JP2006138878A - Antiglare filter and display using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiglare filter having excellent antiglare properties and abrasion resistance, also free from cracks or the like, and having excellent secondary workability, and to provide a display using the same. <P>SOLUTION: The antiglare filter has a resin layer obtained by curing a radiation curable composition containing, as a constituent, radiation curable urethane(meth)acrylate obtained by reacting organic isocyanate having a plurality of isocyanate groups in one molecule, e.g., a compound obtained by subjecting a diisocyanate monomer to isocyanurate modification with polycaprolactone modified alkyl(meth)acrylate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a scratch-resistant antiglare filter having scratch resistance and antiglare properties, and a display using the same.

  In the CRT display, the accelerated electrons collide with the phosphor inside the front glass and give energy, whereby the phosphor emits light, and usually red, green, and blue light are emitted to the front side. Also in the plasma display (PDP), the phosphor emits light, and light of each color is emitted to the front surface. Further, in the liquid crystal display, the liquid crystal itself does not emit light, but is illuminated from the back in order to improve the visibility of the liquid crystal image. Therefore, when viewed as a whole display, light is emitted toward the front. When the display is used indoors, illumination light such as fluorescent light is incident on the display surface, and when the light is reflected, the screen becomes dazzling, and the fluorescent light is reflected, making it difficult to recognize characters, etc. .

  In order to solve this problem, an anti-glare film in which a light-diffusing layer is formed by applying a silica-containing resin paint on a transparent base film is placed on the front of the display, and external light that causes glare It is already done to diffuse the screen and reduce the glare of the screen. For example, a conventional anti-glare film is provided with irregularities on the surface of the light diffusing layer by agglomeration of particles such as aggregating silica, and resin beads having a particle size larger than the thickness of the coating film are added to the surface. Using a shaped film with irregularities on the surface, or using a shaped film with irregularities on the surface, laminating it on the surface of the coating that has not solidified, transferring the irregular shape, and then removing the shaped film, etc. is there.

  On the other hand, in order to effectively reduce the glare of the screen, for example, when an anti-glare filter is used for display purposes, it is often located near the surface layer. Accordingly, scratches are easily caused by contact with a hard object, and the scratches are easily noticeable. In order to solve this problem, conventionally, ultraviolet (UV) curable and electron energy (EB) curable hard coat layers have been formed. However, in the hard coat layer, the use of a hard monomer for increasing the hardness and the increase in strain at the time of curing shrinkage by increasing the cross-linking density results in a decrease in adhesion to the substrate, chipping and cracking. The problem of occurring is likely to occur. In addition, these hard coat layers are hard and brittle, and there arises a problem that secondary processing such as winding and multi-function imparting operations becomes very difficult.

JP 2002-182015 A JP 2002-248712 A

  The present invention provides an anti-scratch anti-glare filter that has excellent anti-glare properties and scratch resistance, has no chipping and cracks, and has excellent processability.

  As a result of intensive studies by the inventors in view of the above problems, a resin having a specific structure in which the composition before curing contains a compound having a polycaprolactone structure as a constituent component is applied to an anti-glare filter. As a result, it was found that not only the scratch resistance but also excellent workability without occurrence of chipping and cracking can be imparted to the antiglare filter, and the present invention has been completed.

  The present invention is an antiglare filter having a resin layer obtained by curing a composition containing a compound having a polycaprolactone structure as a constituent component.

  The scratch-resistant anti-glare filter of the present invention is excellent in anti-glare property and scratch resistance, has excellent workability without causing cracks, and has high heat resistance.

The scratch-resistant antiglare filter of the present invention has a resin layer obtained by curing a composition containing a compound having a polycaprolactone structure as a constituent component as a scratch-resistant layer.
The scratch-resistant layer of the present invention can be provided as an anti-glare layer by imparting an anti-glare function, or the scratch-resistant layer and the anti-glare layer can be provided as individual layers.

  As shown in FIG. 1, the scratch-resistant anti-glare filter 1 of the present invention is provided with a scratch-resistant anti-glare layer 5 having both a scratch-resistant function and an anti-glare function on one side of a transparent substrate 3. It has a laminated structure. Alternatively, as a laminated structure in which the scratch resistance function and the antiglare function are separate layers, for example, as shown in FIG. 2, the antiglare function layer 13 and the antiglare function layer are formed on one surface of the transparent substrate 3. 13 may have a laminated structure in which the scratch-resistant functional layer 15 is provided in contact therewith. Further, the antiglare function layer 13 and the anti-scratch function layer 15 may be interchanged, or the anti-glare function layer 13 and the anti-scratch function layer 15 may be located with the transparent substrate 3 interposed therebetween.

  The first embodiment of the present invention will be described with reference to FIG.

  Since the transparent substrate 3 is used as a screen display device such as a display, it is required to have physical, mechanical, and chemical strengths, and is preferably transparent at least to visible light. .

  The material constituting the transparent substrate 3 includes polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, polyolefin resins such as cyclic polyolefin, polyethylene, and polypropylene, polyvinyl chloride, and polyvinylidene chloride. Vinyl resin, polystyrene, polyarylate, polycarbonate, polymethylpentene, polyamide (nylon-6, nylon-66, etc.), acrylic, triacetylcellulose (TAC), polyethersulfone, or polyetherketone, polymethylmethacrylate An unstretched film made of a resin such as the above, or a stretched film stretched uniaxially or biaxially, and these films may be a single layer or a plurality of layers of two or more layers. It may be.

  The thickness of the transparent substrate 3 is not particularly limited as long as the transparency is satisfied, but is preferably in the range of about 10 μm to 200 μm from the viewpoint of workability. If the thickness is less than 10 μm, the transparent base material 3 is too soft, and is easily stretched or wrinkled by the tension during processing. If the thickness exceeds 200 μm, the flexibility of the film decreases, This is because continuous winding in the process becomes difficult, and there is a problem that workability at the time of laminating a plurality of transparent base materials 3 is greatly deteriorated.

  The side on which the scratch-resistant antiglare layer 5 on the surface of the transparent substrate 3 is laminated, or the other layer is laminated on the surface of the transparent substrate 3 by laminating layers for improving adhesiveness or processing for improving adhesiveness. It may have been done.

The thickness of the scratch-resistant antiglare layer 5 of the present invention is not particularly limited, but is preferably 1 to 60 μm.
The scratch resistant antiglare layer 5 is a scratch resistant resin layer provided with an antiglare function. The method for developing the antiglare function is not particularly limited, and there are a method for containing fine particles and / or a method for obtaining fine irregularities by an embossing roll.

  The scratch-resistant resin layer of the present invention is obtained by curing a composition having a self-healing property and containing at least a compound having a polycaprolactone structure as a constituent component.

