1.9 △ ○ oo X Comparative Example 6 Silicone 1.9 Δ ○ oo X Comparative Example 7 Styrene 1.9 X ○ oo X Comparative Example 8 Acrylic Urethane 0.0 厶 XXXX
[0072] 表 2からわ力るように、アクリルウレタン榭脂粒子は、光拡散層の榭脂バインダー組 成において、イソシァネートを含有していない場合は耐擦傷性、耐溶剤性、耐脱落性 ともに低下し、特に耐溶剤性、耐脱落性の低下が著しいことがわかる。さらに実施例 4 、実施例 5のようにイソシァネート Ζ水酸基の比率は 0. 7〜3. 0の適性範囲にあると 耐溶剤性、耐脱落性がより好ましいことがわかる。また前記比率が適性範囲にあった としても、シリコーン性榭脂粒子やスチレン性榭脂粒子では、耐擦傷性、耐脱落性の 双方とも低いことがわかる。 [0072] As can be seen from Table 2, acrylic urethane resin particles have both scratch resistance, solvent resistance, and detachment resistance in the composition of the resin binder of the light diffusion layer when they do not contain isocyanate. It can be seen that the solvent resistance and dropout resistance are particularly markedly reduced. Furthermore, it can be seen that the solvent resistance and the drop-off resistance are more preferable when the ratio of isocyanate to hydroxyl group is in the appropriate range of 0.7 to 3.0 as in Example 4 and Example 5. Further, even if the ratio is within the proper range, it is understood that both the silicone resistance particles and the styrenic resin particles are low in both scratch resistance and dropout resistance.
[0073] 以下にバインダー榭脂としてポリエステルポリオールをポリイソシァネートで架橋させ た榭脂を用いた場合の光拡散フィルムについて、耐擦傷性、耐脱落性等を検討する  [0073] In the following, the light diffusing film using a polyester polyol cross-linked with a polyisocyanate as a binder resin is examined for scratch resistance, drop-off resistance, etc.
(実施例 7) (Example 7)
<光拡散層用塗料 οの調製工程 >  <Preparation process of light diffusion layer paint ο>
トルエン 765 質量部  Toluene 765 parts by mass
シクロへキサノン 255 質量部  Cyclohexanone 255 parts by mass
アクリルウレタン榭脂粒子 (I) 385 質量部  Acrylic urethane resin particles (I) 385 parts by mass
ポリエステルポリオール「バーノック D6—439」  Polyester polyol "Bernock D6-439"
〔固形分 80%、固形分の水酸基価 140、大日本インキ化学工業社製〕  [80% solid content, hydroxyl value of solid content 140, manufactured by Dainippon Ink & Chemicals, Inc.]
150 質量部  150 parts by mass
ポリイソシァネート「バーノック DN— 950」  Polyisocyanate "Bernock DN-950"
〔固形分 75%、 HDI系、固形分中の有効 NCO含有量 13%、大日本インキ化学工業 社製〕 95 質量部 以上を分散攪拌機で攪拌混合し、光拡散層用塗料 oを得た。このときイソシァネート の水酸基に対する当量比は 0. 7であった。 [Solid content: 75%, HDI, effective NCO content in solid content: 13%, manufactured by Dainippon Ink & Chemicals, Inc.] 95 parts by mass The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material o. At this time, the equivalent ratio of isocyanate to hydroxyl group was 0.7.
基材として、厚さ 100 mのポリエチレンテレフタレート（PET)フィルムを使用し、こ の一方の面に上記光拡散層用塗料 oを、乾燥膜厚約 27 mになるように塗布し、熱 風乾燥させて光拡散層の乾燥塗膜を得た。塗布工程終了後、 40°C恒温室中 48時 間の熱エージング処理を行い光拡散フィルムを作製した。  Using a polyethylene terephthalate (PET) film with a thickness of 100 m as the base material, apply the above light diffusion layer coating material o on one side to a dry film thickness of about 27 m and dry with hot air. Thus, a dry coating film of the light diffusion layer was obtained. After the coating process was completed, a light diffusing film was produced by thermal aging for 48 hours in a 40 ° C constant temperature room.
