JP2006138879A - Antireflection filter and display using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection filter having abrasion resistance based on a self-recovery function, and also having an excellent antireflection function, and to provide a display using the same. <P>SOLUTION: The antireflection filter comprises: 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 ; and an antireflection layer composed of a plurality of antireflection films. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

  When various displays typified by CRT, LCD, and PDP are used indoors, there is a problem that light from an illumination such as a fluorescent light enters the display surface and the screen becomes dazzling when the light is reflected. An antireflection filter is provided. The antireflection film is required to have scratch resistance on the surface.

  Many conventional antireflection filters use a UV-curable hard coat resin to impart scratch resistance (Japanese Patent Laid-Open No. 2002-192647). However, since these are hard and hard to be damaged, they are fragile, so that there is a problem that secondary processing such as winding or multi-function imparting work becomes very difficult. An antireflection filter using a relatively soft urethane resin (Japanese Patent Laid-Open No. 10-219006) is also known, which is free from cracks during winding, but is based on insufficient control of the refractive index. There was a problem of appearance that could not withstand practical use due to uneven color.

JP 2002-192647 A Japanese Patent Application Laid-Open No. 10-219006

  The present invention provides an antireflection filter that has excellent antireflection properties and scratch resistance, is free from cracks, has excellent processability, and has improved color unevenness.

  In view of the above problems, the present inventors have conducted intensive group studies, and as a result, 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 antireflection filter. Thus, the present invention has found that an antireflection filter having an antireflection filter having excellent antireflection properties and scratch resistance, having no cracks and the like, excellent workability, and improved color unevenness can be provided. It came to be completed.

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

  The scratch-resistant antiglare filter of the present invention is excellent in anti-glare property and scratch resistance based on a self-repair function, has excellent workability without causing cracks, and has high heat resistance.

  As shown in FIG. 1, the antireflection filter 1 having scratch resistance according to the present invention is most basically provided with a scratch-resistant layer 5 on one surface of a transparent substrate 3, and the scratch-resistant layer 5 is formed on the scratch-resistant layer 5. It has a laminated structure in which an antireflection layer 7 composed of antireflection films 7a and 7b is laminated.

  Since the transparent substrate 3 of the present invention is used as a screen display device such as a display, it requires physical, mechanical, and chemical strengths, and has transparency to at least visible light. It is preferable.

  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 layer 5 on the surface of the transparent substrate 3 is laminated or the side on which other layers are laminated has been subjected to lamination of layers for improving adhesiveness or treatment for improving adhesiveness. It may be.

  The thickness of the scratch-resistant layer 5 of the present invention is not particularly limited, but is preferably 1 to 60 μm.

  The refractive index of the scratch-resistant layer is preferably in the range of 1.50 to 1.65. Thereby, an antireflection filter with improved color unevenness can be obtained.

  The scratch-resistant 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 layer of the present invention includes (1) a main component of radiation curable urethane (meth) acrylate such as ultraviolet rays and electron beams. A radiation curable composition, (2) a composition containing a polydimethylsiloxane copolymer, polycaprolactone and polysiloxane can be used. The scratch-resistant 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) are reacted respectively.

  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.

  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, a friction coefficient decreases, it can improve surface slipperiness and self-repairability. In the present invention, it is particularly preferable to add a silicone compound.

  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.

The scratch-resistant layer 5 of the present invention is formed by coating and curing a coating liquid prepared by dissolving a composition selected from the curable composition in a solvent as necessary in a transparent substrate 3 and adjusting the viscosity. To do. 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.

  In the antireflection layer 7 of the present invention, for example, (1) a high refractive index layer and a low refractive index layer are sequentially laminated from the scratch-resistant layer 5 side, and (2) a high refractive index layer and a low refractive index, respectively. A refractive index layer, a high refractive index layer, and a low refractive index layer are sequentially stacked, or (3) a medium refractive index layer, a high refractive index layer, and a low refractive index layer are sequentially stacked. Other than these may be used. The example in FIG. 1 corresponds to a layer in which the high refractive index layer and the low refractive index layer in (1) above are laminated. In the examples in (2) and (3), the antireflection film has four layers, respectively. It becomes a laminated structure of layers and three layers.