  The composition containing a compound having a polycaprolactone structure for forming the scratch-resistant resin layer of the present invention includes (1) radiation curable urethane (meth) acrylate such as ultraviolet rays and electron beams as a main component. The radiation curable composition to be contained and (2) a composition containing a polydimethylsiloxane copolymer, polycaprolactone and polysiloxane can be used. The scratch-resistant resin layer of the present invention may be a thermosetting resin or a radiation curable resin such as an ultraviolet ray or an electron beam, but it is preferable to cure the radiation curable composition from the viewpoint of production efficiency.

  The (1) radiation curable composition will be described in detail. The radiation curable composition of the present invention is synthesized, for example, by reacting (i) an organic isocyanate (A) having a plurality of isocyanate groups in one molecule with a polycaprolactone-modified alkyl (meth) acrylate (B). A composition containing a radiation curable urethane (meth) acrylate (C1) as a main component, and (ii) two or more different caprolactone unit repeating numbers per polycaprolactone-modified alkyl (meth) acrylate residue A composition containing as a main component a radiation curable urethane (meth) acrylate (C1), (iii) a radiation curable urethane (meth) acrylate (C1), and a plurality of isocyanate groups in one molecule Organic isocyanate (A) having hydroxyalkyl (meth) acrylate (D) A composition containing a radiation curable urethane (meth) acrylate (C2) synthesized as a main component, (iv) an organic isocyanate having a plurality of isocyanate groups in one molecule (A) And radiation curable urethane (meth) acrylate (C3) synthesized by reacting two or more polycaprolactone-modified alkyl (meth) acrylates (B) having different numbers of repeating caprolactone units. And (v) reacting an organic isocyanate (A) having a plurality of isocyanate groups in one molecule, a polycaprolactone-modified alkyl (meth) acrylate (B) and a hydroxyalkyl (meth) acrylate (D). Radiation curable urethane (meta Compositions acrylate (C4) is contained as the main component is effectively usable.

  Each of the radiation curable compositions (i) to (v) is a compound (E) having a radiation curable functional group copolymerizable with the urethane (meth) acrylate (C) and / or radiation curable. It is also preferable to contain a silicone graft or a block copolymer (F).

  The radiation curable composition (i) will be specifically described.

  The radiation curable composition (i) is synthesized by reacting an organic isocyanate (A) having a plurality of isocyanate groups in one molecule with a polycaprolactone-modified alkyl (meth) acrylate (B). The urethane (meth) acrylate (C1) is contained as a main component.

  The organic isocyanate (A) of the present invention is an organic compound having a plurality of isocyanate groups in one molecule, but the number of isocyanate groups contained in one molecule of the organic isocyanate is preferably 3 or more.

  The organic isocyanate having two isocyanate groups in one molecule includes tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate. And diisocyanate monomers such as methyl-2,6-diisocyanate hexanoate and norbornane diisocyanate.

  The organic isocyanate having three or more isocyanate groups in one molecule includes a compound represented by the following general formula (1) obtained by modifying a diisocyanate monomer with isocyanurate, and a general formula (2) represented by the following formula wherein adduct modification is performed on the diisocyanate monomer. An isocyanate prepolymer such as a compound represented by the following general formula (3) obtained by biuret modification of a diisocyanate monomer, 2-isocyanatoethyl-2,6-diisocyanate caproate, and triaminononane triisocyanate: Can be mentioned. An organic isocyanate having an isocyanurate ring is particularly preferred, whereby heat resistance is improved and light transmittance can be maintained even during heat-resistant storage.

The polycaprolactone-modified alkyl (meth) acrylate (B) of the present invention is a compound represented by the following general formula (4) and has a radiation curable functional group (CH2 =). Specific examples of this polycaprolactone-modified alkyl (meth) acrylate include polycaprolactone-modified hydroxyethyl (meth) acrylate, polycaprolactone-modified hydroxypropyl (meth) acrylate, polycaprolactone-modified hydroxybutyl (meth) acrylate, and the like. Polycaprolactone-modified hydroxyethyl (meth) acrylate is preferable.
By using a radiation curable composition containing urethane (meth) acrylate (C1) as a main component, relatively soft characteristics can be expressed based on the properties of urethane (meth) acrylate.

  The radiation curable composition (ii) will be described. However, only differences from the radiation curable composition (i) will be described.

  The radiation curable composition (ii) contains, as a main component, two or more types of radiation curable urethane (meth) acrylates (C1) having different numbers of repeating caprolactone units per polycaprolactone-modified alkyl (meth) acrylate residue. Has been.

  The average number of repetitions of caprolactone units per polycaprolactone-modified alkyl (meth) acrylate residue between urethane (meth) acrylates contained in the radiation curable composition is preferably in the range of 1 to 3.5. The difference in the number of repetitions is preferably 9 or less for the upper limit and 4 or more for the lower limit.

  Each urethane (meth) acrylate contained in the radiation curable composition is an organic isocyanate (A) having a plurality of isocyanate groups in one molecule, as in the case of the radiation curable composition (i). And polycaprolactone-modified alkyl (meth) acrylate (B).

  According to (ii), the scratch resistance based on the self-healing function of the surface can be improved.

  The radiation curable composition (iii) will be described. However, only differences from the radiation curable composition (i) will be described.

  The radiation curable composition (iii) comprises a radiation curable urethane (meth) acrylate (C1), an organic isocyanate (A) having a plurality of isocyanate groups in one molecule, and a hydroxyalkyl (meth) acrylate (D). Radiation curable urethane (meth) acrylate (C2) synthesized by reacting as a main component.

  Here, the hydroxyalkyl (meth) acrylate can be regarded as a (meth) acrylate monomer having zero repeating caprolactone units.

  In such a case, the average number of repetitions of caprolactone units per (meth) acrylate monomer residue between the two types of urethane (meth) acrylates is preferably in the range of 1 to 3.5. The difference in the number of repetitions is preferably 9 or less for the upper limit and 4 or more for the lower limit.

  The hydroxyalkyl (meth) acrylate (D) is a compound represented by the following general formula (5), such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like. Can be mentioned.

  According to (iii) described above, the scratch resistance based on the self-healing function of the surface can be improved.

  The radiation curable composition (iv) will be described. However, only differences from the radiation curable composition (i) will be described.

  The radiation curable composition (iv) is a urethane (meth) obtained by reacting two or more kinds of polycaprolactone-modified alkyl (meth) acrylate (B) having different repeating numbers of caprolactone units and an organic isocyanate (A). Acrylate (C3) is contained as a main component.

  The average number of repeats between polycaprolactone-modified alkyl (meth) acrylates having different numbers of repeats of caprolactone units is preferably in the range of 1 to 3.5. The difference in the number of repetitions is preferably 9 or less for the upper limit and 4 or more for the lower limit.

  According to the radiation curable composition (iv) described above, the scratch resistance based on the self-healing function of the surface can be improved.

  The radiation curable composition (v) will be described. However, only differences from the radiation curable composition (i, iii) will be described.

  In the curable composition (v), a urethane (meth) acrylate obtained by reacting a polycaprolactone-modified alkyl (meth) acrylate (B) or hydroxyalkyl (meth) acrylate (D) with an organic isocyanate (A) ( C4) is contained as a main component.