[0074] (実施例 8)  [Example 8]
<光拡散層用塗料 Pの調製工程 >  <Preparation process of paint D for light diffusion layer>
トルエン 765 質量部  Toluene 765 parts by mass
シクロへキサノン 255 質量部  Cyclohexanone 255 parts by mass
アクリルウレタン榭脂粒子 (II) 385 質量部  Acrylic urethane resin particles (II) 385 parts by mass
ポリエステルポリオール「バーノック D6—439」  Polyester polyol "Bernock D6-439"
150 質量部  150 parts by mass
ポリイソシァネート「バーノック DN— 950」 95 質量部  Polyisocyanate "Bernock DN-950" 95 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 pを得た。このときイソシァネート の水酸基に対する当量比は 0. 7であった。  The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material p. At this time, the equivalent ratio of isocyanate to hydroxyl group was 0.7.
実施例 7における光拡散層用塗料 oの代わりに上記光拡散層用塗料 pを用いた他 は、実施例 7と同一の方法で、基材上に乾燥塗膜を形成し光拡散フィルムを作製し た。  In the same manner as in Example 7, except that the light diffusion layer coating material p was used instead of the light diffusion layer coating material o in Example 7, a dry coating film was formed on the substrate to produce a light diffusion film. did.
[0075] (実施例 9)  [0075] (Example 9)
<光拡散層用塗料 qの調製工程 >  <Process for preparing light diffusion layer coating q>
トルエン 850 質量部  Toluene 850 parts by mass
シクロへキサノン 290 質量部  Cyclohexanone 290 parts by mass
アクリルウレタン榭脂粒子 (III) 235 質量部  Acrylic urethane resin particles (III) 235 parts by mass
ポリエステルポリオール「バーノック D6—439」  Polyester polyol "Bernock D6-439"
150 質量部  150 parts by mass
ポリイソシァネート「バーノック DN— 950」 130 質量部  Polyisocyanate "Bernock DN-950" 130 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 qを得た。このときイソシァネート の水酸基に対する当量比は 1. 0であった。 The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material q. Isocyanate at this time The equivalent ratio of to hydroxyl group was 1.0.
実施例 7における光拡散層用塗料 oの代わりに上記光拡散層用塗料 qを用い、乾 燥膜厚を約 13 mとした他は、実施例 7と同一の方法で、基材上に乾燥塗膜を形成 し光拡散フィルムを作製した。  In the same manner as in Example 7, except that the light diffusion layer coating material q was used in place of the light diffusion layer coating material o in Example 7, and the dry film thickness was about 13 m. A coating film was formed to produce a light diffusion film.
[0076] (比較例 9) [0076] (Comparative Example 9)
<光拡散層用塗料 rの調製工程 >  <Preparation process of paint for light diffusion layer r>
トルエン 500 質量部  500 parts by mass of toluene
メチルェチルケトン 375 質量部  Methyl ethyl ketone 375 parts by mass
シクロへキサノン 75 質量部  Cyclohexanone 75 parts by mass
スチレン榭脂粒子「SBX— 12」 275 質量部  Styrene resin particles "SBX-12" 275 parts by mass
〔平均粒子径約 12 m、硬化触媒含有なし、積水化成品工業社製〕  [Average particle size of about 12 m, no curing catalyst, manufactured by Sekisui Plastics Co., Ltd.]
ポリエステル榭脂「エリーテル UE3600J 125 質量部  Polyester resin "ELITEL UE3600J 125 parts by mass
〔固形分 100%、水酸基価 4 、ュ-チカ社製〕  (Solid content 100%, hydroxyl value 4, manufactured by Utica)
ポリイソシァネート「バーノック DN— 950」 10 質量部  Polyisocyanate "Bernock DN-950" 10 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用 r塗料を得た。このときイソシァネート の水酸基に対する当量比は 3. 4であった。  The above was stirred and mixed with a dispersion stirrer to obtain a coating material for the light diffusion layer. At this time, the equivalent ratio of isocyanate to hydroxyl group was 3.4.
実施例 7における光拡散層用塗料 oの代わりに上記光拡散層用塗料!:を用い、乾燥 膜厚を約 24 mとした他は、実施例 7と同一の方法で、基材上に乾燥塗膜を形成し 光拡散フィルムを作製した。  In the same manner as in Example 7, except that the light diffusion layer coating!: Was used instead of the light diffusion layer coating! In Example 7 and the dry film thickness was about 24 m. A coating film was formed to produce a light diffusion film.