The high refractive index layer in the above (1) and (2) and the medium refractive index layer in (3) are ZnO, TiO ₂ , CeO ₂ , Sb ₂ O ₅ , SnO ₂ , indium tin oxide, antimony-doped indium oxide. A thin film made of a material selected from the group consisting of tin, In ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , Al ₂ O ₃ , HfO ₂ , and ZrO ₂ , or ultrafine particles made of these materials are dispersed. The resin film can be constituted.

(1), (2), and (3) a low refractive index layer in a thin film made of SiO _2, SiO ₂ gel film or a fluorine-containing or fluorine and silicon ultraviolet curable resin composition containing It can be composed of a cured film.

  The high refractive index layer in (3) is a metal thin film made of a metal selected from the group consisting of Fe, Ni, Cr, Ti, Hf, Zn, Zr, Mo, and Ta, or ultrafine particles made of these metals Can be constituted by a resin film in which is dispersed.

  In the present invention, the scratch-resistant layer and the antireflection layer have been described separately, but the scratch-resistant layer can also be used as one layer of the antireflection film.

  The antireflection filter of the present invention may be subjected to antistatic treatment, and may be given conductivity for this purpose. By imparting electrical conductivity, it is possible to prevent dust from being attached due to charging. Conductivity can be imparted by laminating a conductive layer containing conductive particles between the transparent substrate 3 and the scratch-resistant layer 5, and depending on the required degree of conductivity, the scratch-resistant layer 5 Conductive particles can also be contained therein.

  The scratch-resistant antireflection 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 antiglare function. Layers can be used in a stacked manner.

The antireflection 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. In order to attach the antireflection filter to the application target, the adhesive is preferably applied in advance to the antireflection filter. In addition to using an appropriate adhesive, the adhesive is configured using a commercially available double-sided adhesive tape. You can also. In addition, when applying to a plasma display, it can affix directly on the front glass of a plasma display.
(Example)

  Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following examples, “part” means “part by weight”.

(Synthesis Example 1)
Hexamethylene diisocyanate isocyanurate-modified type (Takeda Pharmaceutical Co., Ltd. Takenate D-170N, isocyanate content: 21%) 50 parts, polycaprolactone-modified hydroxyethyl acrylate (Daicel Chemical Industries, Ltd. Plaxel FA2) 90 parts, and 0.02 part of dibutyltin laurate was 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 urethane acrylate monomer residue is 2.

(Synthesis Example 2)
Hexamethylene diisocyanate isocyanurate modified type (Takenate D-170N, Takeda Pharmaceutical Co., Ltd.) 50 parts, polycaprolactone modified hydroxyethyl acrylate (Dacel Chemical Industries, Plaxel FA1) 50.5 parts, polycaprolactone modified hydroxyethyl acrylate (Daicel Chemical Industry Plaxel FA5) 21.4 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 a mixture of urethane acrylate. The average number of repeats of caprolactone units per urethane acrylate monomer residue is 1.5.

(Synthesis Example 3)
Isocyanurate modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Takeda Pharmaceutical Co., Ltd.), 180 parts of polycaprolactone modified hydroxyethyl acrylate (Placcel FA5 manufactured by Daicel Chemical Industries, Ltd.), 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 urethane acrylate. The number of repeating caprolactone units per urethane acrylate monomer residue is 5.

(Synthesis Example 4)
Isocyanurate modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Takeda Pharmaceutical Co., Ltd.), 29.4 parts of 2-hydroxyethyl acrylate (light ester HOA manufactured by Kyoeisha Chemical Co., Ltd.), and 0.02 of dibutyltin laurate 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 urethane acrylate monomer residue is zero.