  Here, if the hydroxyalkyl (meth) acrylate is regarded as a (meth) acrylate monomer having a zero caprolactone unit repetition number, the radiation curable composition contains two or more types of different caprolactone unit repetition numbers ( It can be considered that urethane (meth) acrylate obtained by reacting a (meth) acrylate monomer and an organic isocyanate is contained as a main component.

  The average of the number of repetitions among (meth) acrylate monomers having different numbers of repetitions of caprolactone units is preferably in the range of 1 to 3.5. The difference in the number of repetitions is preferably 9 or less for the upper limit and 4 or more for the lower limit.

  According to (v) described above, the scratch resistance based on the self-healing function of the surface can be improved.

  The radiation curable functional group-containing compound (E) and / or the radiation curable silicone graft or block copolymer (F) may be added to the radiation curable compositions (i) to (v).

An example of the radiation curable functional group-containing compound (E) is a compound having a radiation curable functional group copolymerizable with urethane (meth) acrylate (C), and has a (meth) acryloyl group as a representative example. Monofunctional or polyfunctional monomers or oligomers may be mentioned. Specifically, monohydroxyethyl (meth) acrylate phthalate, 2-ethoxyhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polycaprolactone-modified hydroxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N-vinylpyrrolidone, acryloylmorpholine, isobornyl (meth) Monofunctional monomers such as acrylate, vinyl acetate, styrene; neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,6-hexanedio Rudi (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate , Difunctional monomers such as dipropylene glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane 3 mol propylene oxide adduct tri (meth) acrylate , Trimethylolpropane 6-mole ethylene oxide adduct tri (meth) acrylate, glycerin propoxytri (meth) acrylate, dipentaerythritol hexa (meta Polyfunctional monomers such as acrylate and hexa (meth) acrylate of dipentaerythritol caprolactone adduct; unsaturated polyester, polyester (meth) acrylate, polyether (meth) acrylate, acrylic (meth) acrylate, urethane (meth) Examples thereof include oligomers such as acrylate and epoxy (meth) acrylate.
By adding the radiation curable functional group-containing compound (E), the radiation curable composition can be reduced in viscosity and hybridized, and the adhesion of the resin layer to the transparent substrate and the solvent resistance can be improved. Can do.

  The radiation curable silicone graft or block copolymer (F) in the present invention comprises a polydimethylsiloxane portion (graft or block), a radiation curable urethane (meth) acrylate (C) (the isocyanate prepolymer compound (A) and A compound having a radiation-curable functional group copolymerizable with polycaprolactone-modified hydroxyethyl (meth) acrylate (B)), and may be a graft copolymer or block copolymer. It may be a coalescence. By introducing the silicone component into the crosslinked structure by the radiation curable silicone graft or block copolymer (F), the self-healing property of the impact resistant layer is further improved.

This radiation curable silicone graft or block copolymer (F) comprises a graft type reactive silicone (f1-1) or a block type reactive silicone (f1-2), a glycidyl group, an isocyanate group, a hydroxyl group, and a carboxyl. A vinyl monomer having a functional group such as a group (f2-1,2-2,2-3,2-4) and, if necessary, the reactive silicone (f1-1 and / or f1-2) ) And other vinyl monomers (f3) copolymerizable with the above-mentioned vinyl monomers (f2-1, 2-2, 2-3, 2-4)
And a compound (f4-1, 4-2, 4-3,4-4) having a radiation-curable functional group.

  Examples of the graft type reactive silicone (f1-1) include those having an unsaturated double bond at one end, such as a compound represented by the following formula (6).

Block type reactive silicone (f1-2
) Includes, for example, a compound represented by the following formula (7).

  Examples of the vinyl monomer (f2-1) having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, and glycidyl allyl ether. Examples of the vinyl monomer (f2-2) having an isocyanate group include: Examples include 2-isocyanatoethyl (meth) acrylate, methacryloyl isocyanate, vinyl isocyanate, etc. Examples of the vinyl monomer having a hydroxyl group (f2-3) include 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth). Acrylate, polyethylene glycol mono (meth) acrylate, phenoxyhydroxypropyl acrylate and the like. Examples of the vinyl monomer having a carboxyl group (f2-4) include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, Examples thereof include maleic acid and maleic anhydride.

  Examples of the other vinyl monomer (f3) copolymerizable with the reactive silicone (f1-1 and / or f1-2) include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n- Butyl acrylate, isobutyl acrylate, t-butyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, stearyl methacrylate, lauryl methacrylate, etc. Aliphatic or cyclic acrylate or methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propylene Vinyl ethers such as vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, styrenes such as styrene and α-methylstyrene, nitrile monomers such as acrylonitrile and methacrylonitrile, fatty acid vinyl such as vinyl acetate and vinyl propionate, chloride Examples thereof include halogen-containing monomers such as vinyl, vinylidene chloride, vinyl fluoride, and vinylidene fluoride, olefins such as ethylene and propylene, and dienes such as isoprene, chloroprene, and butadiene. These vinyl monomers (f3) are not reactive with the functional groups of the vinyl monomers (f2-1, 2-2, 2-3, 2-4).

  Moreover, as a compound (f4-1) which can react with a glycidyl group and has a radiation-curable functional group, acrylic acid having a carboxyl group, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, etc. Examples of the compound (f4-2) capable of reacting with an isocyanate group and having a radiation curable functional group include 2-hydroxyethyl (meth) acrylate having a hydroxyl group, hydroxypropyl (meth) acrylate, 2- Alcohol types such as hydroxybutyl (meth) acrylate and polyethylene glycol mono (meth) acrylate, epoxy types such as butoxyhydroxyacrylate and phenoxyhydroxypropyl acrylate, or dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate Examples of the compound (f4-3) capable of reacting with a hydroxyl group and having a radiation curable functional group include 2-isocyanatoethyl (meth) acrylate, methacryloyl isocyanate, vinyl isocyanate. Examples of the compound (f4-4) capable of reacting with a carboxyl group and having a radiation curable functional group include glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether, and the like. In addition, the above illustration does not limit this invention.

  You may add a photoinitiator (G) to each said radiation-curable composition. Thereby, the curing characteristics of the radiation curable composition, such as an increase in the curing rate, can be improved.

  Examples of the photoinitiator (G) of the present invention include isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler ketone, o-benzoylmethyl benzoate, acetophenone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, ethyl anthraquinone, p -Dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, 1-hydroxycyclohexyl phenyl ketone (for example, Irgacure 184 manufactured by Ciba Geigy Co., Ltd.), 2-hydroxy-2-methyl-1-phenyl-propane-1 -On (for example, Darocur 1173 manufactured by Ciba-Geigy Co., Ltd.), 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, Irgacure manufactured by Ciba-Geigy Co., Ltd.) 51), 2-benzyl-2-dimethylamino-l (4-morpholinophenyl) - butanone-1, bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide, and the like methylbenzyl formate.