[0077] (比較例 10) [0077] (Comparative Example 10)
<光拡散層用塗料 sの調製工程 >  <Preparation process of light diffusion layer paint s>
トルエン 900 質量部  900 parts by mass of toluene
シクロへキサノン 120 質量部  Cyclohexanone 120 parts by mass
シリコーン榭脂粒子「トスパール 2000B」 150 質量部  Silicone oil particles “Tospearl 2000B” 150 parts by mass
アクリル榭脂「ダイヤナール BR— 85」 72 質量部  Acrylic resin "Dianar BR-85" 72 parts by mass
〔固形分 100%、水酸基価無し、三菱レイヨン社製〕  [100% solids, no hydroxyl value, manufactured by Mitsubishi Rayon Co., Ltd.]
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 sを得た。  The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material s.
実施例 7における光拡散層用塗料 oの代わりに上記光拡散層用塗料 sを用い、乾燥 膜厚を約 13 mとした他は、実施例 7と同一の方法で、基材上に乾燥塗膜を形成し 光拡散フィルムを作製した。 The light diffusion layer coating material s was used in place of the light diffusion layer coating material o in Example 7, and dried. A light-diffusing film was produced by forming a dry coating film on the substrate in the same manner as in Example 7 except that the film thickness was about 13 m.
[0078] (比較例 11) [0078] (Comparative Example 11)
<光拡散層用塗料 tの調製工程 >  <Preparation process of paint for light diffusion layer t>
トルエン 810 質量部  Toluene 810 parts by mass
シクロへキサノン 150 質量部  Cyclohexanone 150 parts by mass
ジブチル錫ジラウレート 0. 5 質量部  Dibutyltin dilaurate 0.5 parts by mass
アクリル榭脂粒子「MBX— 20」 315 質量部  Acrylic resin particles "MBX-20" 315 parts by mass
〔平均粒子径約 17 m、硬化触媒含有なし、積水化成品工業社製〕  [Average particle size of about 17 m, no curing catalyst, manufactured by Sekisui Plastics Co., Ltd.]
アクリルポリオール「アタリディック A— 801— P」  Acrylic polyol "Ataridic A-801-P"
265 質量部  265 parts by mass
ポリイソシァネート「バーノック DN— 950」 36 質量部  Polyisocyanate "Bernock DN-950" 36 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 tを得た。このときイソシァネート の水酸基に対する当量比は 0. 4であった。  The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material t. At this time, the equivalent ratio of isocyanate to hydroxyl group was 0.4.
実施例 7における光拡散層用塗料 oの代わりに上記光拡散層用塗料 tを用い、乾燥 膜厚を約 30 mとしたほかは、実施例 7と同一の方法で、基材上に乾燥塗膜を形成 し光拡散フィルムを作製した。  In the same manner as in Example 7, except that the light diffusion layer coating material t was used in place of the light diffusion layer coating material o in Example 7 and the dry film thickness was about 30 m, dry coating was performed on the substrate. A film was formed to produce a light diffusion film.
[0079] (比較例 12) [0079] (Comparative Example 12)
<光拡散層用塗料 uの調製工程 >  <Process for preparing light diffusion layer coating u>
トルエン 765 質量部  Toluene 765 parts by mass
シクロへキサノン 255 質量部  Cyclohexanone 255 parts by mass
アクリル榭脂粒子「MBX— 20」 385 質量部  Acrylic resin particles "MBX-20" 385 parts by mass
ポリエステルポリオール「バーノック D6—439」  Polyester polyol "Bernock D6-439"
150 質量部  150 parts by mass
ポリイソシァネート「バーノック DN— 950」 95 質量部  Polyisocyanate "Bernock DN-950" 95 parts by mass
以上を分散攪拌機で攪拌混合し、光拡散層用塗料 uを得た。このときイソシァネ ートの水酸基に対する当量比は 0. 7であった。  The above was stirred and mixed with a dispersion stirrer to obtain a light diffusion layer coating material u. At this time, the equivalent ratio of isocyanate to hydroxyl group was 0.7.
実施例 7における光拡散層用塗料 oの代わりに上記光拡散層用塗料 uを用い、乾 燥膜厚を約 30 mとしたほかは、実施例 7と同一の方法で、基材上に乾燥塗膜を形 成し光拡散フィルムを作製した。 In place of the light diffusion layer coating material o in Example 7, the light diffusion layer coating material u was used and dried. A light-diffusing film was produced by forming a dry coating film on the substrate in the same manner as in Example 7, except that the dry film thickness was about 30 m.