(Synthesis Example 5)
20 parts of polycaprolactone triol having a hydroxyl value of 200, 80 parts of polycaprolactone triol having a hydroxyl value of 540 and 0.4 parts of a light stabilizer (MARK LA-77 manufactured by Asahi Denka Co., Ltd.) are heated and melted at 80 ° C. for 2 hours. The mixture was stirred and vacuum degassed to produce a rope polyol composition. Further, 100 parts of an isocyanate group-containing 21.4% by weight of nurate-modified hexamethylene diisocyanate and 0.003 part of dibutyltin laurate were stirred and mixed to produce a uniform isocyanate liquid. Next, the two stations are stirred and mixed while adjusting the weight ratio so that the NCO index is 95, and heated in a polymerization oven at 80 ° C. for 20 minutes to substantially complete the polymerization to obtain a urethane coating solution. It was.

  100 parts of urethane acrylate obtained in Synthesis Example 1 was mixed with 2 parts of a photoinitiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) to obtain a coating composition comprising a radiation curable composition that imparted scratch resistance. The coating composition was applied on a triacetyl cellulose film (refractive index = 1.49) by a reverse roll coating method so as to have a film thickness of 3 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 produce a scratch-resistant layer (refractive index = 1.56) based on self-healing properties. Next, 50% by weight of hollow silica sol having an average particle diameter of 60 nm with respect to 100 mol% of Si (OC2H5) 4 was added to prepare a low refractive index coating agent using 1.0N-HCl as a catalyst. The low refractive index coating agent is applied to the scratch resistant layer side of the antireflective filter from which the low refractive index coating agent is obtained using a micro gravure method so as to have a film thickness of 100 nm (when dried), and dried at 120 ° C. for 1 minute. Thus, a low refractive index layer was formed (refractive index = 1.38).

  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) Scratch resistant layer (refractive index based on self-healing function) in the same manner as in Example 1 except that 20 parts and 2 parts of photoinitiator (Irgacure 184 manufactured by Ciba Geigy) were mixed to prepare a radiation curable composition. = 1.51) was obtained. The average number of repetitions of caprolactone units per acrylate monomer residue in the urethane acrylate contained in the radiation curable composition was 1.5. The difference in the number of repetitions between urethane acrylates contained in this radiation curable composition is 4 at the maximum. Next, a low refractive index coating agent was applied with a film thickness of 100 nm (when dried) to the scratch-resistant layer side of the antireflection filter obtained in the same manner as in Example 1 and dried at 120 ° C. for 1 minute. As a result, a low refractive index layer was formed (refractive index = 1.38).

  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 A scratch-resistant layer (refractive index = 1.63) based on a self-healing function was prepared in the same manner as in Example 1 except that 2 parts of an initiator (Irgacure 184 manufactured by Ciba Geigy) was mixed to prepare a radiation curable composition. To obtain an antireflection filter having. In addition, the average number of repetitions of caprolactone units per acrylate monomer residue in the urethane acrylate contained in this radiation curable composition is 2.5. The difference in the number of repetitions between the two types of urethane acrylate contained in the radiation curable composition is 5. Next, a low refractive index coating agent using 1.0N-HCl as a catalyst with respect to 100 mol% of Si (OC2H5) 4 was prepared. The low refractive index coating agent is applied to the scratch resistant layer side of the antireflective filter from which the low refractive index coating agent is obtained using a micro gravure method so as to have a film thickness of 100 nm (when dried), and dried at 120 ° C. for 1 minute. Thus, a low refractive index layer was formed (refractive index = 1.48).

  On the same triacetyl cellulose film as used in Example 1, a paint containing ATO (antimony-doped indium tin oxide) ultrafine particles (manufactured by Shinto Paint Co., Ltd., ATO ultrafine particle paint) was applied. An antistatic layer (refractive index = 1.53) was provided. Next, a scratch-resistant layer and a low refractive index layer were sequentially laminated on the obtained antistatic layer side in the same manner as in Example 1.