  An antistatic agent may be added to the actinic radiation curable composition. In this way, an antistatic effect can be imparted to the antiglare layer.

  Examples of antistatic agents include anionic antistatic agents such as alkyl phosphates, cationic antistatic agents such as quaternary ammonium salts, nonionic antistatic agents such as polyoxyethylene alkyl ethers, lithium, sodium, and potassium. And an antistatic agent using an alkali metal salt. Among these, an antistatic agent using a lithium salt is preferable.

  You may add a solvent, a leveling agent, a ultraviolet absorber, etc. to the said radiation-curable composition. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol and isobutanol, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Examples of the solvent include ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and isobutyl acetate.

  Examples of leveling agents include acrylic copolymers, silicone-based and fluorine-based leveling agents. Specific examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, oxalic anilide-based, triazine-based and hindered amine-based ultraviolet absorbers.

  The reaction of synthesizing urethane (meth) acrylate (C) by reacting organic isocyanate (A) with polycaprolactone-modified alkyl (meth) acrylate (B) or hydroxyalkyl (meth) acrylate (D) is carried out in a solvent. Also good. Examples of solvents include aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate. Can be mentioned. In addition, the above reaction can be performed in a solvent-free system or in a compound having a radiation curable functional group, such as styrene, isobornyl acrylate, acryloyl morpholine, diethylene glycol diacrylate, triethylene glycol diacrylate, or the like. You can also

  The reaction temperature for reacting the organic isocyanate (A) with the polycaprolactone-modified alkyl (meth) acrylate (B) or hydroxyalkyl (meth) acrylate (D) is preferably from room temperature to 100 ° C., and the reaction time is from 1 to 10 Time is preferred.

  When synthesizing urethane (meth) acrylate by reacting organic isocyanate with polycaprolactone-modified alkyl (meth) acrylate or hydroxyalkyl (meth) acrylate, a catalyst or a polymerization inhibitor may be added to the reaction system. Examples of the catalyst include dibutyltin laurate, dibutyltin diethylhexoate, dibutyltin sulfite and the like. On the other hand, examples of the polymerization inhibitor include hydroquinone monomethyl ether.

  When synthesizing urethane (meth) acrylate by reacting organic isocyanate with polycaprolactone-modified alkyl (meth) acrylate or hydroxyalkyl (meth) acrylate, a long-chain alkyl alcohol is added to the reaction system, and the long-chain alkyl alcohol is added. You may make it react with organic isocyanate. If the resin layer is formed from the radiation curable composition containing urethane (meth) acrylate thus obtained, the scratch resistance can be improved by improving the surface slipperiness.

  You may add any of a long-chain alkyl group containing compound, a silicone type compound, and a fluorine-type compound to the said radiation-curable composition. Thereby, the improvement of surface slipperiness and self-repairability can be improved.

  The long-chain alkyl group-containing compound is preferably a polyether-modified long-chain alkyl alcohol. If a polyether-modified long-chain alkyl alcohol is used, an antistatic effect can be imparted. Examples of the polyether-modified long-chain alkyl alcohol include polyether-modified cetyl alcohol and polyether-modified stearyl alcohol.

  Moreover, it is preferable that carbon number of the alkyl group of the said long-chain alkyl group containing compound is 13-25. If the carbon number of this alkyl group is set within the above range, the scratch resistance based on the self-healing function can be improved. Specific examples of the long-chain alkyl group-containing compound having an alkyl group having 13 to 25 carbon atoms include tridecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, polyoxyethylene cetyl alcohol, polyoxyethylene stearyl alcohol, glycerol mono Long chain alkyl alcohols such as stearate; such as tridecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate A radiation curable compound is mentioned. Among these, the radiation curable compound has a radiation curable functional group.

  Specific examples of the silicone compound include polydimethylsiloxane, alkyl-modified polydimethylsiloxane, carboxyl-modified polydimethylsiloxane, amino-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, fluorine-modified polydimethylsiloxane, and (meth) acrylate-modified polydimethyl. Examples thereof include siloxane (for example, GUV-235 manufactured by Toagosei Co., Ltd.).

  Specific examples of the fluorine-based compound include compounds having a fluoroalkyl group such as a fluoroalkyl carboxylate, a fluoroalkyl quaternary ammonium salt, and a fluoroalkylethylene oxide adduct; a perfluoroalkyl carboxylate and a perfluoroalkyl quaternary ammonium salt. A compound having a perfluoroalkyl group such as a perfluoroalkylethylene oxide adduct; a compound having a fluorocarbon group; a tetrafluoroethylene polymer; a copolymer of vinylidene fluoride and tetrafluoroethylene; a copolymer of vinylidene fluoride and hexafluoropropylene Fluorine-containing (meth) acrylic acid ester; Fluorine-containing (meth) acrylic acid ester polymer; Fluorine-containing (meth) acrylic acid alkyl ester polymer; Fluorine-containing (meth) acrylic acid Copolymers of esters and other monomers.

