JP2007108765A - Anti-reflection material, method for producing anti-reflection material, protective film for polarizing plate, and polarizing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-reflection material which has high surface hardness, is hardly scratched, has high durability and low reflectance, prevents external light from being made incident thereto and consequently has a wide-view angle, and has high light transmittance and high adhesive strength to a transparent base material. <P>SOLUTION: The anti-reflection material is produced by forming an anti-reflection layer on the transparent base material. The anti-reflection layer is constituted of a plurality of layers. At least one layer of the plurality of layers is formed from a composition containing a metal alkoxide condensate, a cross-linking polymer and a solvent. The cross-linking polymer has -CH=CH-CO- groups in the main chain and/or, in the side chains. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antireflection material suitable as a film to be bonded to a polarizing plate of a liquid crystal display device, a method for producing the antireflection material, a polarizing plate protective film, and a polarizing plate, for example.

  Liquid crystal display devices (LCDs) can be directly connected to IC circuits with low voltage and low power consumption, and in particular, because they can be made thin, they are widely used as display devices for word processors and personal computers. Has been. This LCD has a basic configuration in which, for example, polarizing plates are provided on both sides of a liquid crystal cell.

  By the way, the polarizing plate passes only light having a polarization plane in a certain direction. Therefore, the LCD plays an important role in visualizing the change in the alignment of the liquid crystal due to the electric field. That is, the performance of the LCD greatly depends on the performance of the polarizing plate. A general structure of a polarizing plate is shown in FIG. In FIG. 1, reference numeral 1 denotes a polarizer, and a polarizing plate protective film 2 is laminated on both sides of the polarizer 1. The LCD is configured by laminating the polarizing plate having such a configuration on the liquid crystal cell.

  The polarizer 1 is obtained by adsorbing and stretching iodine or the like on a polymer film. That is, a solution called H ink containing a dichroic substance (iodine) is wet-adsorbed on a polyvinyl alcohol film, and then the film is uniaxially stretched to orient the dichroic substance in one direction. It is. The polarizing plate protective film 2 is provided for the purpose of improving durability.

  Accordingly, it is desired that the material has high durability, for example, has high surface hardness and is hardly damaged. Furthermore, it is desirable that the reflectance is low in order to prevent reflection of external light.

  Therefore, the problem to be solved by the present invention is that the surface hardness is high, scratches do not easily occur, durability is high, and the reflectance is low, and reflection of external light is prevented, and as a result, the viewing angle is also reduced. It is to provide a material that spreads and has high light transmittance and high adhesion to a transparent substrate.

The above issues are
An antireflection material in which an antireflection layer is provided on a transparent substrate,
The antireflection layer is composed of a plurality of layers,
At least one of the plurality of layers is composed of a composition containing a condensate of metal alkoxide, a crosslinkable polymer, and a solvent,
The crosslinkable polymer is solved by an antireflective material characterized by having a —CH═CH—CO— group in its main chain and / or side chain.

Also, an antireflection material provided with an antireflection layer on a transparent substrate,
The antireflection layer is composed of a plurality of layers,
At least one of the plurality of layers is composed of a composition containing a condensate of metal alkoxide, a crosslinkable polymer, and a solvent,
The crosslinkable polymer is solved by an antireflection material having an azide group in the main chain and / or side chain.

Also, an antireflection material provided with an antireflection layer on a transparent substrate,
The antireflection layer is composed of a plurality of layers,
At least one of the plurality of layers is composed of a composition containing a condensate of metal alkoxide, a crosslinkable polymer, and a solvent,
The ratio of the metal alkoxide condensate and the crosslinkable polymer is solved by an antireflection material characterized in that the metal alkoxide condensate / crosslinkable polymer = 3 to 50 (mass ratio).

  In addition, the antireflective material described above is solved by an antireflective material characterized in that the crosslinkable polymer has a —CH═CH—CO— group in its main chain and / or side chain. .

  In addition, the antireflection material described above is solved by an antireflection material characterized in that the crosslinkable polymer has an azide group in its main chain and / or side chain.

  Further, in the antireflection material described above, the ratio of the metal alkoxide condensate and the crosslinkable polymer is a metal alkoxide condensate / crosslinkable polymer = 3 to 50 (mass ratio). Solved by prevention material.

Also, an antireflection material provided with an antireflection layer on a transparent substrate,
The antireflection layer is composed of a plurality of layers,
At least one of the plurality of layers is composed of a composition containing a metal alkoxide condensate, a cationic polymerization compound, and a solvent,
The ratio of the metal alkoxide condensate and the cationic polymerization compound is solved by an antireflection material characterized in that the metal alkoxide condensate / cationic polymerization compound = 3 to 50 (mass ratio).

  The antireflection material, wherein the cationic polymerization compound is selected from the group consisting of an oxirane cyclic compound, an oxetane cyclic compound, a thiitan cyclic compound, and a thietan cyclic compound. Solved by the material.

  In addition, the antireflection material, which is a composition containing a metal alkoxide condensate, is solved by an antireflection material characterized by further containing an epoxy-based active energy ray-reactive compound.

  In addition, the antireflection material described above, which is a composition containing a metal alkoxide condensate, is solved by an antireflection material characterized by further containing an epoxy-based active energy ray-reactive compound and a polymerization initiator. The

  The antireflection material according to the above, wherein the composition containing a condensate of metal alkoxide further contains an epoxy-based active energy ray reactive compound, a polymerization initiator, and water. Solved by.