On the same triacetyl cellulose film as used in Example 1, a paint containing ATO (antimony-doped indium tin oxide) ultrafine particles (manufactured by Shinto Paint Co., Ltd., ATO ultrafine particle paint) was applied. An antistatic layer (refractive index = 1.53) was provided. Next, an anti-scratch layer was prepared in the same manner as in Example 1 on the obtained antistatic layer side, and the ZrO ₂ fine particle coating solution No. 1221 (coating liquid consisting of 0.3 parts by weight of binder (ionizing radiation curable organosilicon compound) with respect to 100 parts by weight of ZrO ₂ fine particles: trade name, manufactured by Sumitomo Osaka Cement Co., Ltd.) so that the film thickness becomes 57 nm. The coating was applied by gravure reverse coating, and an electron beam was irradiated at an acceleration voltage of 175 KeV for 5 Mrad to cure the coating film to form a medium refractive index layer (refractive index = 1.71). A weight of radiation curable resin (X-12-2400: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and ZrO ₂ ultrafine particles (No. 926: trade name, manufactured by Sumitomo Osaka Cement Co., Ltd.) are weighted on the produced medium refractive index layer weight. A liquid resin composition blended at a ratio of 2: 1 was applied by gravure reverse coating so as to be 7 μm / dry, and an electron beam was irradiated at an acceleration voltage of 175 KeV for 5 Mrad to cure the coating film. Ratio = 1.88). Further, a low refractive index layer was produced in the same manner as in Example 1 on the produced high refractive index layer.

An antireflection filter was obtained in the same manner as in Example 1 except that the urethane resin (refractive index = 1.68) obtained in Synthesis Example 5 was used as the scratch-resistant layer.
(Comparative Example 1)

  As a resin for the scratch-resistant layer, 37 parts by weight of polymethyl methacrylate as a thermoplastic resin with respect to 100 parts by weight of a resin composition composed of a mixture of polyester acrylate and polyurene acrylate (EXG: trade name: manufactured by Dainichi Seika) A low refractive index layer was produced in the same manner as in Example 1 except that a scratch-resistant layer (refractive index = 1.48) using a partially blended material was used, and a reflective layer having a scratch-resistant layer based on a hard coat layer. A prevention filter was obtained.

(Evaluation)
The filters obtained in the examples and comparative examples were evaluated. The results are shown in FIG. All of the antireflection filters of Examples 1 to 5 had good performance. Further, the antireflection filter of Example 6 had a slight color unevenness. Further, the antireflection filter of Comparative Example 1 was not satisfactory in bending resistance.

[Evaluation methods]
Luminous reflectance: Measured with a spectrophotometer (product number: UV-3100PC, company name: Shimadzu Corporation) in accordance with JIS-Z8701.
-Bending resistance (workability): When the produced antireflection filter is wound around a cylinder with a diameter of 2.5 cm, the filter does not cause breakage such as cracks or cracks. .
Scratch resistance: The amount of change in haze (%) of a rubbing rubbing 20 times with a load of 500 grams was measured using # 0000 steel wool on the produced anti-glare filter. A haze change of less than 1% was evaluated as ◯, and 1% or more as x.
-Color unevenness: When the color unevenness could not be recognized visually, it was evaluated as ◯, and when it could be recognized as x.
Refractive index: Measured with an ellipsometer (product number: UVISELTM, company name: JOBIN YVON).

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

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ......... Antireflection filter 3 ......... Transparent substrate 5 ......... Abrasion-resistant layer 7a, 7b ......... Antireflection film

Claims (7)

  An antireflection filter having an abrasion-resistant layer obtained by curing a composition containing a compound having a polycaprolactone structure as a constituent component.   The antireflection filter according to claim 1, wherein the scratch-resistant layer has a refractive index in the range of 1.50 to 1.65.   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. The antireflection filter according to claim 1, wherein the antireflection filter is a radiation curable composition.   The antireflection filter according to claim 3, wherein the urethane (meth) acrylate has an isocyanurate ring.   The antiglare filter according to claim 2 or 3, wherein the urethane (meth) acrylate has at least one of a long-chain alkyl group-containing compound, a silicone compound, and a fluorine compound in the skeleton.   The antireflection filter according to claim 1, further comprising an antistatic layer. A display in which the antireflection filter according to any one of claims 1 to 6 is disposed on the observation side of the display.

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