  Further supplementing with respect to the fluorine-based compound, specific examples of the fluorine-containing (meth) acrylic acid ester include those listed below. That is, 3-perfluorohexyl-2-hydroxypropyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 3-perfluorohexyl-2-((meth) acryloyloxy) propyl = 2-((meth) acryloyl Oxymethyl) -2- (hydroxymethyl) propionate, 3-perfluorooctyl-2-hydroxypropyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 3-perfluorooctyl-2-((meth) acryloyloxy ) Propyl-2-((meth) acryloyloxymethyl) -2- (hydroxymethyl) propionate, 2-perfluorohexyl- (1-hydroxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 2 Perfluorohexyl-1-((meth) acryloyloxymethyl) ethyl = 2-((meth) acryloyloxymethyl) -2- (hydroxymethyl) propionate, 2-perfluorooctyl- (1-hydroxymethyl) ethyl = 2,2 -Bis ((meth) acryloyloxymethyl) propionate, 2-perfluorooctyl-1-((meth) acryloyloxymethyl) ethyl = 2-((meth) acryloyloxymethyl) -2- (hydroxymethyl) propionate, 3- Perfluorobutyl-2- (meth) acryloyloxypropyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 3-perfluorohexyl-2- (meth) acryloyloxypropyl = 2,2-bis ((meth) Acryloyloxy Til) propionate, 3-perfluorooctyl-2- (meth) acryloyloxypropyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 3-perfluorocyclopentylmethyl-2- (meth) acryloyloxypropyl = 2 , 2-bis ((meth) acryloyloxymethyl) propionate, 3-perfluorocyclohexylmethyl-2- (meth) acryloyloxypropyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 3-perfluorocycloheptylmethyl 2- (meth) acryloyloxypropyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 2-perfluorobutyl- (1- (meth) acryloyloxymethyl) ethyl = 2,2-bis ((me T) acryloyloxymethyl) propionate, 2-perfluorohexyl- (1- (meth) acryloyloxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 2-perfluorooctyl- (1- (meta ) Acryloyloxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 2-perfluorocyclopentylmethyl- (1- (meth) acryloyloxymethyl) ethyl = 2,2-bis ((meth) acryloyl) Oxymethyl) propionate, perfluorooctylethyl (meth) acrylate, 2-perfluorocyclohexylmethyl- (1- (meth) acryloyloxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propioner 2-perfluorocycloheptylmethyl- (1- (meth) acryloyloxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 2,2,2-trifluoroethyl (meth) acrylate , (Meth) acrylic acid-2,2,3,3,3-pentafluoropropyl, (meth) acrylic acid-2,2,3,3,4,4,4-heptafluorobutyl, (meth) acrylic acid -2,2,3,3,4,4,5,5,5-nonafluoropentyl, (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6,6 Undecafluorohexyl, (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl, (meth) acrylic acid-2 , 2,3,3,4,4,5,5,6,6 , 7,8,8,8-pentadecafluorooctyl, (meth) acrylic acid-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (Meth) acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecyl, (Meth) acrylic acid-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl, (meth) acrylic acid 2-trifluoromethyl-3,3,3-trifluoropropyl, (meth) acrylic acid-3-trifluoromethyl-4,4,4-trifluorobutyl, (meth) acrylic acid-1-methyl-2 , 2,3,3,3-pentafluoropropyl, 1-methyl-2,2,3,3 (meth) acrylic acid , 4,4,4-heptafluorobutyl, di (meth) acrylic acid-2,2,2-trifluoroethylethylene glycol, di (meth) acrylic acid-2,2,3,3,3-pentafluoropropyl Ethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,4-heptafluorobutylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,5 , 5,5-nonafluoropentylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6,6-undecafluorohexylethylene glycol, di (meth) ) Acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptylethylene glycol, di (meth) acrylic acid-2,2,3 3, 4, 4, 5, 5, 6, , 7,7,8,8,8-pentadecafluorooctylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8 , 8,9,9,10,10,10-nonadecafluorodecylethylene glycol, di (meth) acrylic acid-2,2,3,3-tetrafluorobutanediol, di (meth) acrylic acid-2,2 , 3,3,4,4-hexafluoropentadiol, di (meth) acrylic acid-2,2,3,3,4,4,5,5-octafluorohexanediol, di (meth) acrylic acid-2 , 2,3,3,4,4,5,5,6,6-decafluoroheptanediol, di (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6 , 7,7-dodecafluorooctanediol, di (meth) acrylic acid-2, , 3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorononanediol, di (meth) acrylic acid-2,2,3,3,4,4,4 5,5,6,6,7,7,8,8,9,9-hexadecafluorodecanediol, di (meth) acrylic acid-2,2,3,3,4,4,5,5,6 , 6,7,7,8,8,9,9,10,10-octadecafluoroundecanediol, di (meth) acrylic acid-2,2,3,3,4,4,5,5,6 6,7,7,8,8,9,9,10,10,11,11-eicosafluorododecanediol and the like.

In order to cure the radiation curable composition of the present invention, ultraviolet rays or electron beams are irradiated. As irradiation conditions in the case of irradiating with ultraviolet rays, it is preferable to use a mercury lamp, a metal halide lamp, or the like, and it is preferable to irradiate ultraviolet rays having an integrated light quantity of 100 to 5000 mJ / cm ² . Moreover, as irradiation conditions in the case of irradiating an electron beam, it is preferable to irradiate an electron beam of 1-20 Mrad with an acceleration voltage of 150-250 keV.

  The blending ratio of the radiation curable resin composition is, for example, urethane (meth) acrylate (C1), a compound (E) having a radiation curable functional group, a radiation curable silicone graft or a block copolymer (F), and light. In the mixing ratio of the initiator (G), the solid content ratio (weight) is preferably 20 to 99: 0 to 40: 0 to 40: 0.5 to 10, particularly 30 to 90: 5 to 35: 5. It is preferable that it is -35: 1-5.

  The composition containing the (2) polydimethylsiloxane copolymer, polycaprolactone and polysiloxane will be described. Each of polycaprolactone and polysiloxane may be introduced into the skeleton of the polydimethylsiloxane copolymer, or may exist separately.

  The polydimethylsiloxane copolymer in the present invention is a copolymer having a polydimethylsiloxane portion and a polymer chain portion of a vinyl monomer, and may be a block copolymer or a graft copolymer. There may be.

  The synthesis of the polydimethylsiloxane block copolymer can be performed by a living polymerization method, a polymer initiator method, a polymer chain transfer method, or the like. It is preferably carried out by the method.

のごとき高分子アゾ系ラジカル重合開始剤を使用してビニルモノマーと共重合させることにより、効率よくブロック共重合体を合成することができる。また、ペルオキシモノマーと不飽和基を有するポリジメチルシロキサンとを低温で共重合させて、過酸化物基を側鎖に導入したプレポリマーを合成し、該プレポリマーをビニルモノマーと共重合させる二段階の重合を行うこともできる。 In the polymer initiator method, for example,

A block copolymer can be efficiently synthesized by copolymerizing with a vinyl monomer using a polymer azo radical polymerization initiator such as Also, a two-stage process in which a peroxy monomer and polydimethylsiloxane having an unsaturated group are copolymerized at a low temperature to synthesize a prepolymer having a peroxide group introduced into a side chain, and the prepolymer is copolymerized with a vinyl monomer. The polymerization can also be carried out.

のごときシリコーンオイルに、ＨＳ−ＣＨ_２ＣＯＯＨや、ＨＳ−ＣＨ_２ＣＨ₂ＣＯＯＨ等を付加してＳＨ基を有するシリコーン化合物とした後、該ＳＨ基の連鎖移動を利用して該シリコーン化合物とビニルモノマーとを共重合させることにより、ブロック共重合体を合成することができる。 In the polymer chain transfer method, for example,

After adding HS—CH ₂ COOH, HS—CH ₂ CH ₂ COOH, etc. to a silicone oil such as a silicone compound having an SH group, the silicone compound and vinyl are utilized by utilizing chain transfer of the SH group. A block copolymer can be synthesized by copolymerizing with a monomer.

のごときポリジメチルシロキサンのメタクリルエステル等とビニルモノマーとを共重合させることにより、容易にかつ収率良くグラフト共重合体を合成することができる。 On the other hand, for polydimethylsiloxane graft copolymers, for example,

By copolymerizing a methacrylic ester of polydimethylsiloxane and the like with a vinyl monomer, a graft copolymer can be synthesized easily and with a high yield.

  Examples of vinyl monomers used in the copolymer with polydimethylsiloxane include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n -Butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, styrene, α-methyl styrene, acrylonitrile, methacrylonitrile, Vinyl acetate, vinyl chloride, vinylidene chloride, vinyl Vinyl chloride, vinylidene fluoride, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, citraconic acid, acrylamide, methacrylamide, N-methylolacrylamide, N , N-dimethylacrylamide, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, diacetone acrylamide and the like. Also, vinyl monomers having an OH group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and allyl alcohol can be used. A reaction product with acid, itaconic acid, crotonic acid, maleic acid or the like can also be used. In addition, the above illustration does not limit the present invention.