[0080] (比較例 13) [0080] (Comparative Example 13)
実施例 7において、アクリルウレタン榭脂粒子 (I)に替えてアクリルウレタン榭脂粒子 (V)を用いたほかは、実施例 7と同一の方法で、基材上に乾燥塗膜を形成し、光拡 散フィルムを作製した。  In Example 7, except that acrylic urethane resin particles (V) were used instead of acrylic urethane resin particles (I), a dry coating film was formed on the substrate in the same manner as in Example 7, A light diffusing film was produced.
[0081] 以上の実施例 7〜9、比較例 9〜13の各実施例、比較例に記した光拡散層を有する 光拡散フィルムについて以下の評価を行った。  [0081] The following evaluations were performed on the light diffusion films having the light diffusion layers described in Examples 7 to 9 and Comparative Examples 9 to 13 and Comparative Examples.
(榭脂粒子の脱落性の評価）  (Evaluation of detachment properties of sallow particles)
実施例 1〜6、比較例 1〜8に対して行ったと同様の表面性試験機を用い、同様の 方法で光拡散層面の榭脂粒子の脱落状態を顕微鏡にて観察した。評価結果を表 3 に示した。榭脂粒子の脱落性の評価には、実施例 1〜6、比較例 1〜8について行つ たと同様の基準を用いた。  Using the same surface property tester as performed for Examples 1 to 6 and Comparative Examples 1 to 8, the falling state of the resin particles on the surface of the light diffusion layer was observed with a microscope in the same manner. Table 3 shows the evaluation results. The same criteria as used for Examples 1 to 6 and Comparative Examples 1 to 8 were used for evaluation of the detachment properties of the greave particles.
[0082] (光拡散層の耐擦傷性の評価） [0082] (Evaluation of scratch resistance of light diffusion layer)
実施例 1〜6、比較例 1〜8で耐擦傷性試験を行ったときと同様の表面性試験機、 ステンレス製ボール圧子を用い、 50gfの荷重をかけて移動速度 60mmZ秒で 50往 復、光拡散面を摩擦した。摩擦後に残った傷を目視にて観察した。評価結果を表 3 に示した。表中、傷の評価には、実施例 1〜6、比較例 1〜8について行ったと同じ基 準を用いて行った。  Using the same surface property tester as in the scratch resistance test in Examples 1 to 6 and Comparative Examples 1 to 8, using a stainless steel ball indenter, applying 50 gf load, moving back and forth at 60 mmZ seconds, The light diffusing surface was rubbed. The scratches remaining after rubbing were visually observed. Table 3 shows the evaluation results. In the table, scratches were evaluated using the same standards as those used for Examples 1 to 6 and Comparative Examples 1 to 8.
[0083] (光学特性の評価） [0083] (Evaluation of optical properties)
実施例 1〜3、比較例 1〜4に対して行ったと同様の方法で、光拡散フィルムの全光 線透過率とヘイズを測定した。評価結果を表 3に示した。  The total light transmittance and haze of the light diffusion film were measured in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 4. The evaluation results are shown in Table 3.