のごとき２官能ポリカプロラクトンジオール類や、

のごとき３官能ポリカプロラクトントリオール類、その他４官能ポリカプロラクトンポリオール等を使用することができる。該ポリカプロラクトンをポリジメチルシロキサン系共重合体の骨格に導入する場合には、ラクトン変成ヒドロキシエチル（メタ）アクリレート類を使用するのが好ましく、例えば、

の構造式で示されるラジカル重合性ポリカプロラクトンが挙げられる。 As polycaprolactone in the composition (2), for example,

Bifunctional polycaprolactone diols such as

Trifunctional polycaprolactone triols, other tetrafunctional polycaprolactone polyols, etc. can be used. When introducing the polycaprolactone into the skeleton of the polydimethylsiloxane copolymer, it is preferable to use lactone-modified hydroxyethyl (meth) acrylates, for example,

And radically polymerizable polycaprolactone represented by the structural formula:

  Examples of the polysiloxane in the present invention include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltoxioxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycol. Sidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxy Hydrolysis of propylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, etc. A partially hydrolyzed product of a silane compound having a silyl group, an organosilica sol in which silicic anhydride fine particles are stably dispersed in an organic solvent, or the above-mentioned silane compound having radical polymerizability added to the organosilica sol Can be used. In addition, the above illustration does not limit the present invention. The polysiloxane plays an important role in imparting heat resistance, stain resistance and the like to the resulting composition and improving the surface hardness of the coating film.

  The polydimethylsiloxane copolymer in the present invention is usually produced by solution polymerization. In this solution polymerization, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate, ethanol, isopropanol Alcohol solvents such as butanol and isobutanol are used alone or as a mixed solvent. If desired, oil-soluble polymerization initiators such as benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, and azobisisobutyronitrile are used. Is used. The reaction temperature of the solution polymerization is preferably 50 to 150 ° C., and the reaction time is preferably 3 to 12 hours.

  In the case where polycaprolactone and / or polysiloxane is introduced into the skeleton of the polydimethylsiloxane copolymer, the polycaprolactone and / or polysiloxane is added when polymerizing the polydimethylsiloxane copolymer. What is necessary is just to add and copolymerize.

  The amount of the polydimethylsiloxane moiety in the polydimethylsiloxane copolymer (including those in which polycaprolactone and / or polysiloxane is introduced into the skeleton) in the present invention is preferably 1 to 30% by weight. In particular, it is preferably 1 to 20% by weight. This polydimethylsiloxane part has a function of imparting lubricity to the coating film surface and imparting scratch resistance by lowering the coefficient of friction, but if the amount of the polydimethylsiloxane part is less than 1% by weight, such an effect is exerted. On the other hand, if the amount of the polydimethylsiloxane portion exceeds 30% by weight, the stain resistance of the coating film decreases. The molecular weight of the polydimethylsiloxane portion is preferably about 1000 to 30000, and the molecular weight that is effectively oriented on the surface of the coating film and imparts lubricity is particularly preferably about 5000 to 20000.

  The polycaprolactone in the present invention may be introduced into the skeleton of the polydimethylsiloxane copolymer, or may be present individually in the composition (in this case, externally added during coating production). It is preferably 5 to 50% by weight in the resin solid content. This polycaprolactone imparts high rebound resilience and good adhesion to the resin coating, and has a function of absorbing the rubbing force by energy elastic deformation when subjected to rubbing force. If the amount is less than 5% by weight, the scratch resistance and chipping resistance of the coating film are lowered. On the other hand, if the amount of the polycaprolactone exceeds 50% by weight, the stain resistance of the resin coating film is lowered.

  The polysiloxane in the present invention may be introduced into the skeleton of the polydimethylsiloxane copolymer, or may be present individually in the composition (in this case, externally added during coating production). The resin solid content is preferably 1 to 20% by weight. This polysiloxane has a function of imparting stain resistance, weather resistance, and heat resistance to the resin coating film and improving the surface hardness of the coating film. However, when the amount of the polysiloxane is less than 1% by weight, such an effect is required. On the other hand, if the amount of the polysiloxane exceeds 20% by weight, the scratch resistance of the resin coating film decreases.

  In order to cure the resin composition (2) of the present invention, the polydimethylsiloxane copolymer (including those in which polycaprolactone and / or polysiloxane is introduced into the skeleton) is urethane-crosslinked and / or melamine. Crosslinking is preferred. In order to urethane-crosslink the polydimethylsiloxane copolymer, methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of tolylene diisocyanate, hexamethylene is used for the polydimethylsiloxane copolymer having an OH group. Polyisocyanates such as diisocyanate trimethylolpropane adduct, isophorone diisocyanate trimethylolpropane adduct, tolylene diisocyanate isocyanurate, hexamethylene diisocyanate isocyanurate, isophorone diisocyanate isocyanurate, hexamethylene diisocyanate biuret Alternatively, a urethane cross-linking agent such as a block type isocyanate of the above polyisocyanate can be used. On the other hand, a melamine cross-linking agent such as alkoxymethylol melamine can be used to melamine cross-link the polydimethylsiloxane copolymer.

In the first embodiment, a method for causing the anti-glare function to develop in the scratch-resistant resin layer is not particularly limited. There is a method to obtain unevenness.
The fine particles constituting the antiglare function of the present invention are non-aggregating light-transmitting fine particles, and the refractive index of light and the light-transmitting resin (in the first embodiment, the scratch-resistant resin) is extremely small. By being close, it has transparency when dispersed in the translucent resin, and the particle diameter of the translucent fine particles is preferably in the range of 1.0 to 5.0 μm. When the particle size is less than 1.0, sufficient light diffusibility does not occur even when added, and when the particle size exceeds 5.0 μm, image definition and light transmittance cannot be sufficiently obtained. Specific non-aggregating light-transmitting fine particles include organic particles such as styrene beads (refractive index: 1.60), melamine beads (refractive index: 1.57), acrylic beads (refractive index: 1.49). ), Acrylic-styrene beads (refractive index: 1.54), polycarbonate beads, polyethylene beads, polyvinyl chloride beads, etc., among which styrene beads and acrylic-styrene beads are preferable. Among the non-aggregating light-transmitting fine particles, inorganic ones include SiO ₂ (refractive index; 1.5 to 2.0), Al—SiO ₂ (refractive index; 1.65), GeO ₂ ( Refractive index; 1.65) can be used, and SiO ₂ is particularly preferable. Since all of the above-mentioned translucent fine particles are non-aggregating, an effective internal scattering property can be obtained due to a difference in refractive index from the translucent resin, and it becomes possible to prevent glare.