[0084] [表 3] 光拡散フィルムの構成 if価結 [0084] [Table 3] Structure of light diffusion film
樹脂粒子 バインダー  Resin particle binder
体積平均 硬化触媒 耐 耐 光学特性  Volume average curing catalyst Anti-optical properties
ヘイズ 透適率 構成樹脂 i 構成樹脂 脱落性  Haze Permeability Component resin i Component resin
粒子経 (質量 %) 擦傷性 (%) (%)  Particle size (mass%) Abrasion (%) (%)
リエス亍ルポリオ- 実施例 7 アクリルウレタン 16 0. 05 ホ'  Riesel Polio- Example 7 Acrylic urethane 16 0. 05 E
ルとホ 'リイソシァネ -ト o Ο 96 99 実施例 8 アクリルウレタン 16 0. 05 ホリエス亍ルポリオ- ルとホ 'リイソシァネート o ο 96 99 実施例 9 アクリルウレタン 6 0. 04 ホ'リエステルポリオ - ルとホ 'リイソシァネ-ト o ο 95 99 比較例 9 スチレン樹脂 1 2 - ホ'リエス亍ル樹脂と X Δ 96 98  Example 8 Acrylic urethane 16 0.05 Polyisole polyol and resin 'O 96 99 Example 9 Acrylic urethane 6 0.04 Polyester polyol- 'Lyisocyanate o ο 95 99 Comparative Example 9 Styrene resin 1 2-E' Riselle resin and X Δ 96 98
ホ。リイソシァネ-ト  Ho. Lysocyanate
比較例 10シリコ-ン樹脂 6 - 熱可塑型 X  Comparative Example 10 Silicone Resin 6-Thermoplastic X
アクリル樹脂 94 99 アクリルホ'リオ-ルと  Acrylic resin 94 99 Acrylic resin
比較例 1 1 アクリル樹脂 1 7 塗料中に添加 X Δ 96 99  Comparative Example 1 1 Acrylic resin 1 7 Add to paint X Δ 96 99
ホ'リイソシァネ一ト  Ho's Lithocyanate
ホ-リエステルホ "リ才ール  Holyester Ho
比較例 1 2 アクリル樹脂 17 Δ~ χ 厶 96 ΘΘ  Comparative Example 1 2 Acrylic resin 17 Δ ~ χ 厶 96 ΘΘ
とホ'リイソシァネート  And Ho'liisocyanate
ホ-リエス亍ルホ "リ才ール  Holys Sulho
比較例 1 3 アクリルウレタン 1 6 Δ~ χ 厶 96 99  Comparative Example 1 3 Acrylic Urethane 1 6 Δ ~ χ 厶 96 99
とホ'リイソシァネート  And Ho'liisocyanate
[0085] 表 3より明らかなように硬化触媒を有するアクリルウレタン榭脂粒子を用いた実施例 7〜実施例 9は、良好なヘイズと透過率に加え耐擦傷性と耐脱落性を有している。比 較例 9のスチレン榭脂粒子、比較例 11, 12のアクリル榭脂粒子の場合はアクリルウレ タン榭脂粒子に比べて耐擦傷性が低下しており、また比較例 9〜 13の全ての榭脂粒 子は硬化触媒を含んで 、な 、ので耐脱落性が低下する。比較例 11のように塗料中 に硬化触媒を添加しても、耐脱落性は改良されないことがわ力る。 [0085] As is apparent from Table 3, Examples 7 to 9 using acrylic urethane resin particles having a curing catalyst have not only good haze and transmittance but also scratch resistance and shedding resistance. Yes. In the case of the styrene resin particles of Comparative Example 9 and the acrylic resin particles of Comparative Examples 11 and 12, the scratch resistance is lower than that of the acrylic urethane resin particles. Since the fat particles do not contain a curing catalyst, the drop-off resistance decreases. As shown in Comparative Example 11, even when a curing catalyst is added to the paint, the drop-off resistance is not improved.
産業上の利用可能性  Industrial applicability
[0086] 本発明の光拡散フィルムは、光拡散材として、光拡散層の榭脂バインダーにおいて 前記ポリイソシァネートによる架橋反応の触媒となる硬化触媒を含有しているアクリル ウレタン榭脂粒子を用い、榭脂バインダーとしてアクリルポリオールまたはポリエステ ルポリオールがポリイソシァネートで架橋された共重合体を用いて 、るために、榭脂 粒子と榭脂バインダーとの界面における榭脂バインダーの架橋反応が優先的かつ速 やかに進行し、榭脂バインダー力ゝら榭脂粒子が脱落し難 ヽ光拡散層を提供する事が できる。さらにアクリルウレタン榭脂粒子自体が従来のアクリル榭脂粒子、スチレン榭 脂粒子等に比べて耐擦傷性が良好であり、また、榭脂バインダーとして、塗膜硬度の 得やす 、ポリイソシァネート架橋による共重合体を用いて 、るために光拡散層面が 傷つき難い。一方、硬化触媒量は光学特性を阻害する程度まで添加する必要はなく 、従来の光拡散フィルムと同様の光透過性と光拡散性を維持することが可能である。 [0086] The light diffusing film of the present invention uses, as a light diffusing material, acrylic urethane resin particles containing a curing catalyst that serves as a catalyst for the crosslinking reaction with the polyisocyanate in the resin binder of the light diffusing layer. In order to use a copolymer in which acrylic polyol or polyester polyol is crosslinked with polyisocyanate as a resin binder, the crosslinking reaction of the resin binder at the interface between the resin particles and the resin binder has priority. It is possible to provide a light diffusing layer that progresses smoothly and quickly and is difficult for the resin particles to fall off due to the power of the resin binder. Furthermore, the acrylic urethane resin particles themselves have better scratch resistance than conventional acrylic resin particles, styrene resin particles, etc., and as a resin binder, it is easy to obtain coating film hardness, polyisocyanate crosslinking Therefore, the surface of the light diffusing layer is hardly damaged. On the other hand, it is not necessary to add the curing catalyst amount to the extent that the optical properties are hindered, and it is possible to maintain the same light transmittance and light diffusibility as those of conventional light diffusion films.