In the anti-glare filter of this invention, the difference of the refractive index of light of a translucent fine particle and a translucent resin needs to be 0.05-0.15. The refractive index of the translucent resin is about 1.5 in the case of the radiation curable resin, but in the case of other resins, if the refractive index of the light is low, the refractive index is larger than the allowable refractive index difference. The transparency of the translucent fine particles may be reduced. In such a case, TiO ₂ (refractive index; 2.3 to 2.7), Y ₂ O ₃ (refractive index; 1.87), La, which are fine particles having a high refractive index of light, with respect to the translucent resin. By adding ₂ O ₃ (refractive index; 1.95), ZrO ₂ (refractive index; 2.05), Al ₂ O ₃ (refractive index; 1.63), or the like, the refractive index of the translucent resin The refractive index difference from the translucent fine particles can be adjusted. This method is effective when inorganic translucent fine particles are used.

  The non-aggregating translucent fine particles are added in a ratio of 5 to 30 parts by weight with respect to 100 parts by weight of the translucent resin. If the non-aggregating light-transmitting fine particles are less than 5 parts by weight, sufficient light diffusibility cannot be obtained, so that antiglare and anti-reflection properties of the resulting antiglare film cannot be sufficiently obtained. On the other hand, if the amount exceeds 30 parts by weight, the light diffusibility is improved, but the haze value (= haze value) is increased, the transmitted image clarity is decreased, and the light transmittance (= total light transmittance) is increased. The disadvantage of lowering occurs.

  Next, the scratch resistant antiglare filter 11 according to the second embodiment in which the scratch resistant function and the antiglare function are provided as separate layers will be described. However, only differences from the scratch-resistant antiglare filter 1 according to the first embodiment will be described.

  As shown in FIG. 2, the scratch-resistant anti-glare filter 11 has a laminated structure in which the anti-glare layer 13 and the scratch-resistant layer 15 are provided on the transparent substrate 3.

  The scratch-resistant layer 13 is a compound having at least a polycaprolactone structure having self-healing properties similar to that of the scratch-resistant resin layer (not provided with an antiglare function) described in the first embodiment. It is a resin layer obtained by hardening the composition contained as a structural component. By using this resin layer, the antiglare filter can have scratch resistance, and can also have excellent workability without occurrence of chipping and cracking.

  The antiglare layer 15 is not particularly limited, but a resin layer in which non-aggregating translucent fine particles are dispersed in a translucent resin can be suitably used.

  The non-aggregating translucent fine particles here are the same as the light fine particles described in the first embodiment.

  The translucent resin referred to here is one obtained by crosslinking and curing an ionizing radiation curable resin, one obtained by crosslinking and curing an ionizing radiation curable resin together with a solvent drying type resin, and in particular, a thermoplastic resin as a solvent drying type resin. Some of them are hardened by thermosetting resins.

  Among these, those in the range of ionizing radiation curable resins include oligomers or prepolymers that are mainly acrylates, or monofunctional or polyfunctional monomers. Examples of oligomers or prepolymers include relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and polyhydric alcohols (metabolites). ) Acrylate. These ionizing radiation curable resins may contain the following monofunctional monomers or polyfunctional monomers as reactive diluents. Monofunctional monomers include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, or N-pyrrolidone, and polyfunctional monomers include trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, Propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, or neopentyl glycol di ( There are (meth) acrylates. Moreover, these monofunctional monomers or polyfunctional monomers can be used by crosslinking only with monomers without the above-mentioned oligomers or prepolymers, or they can be mixed with thermoplastic resins or thermosetting resins. Can also be used.

  Examples of solvent-drying resins that may be added to the ionizing radiation curable resin include mainly cellulose-based resins such as nitrocellulose resin, acetylcellulose resin, cellulose acetate propionate resin, and ethylhydroxyethylcellulose resin, which have high transparency. ,preferable.

  Thermosetting resins used as translucent resins include phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, unsaturated polyester resins, polyurethane resins, epoxy resins, amino alkyd resins, urea melamine resins, or There are silicone resins. When using a thermosetting resin, a crosslinking agent or a polymerization initiator is added as necessary.

The scratch-resistant antiglare layer 5, the antiglare layer 13 or the scratch-resistant layer 15 of the present invention is prepared by dissolving a composition selected from the curable composition in a solvent as necessary in the transparent substrate 3 or other layers. Then, the coating liquid whose viscosity is adjusted is formed by coating and curing. The coating is a method of various coatings such as normal Meyer bar coating, doctor blade coating, gravure coating, gravure reverse coating, kiss reverse coating, three roll reverse coating, slit reverse die coating, die coating, or comma coating. 1-60 g / m ² , preferably 3-15 g / m ² (in terms of solid content, hereinafter the same) coating / solvent is dried.

  The scratch-resistant antiglare filter of the present invention has one or more functions of one layer or an infrared absorption function, an electromagnetic wave shielding function, a color tone adjusting function, a neon light shielding function, or an antireflection function. Layers can be used in a stacked manner.

The anti-glare filter of the present invention is highly valuable when applied to various displays, particularly plasma displays. In this application, for example, an adhesive is used. The adhesive is preferably applied in advance to the anti-glare filter in order to attach the anti-glare filter to the application target, and is configured using a suitable double-sided adhesive tape in addition to an appropriate adhesive. You can also. In addition, when applying to a plasma display, it can affix directly on the front glass of a plasma display.
(Example)

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Note that the present invention is not limited by these descriptions.

(Synthesis Example 1)
Hexamethylene diisocyanate isocyanurate modified type (Mitsui Takeda Chemicals, Takenate D-170N, isocyanate content: 21%) 50 parts, polycaprolactone modified hydroxyethyl acrylate (Daicel Chemical Industries, Plaxel FA2) 90 parts, And 0.02 part of dibutyltin laurate. Then, it was kept at room temperature for 30 minutes, further heated to 70 ° C. and kept at the same temperature for 5 hours to obtain urethane acrylate. The number of repeating caprolactone units per acrylate monomer residue in this urethane acrylate is 2.

(Synthesis Example 2)
Hexamethylene diisocyanate isocyanurate-modified type (Mitsui Takeda Chemicals, Takenate D-170N) 50 parts, polycaprolactone-modified hydroxyethyl acrylate (Daicel Chemical Industries, Plaxel FA1) 50.5 parts, polycaprolactone-modified hydroxyethyl 21.4 parts of acrylate (Daicel Chemical Industries, Ltd. Plaxel FA5) and 0.02 part of dibutyltin laurate were mixed. Then, it was kept at room temperature for 30 minutes, further heated to 70 ° C. and kept at the same temperature for 5 hours to obtain a mixture of urethane acrylate. In addition, the average number of repetitions of caprolactone units per acrylate monomer residue in these urethane acrylates is 1.5.

(Synthesis Example 3)
Hexamethylene diisocyanate isocyanurate modified type (Mitsui Takeda Chemicals, Takenate D-170N) 50 parts, polycaprolactone modified hydroxyethyl acrylate (Daicel Chemical Industries, Plaxel FA5) 180 parts, and dibutyltin laurate 0.02 The parts were mixed. Then, it was kept at room temperature for 30 minutes, further heated to 70 ° C. and kept at the same temperature for 5 hours to obtain urethane acrylate. The number of repeating caprolactone units per acrylate monomer residue in this urethane acrylate is 5.

(Synthesis Example 4)
Hexamethylene diisocyanate isocyanurate-modified type (Mitsui Takeda Chemicals, Takenate D-170N) 50 parts, 2-hydroxyethyl acrylate (Kyoeisha Chemical Co., Ltd. light ester HOA) 29.4 parts, and dibutyltin laurate 0. 02 parts were mixed. Then, it was kept at room temperature for 30 minutes, further heated to 70 ° C. and kept at the same temperature for 5 hours to obtain urethane acrylate. In addition, the repeating number of the caprolactone unit per acrylate monomer residue in this urethane acrylate is zero.

  Polymethyl methacrylate having a particle diameter of 5 μm is mixed as resin beads for imparting antiglare properties to 100 parts of urethane acrylate obtained in Synthesis Example 1 by mixing 2 parts of a photoinitiator (Irgacure 184 manufactured by Ciba Geigy). 4 parts by weight of acrylate beads were blended with 100 parts by weight of resin. Furthermore, 0.2 parts by weight of silica beads having a particle size of 0.25 μm as a resin beads settling inhibitor was added to 100 parts by weight of the resin to give a radiation curable composition that imparts antiglare properties. The radiation curable composition was applied on a triacetyl cellulose film by a reverse roll coating method so as to have a film thickness of 7 μm (when dried). Next, it was passed under a 160 W ultraviolet irradiation device at a speed of 5 m / min, and the resin was cured to obtain an antiglare filter having scratch resistance based on a self-repair function. The number of repeating caprolactone units per acrylate monomer residue in the urethane acrylate contained in the radiation curable composition is 2.

  60 parts of a mixture of urethane acrylates obtained in Synthesis Example 2, 20 parts of triethylene glycol diacrylate (Kyoeisha Chemical Co., Ltd. Light Acrylate 3EG-A), phthalic acid monohydroxyethyl acrylate (Toagosei Co., Ltd. M-5400) Except that 20 parts and 2 parts of photoinitiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) were mixed to prepare a radiation curable composition, resin beads, anti-settling agent, and coating method were the same as in Example 1. An antiglare filter having scratch resistance based on the repair function was obtained. In addition, the average number of repetitions of caprolactone units per acrylate monomer residue in the urethane acrylate contained in the radiation curable composition is 1.5. The difference in the number of repetitions between urethane acrylates contained in the radiation curable composition is 4 at the maximum.

  51.5 parts of urethane acrylate obtained in Synthesis Example 3, 18.5 parts of urethane acrylate obtained in Synthesis Example 4, 28 parts of triethylene glycol diacrylate (Light Acrylate 3EG-A manufactured by Kyoeisha Chemical Co., Ltd.), and light Resin beads, anti-settling agent, and coating method were the same as in Example 1 except that 2 parts of an initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) was mixed to prepare a radiation curable composition. An antiglare filter having scratching properties was obtained. In addition, the average number of repetitions of caprolactone units per acrylate monomer residue in the urethane acrylate contained in the radiation curable composition is 2.5. Moreover, the difference of the said repeating number between two types of urethane acrylate contained in this radiation-curable composition is 5.

(Comparative Example 1)
As a radiation curable composition for the antiglare layer, polymethyl methacrylate is used as a thermoplastic resin for 100 parts by weight of a resin composition comprising a mixture of polyester acrylate and polyurethane acrylate (EXG: trade name: manufactured by Dainichi Seika). 37 parts by weight of acrylate was blended. As resin beads for imparting antiglare properties, 4 parts by weight of poly (methyl methacrylate) beads having a particle diameter of 5 μm were blended with respect to 100 parts by weight of the resin. As an anti-settling agent for resin beads, 0.2 part by weight of silica beads having a particle size of 0.25 μm was blended with respect to 100 parts by weight of the resin to obtain an antiglare property. The coating composition was applied on a triacetyl cellulose film by a reverse roll coating method so as to have a film thickness of 7 μm (when dried). Next, the film was passed under a 160 W ultraviolet irradiator at a speed of 5 m / min to cure the resin, thereby obtaining an antiglare filter having scratch resistance based on the hard coat layer.

(Evaluation)
The results of evaluating the filters obtained in the examples and comparative examples are shown in FIG. The antiglare filters of Examples 1 to 3 all had good performance, but the antiglare filter of Comparative Example 1 was not satisfactory in bending resistance and heat resistance.

[Evaluation methods]
Anti-glare property: The anti-glare property was determined by copying it onto a scratch-resistant anti-glare filter produced with a bare fluorescent lamp without louver, and visually evaluating the glare of the regular reflection light according to the following criteria. ○: Dazzle is not felt, ×: Dazzle is felt.
-Bending resistance: When the produced anti-scratch antiglare filter was wound around a cylinder having a diameter of 2.5 cm, the filter did not cause breakage such as cracks or cracks, and the breakage occurred was rated as x.
-Heat resistance: When the produced anti-glare filter was allowed to stand in an atmosphere of 60 ° C for 100 hours, the case where the change in the appearance of the filter did not occur was evaluated as ◯, and the case where the change in the appearance occurred was evaluated as x.
Scratch resistance: The amount of change in haze (%) after rubbing 20 times with a load of 500 grams using a # 0000 steel wool on the scratch-resistant antiglare filter was measured.

It is explanatory drawing of the anti-glare filter of this invention. It is explanatory drawing of the anti-glare filter of this invention. It is an evaluation result about an Example and a comparative example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ......... Anti-glare filter 3 ......... Transparent substrate 5 ......... Abrasion-resistant anti-glare layer 11 ......... Anti-glare filter 13 ......... Anti-glare layer 15 ......... An abrasion-resistant layer

Claims (6)

  An antiglare filter having a resin layer obtained by curing a composition containing a compound having a polycaprolactone structure as a constituent component.   The composition contains, as a constituent, a radiation curable urethane (meth) acrylate obtained by reacting an organic isocyanate having a plurality of isocyanate groups in one molecule with a polycaprolactone-modified alkyl (meth) acrylate. 2. The antiglare filter according to claim 1, which is a radiation curable composition.   The antiglare filter according to claim 2, wherein the urethane (meth) acrylate has an isocyanurate ring.   The anti-glare filter according to claim 2 or 3, wherein the resin has at least one of a long-chain alkyl group-containing compound, a silicone compound, and a fluorine compound in the skeleton.   The antiglare filter according to any one of claims 1 to 4, wherein the resin layer contains translucent fine particles or has fine irregularities on a surface thereof. A display in which the antiglare filter according to any one of claims 1 to 5 is disposed on the observation side of the display.

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