Claims

請求の範囲 The scope of the claims
[1] 透明なシート状基材の少なくとも一方の面に、榭脂バインダー中に榭脂粒子を分散 させた光拡散層を設けた光拡散フィルムであって、前記榭脂バインダーはアクリルポ リオールまたはポリエステルポリオールがポリイソシァネートで架橋された共重合体で あり、かつ前記榭脂粒子が、前記榭脂バインダーにおいて前記ポリイソシァネートに よる架橋反応の触媒となる硬化触媒を含有しているアクリルウレタン榭脂粒子である 事を特徴とする光拡散フィルム。  [1] A light diffusing film in which a light diffusing layer in which waving particles are dispersed in a waving binder is provided on at least one surface of a transparent sheet-like base material, the waving binder being acrylic polyol or polyester Acrylic urethane in which a polyol is a copolymer crosslinked with a polyisocyanate, and the resin particles contain a curing catalyst that serves as a catalyst for a crosslinking reaction with the polyisocyanate in the resin binder. A light diffusing film characterized by being a resin particle.
[2] 前記共重合体は、アクリルポリオールがポリイソシァネートで架橋されてなり、かつ前 記アクリルポリオールの構成要素として水酸基を有するアクリルモノマー単位を 1〜5 0質量％含有する共重合体である請求項 1に記載の光拡散フィルム。  [2] The copolymer is a copolymer obtained by crosslinking an acrylic polyol with a polyisocyanate and containing 1 to 50% by mass of an acrylic monomer unit having a hydroxyl group as a constituent element of the acrylic polyol. The light diffusing film according to claim 1.
[3] 前記硬化触媒は、ジブチル錫ジラウレートまたはジォクチル錫ジラウレートを含有す る請求項 1または 2に記載の光拡散フィルム。  [3] The light diffusing film according to [1] or [2], wherein the curing catalyst contains dibutyltin dilaurate or dioctyltin dilaurate.
[4] 前記硬化触媒は前記アクリルウレタン榭脂粒子に対して 0. 0001〜0. 5質量％含有 されてる請求項 3に記載の光拡散フィルム。  [4] The light diffusing film according to [3], wherein the curing catalyst is contained in an amount of 0.0001 to 0.5% by mass with respect to the acrylic urethane resin particles.
[5] 前記アクリルポリオールの水酸基価が 25以上 500以下、前記ポリイソシァネート中の イソシァネートの前記水酸基に対する当量比力 0. 7〜3. 0である請求項 1または 2 に記載の光拡散フィルム。  [5] The light diffusing film according to claim 1 or 2, wherein the acrylic polyol has a hydroxyl value of 25 or more and 500 or less, and an equivalent specific force of the isocyanate to the hydroxyl group in the polyisocyanate is 0.7 to 3.0. .
[6] 前記共重合体はポリエステルポリオールがポリイソシァネートで架橋されてなり、かつ 前記ポリエステルポリオールの水酸基価が 5以上 300以下、前記ポリイソシァネート 中のイソシァネートの前記水酸基に対する当量比力 0. 7〜3. 0である共重合体で ある請求項 1に記載の光拡散フィルム。  [6] The copolymer is formed by crosslinking a polyester polyol with a polyisocyanate, and the polyester polyol has a hydroxyl value of 5 or more and 300 or less, and an equivalent specific force of the isocyanate in the polyisocyanate with respect to the hydroxyl group is 0. 2. The light diffusing film according to claim 1, which is a copolymer of 7 to 3.0.
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