In addition, the above-described antireflection material constituent requirements are provided,
The refractive index is higher than the refractive index of the layer composed of the composition containing the metal alkoxide condensate above the layer composed of the composition containing the metal alkoxide condensate in the antireflection material layer. This is solved by an antireflection material characterized by comprising a low refractive index layer having a low refractive index.

In addition, the above-described antireflection material constituent requirements are provided,
The refractive index is higher than the refractive index of the layer composed of the composition containing the metal alkoxide condensate above the layer composed of the composition containing the metal alkoxide condensate in the antireflection material layer. Low refractive index layer is constructed,
Refraction is lower than the refractive index of the layer composed of the composition containing the metal alkoxide condensate below the layer composed of the composition containing the metal alkoxide condensate in the antireflection material layer. The problem is solved by an antireflective material characterized by comprising a medium refractive index layer having a low refractive index and a refractive index higher than that of the low refractive index layer.

  In addition, the antireflection material, which is composed of a composition containing a metal alkoxide condensate, is formed by irradiating the applied composition layer with active energy rays. Solved by an anti-reflective material characterized in that.

  The antireflection material as described above, wherein the transparent base material is composed of a material selected from the group consisting of a lower fatty acid ester of cellulose and uniaxially stretched polyethylene terephthalate. Solved by.

  Moreover, it is said antireflection material, Comprising: It solves with the antireflection material characterized by the transparent base material being comprised using the cellulose triacetate.

Moreover, it is a manufacturing method of said antireflection material,
This is solved by a method for producing an antireflective material, which comprises applying a composition containing the metal alkoxide condensate and then irradiating the composition with active energy rays.

  Moreover, it solves with the polarizing plate protective film characterized by comprising with said antireflection material.

  Moreover, it solves with the polarizing plate characterized by the film comprised with said antireflection material being bonded together to a polarizer.

  A polarizing plate having excellent transmittance and degree of polarization and high durability can be obtained.

  The composition for high refractive index (antireflection material) of the present invention contains a condensate of metal alkoxide, a crosslinkable polymer, and a solvent. Further, it contains a metal alkoxide condensate, a cationic polymerization compound, and a solvent. Moreover, a metal alkoxide and / or its condensate, an epoxy-type active energy ray reactive compound, and a solvent are contained. Moreover, a metal alkoxide and / or its condensate, an epoxy-type active energy ray reactive compound, a polymerization initiator, and a solvent are contained. Moreover, a metal alkoxide and / or its condensate, an epoxy-type active energy ray reactive compound, a polymerization initiator, a solvent, and water are contained. In particular, an antireflection material in which an antireflection layer is provided on a transparent substrate, wherein the antireflection layer is composed of a plurality of layers, and at least one of the plurality of layers has the high refractive index. It is comprised using the composition for use. Furthermore, it is an antireflection material in which an antireflection layer is provided on a transparent substrate, and the antireflection layer is composed of a plurality of layers, and at least one of the plurality of layers has the above high refraction. A low refractive index having a refractive index lower than the refractive index of the high refractive index layer on the upper side of the high refractive index layer formed using the high refractive index composition. A layer is composed. The antireflection material is provided with an antireflection layer on a transparent substrate, and the antireflection layer is composed of a plurality of layers, and at least one of the plurality of layers has the high refractive index. A low refractive index layer having a refractive index lower than the refractive index of the high refractive index layer above the high refractive index layer comprising the high refractive index composition. The refractive index of the low refractive index layer is lower than the refractive index of the high refractive index layer on the lower side of the high refractive index layer formed using the high refractive index composition. A medium refractive index layer having a refractive index higher than the refractive index is formed.

  The manufacturing method of the antireflection material of this invention is a manufacturing method of said antireflection material. And after apply | coating said high refractive index composition, this is irradiated with an active energy ray, It is characterized by the above-mentioned.

  The polarizing plate protective film of the present invention is composed of the antireflection material described above.

  The polarizing plate of the present invention is characterized in that a film composed of the above antireflection material is bonded to a polarizer.

  That is, an antireflective material having a high refractive index layer formed using the above composition for high refractive index on a transparent substrate, the high refractive index layer is a condensate of metal alkoxide (or metal alkoxide) and Since it contains a specific polymer, it has high adhesion to the high refractive index layer and the adjacent layer (in the case where the transparent substrate is an adjacent layer, this transparent substrate), and has high surface hardness and scratches. It is hard to get up and is durable.

  The antireflective material in which the low refractive index layer having a lower refractive index than the refractive index of the high refractive index layer is formed on the high refractive index layer, the high refractive index layer is a condensate of metal alkoxide (or Metal alkoxide) and a specific polymer, the adhesion of the high refractive index layer is high, the surface hardness is high, scratches are unlikely to occur, the durability is high, and the reflectance is low. The reflection of light is prevented.

  A polarizing plate in which an antireflection material exhibiting such features is bonded to a polarizer has a wide viewing angle and provides an excellent LCD.

  The following are used as the metal alkoxide in the composition for high refractive index of the present invention. That is, titanium, zirconium, indium, tin, thallium, or the like is used as the metal of the metal alkoxide. Of course, other things may be used. As the alkoxide, an alkoxide having 5 or less carbon atoms is preferable.

  For example, titanium n-butoxide, titanium methoxide, titanium ethoxide, titanium n-propoxide, titanium isopropoxide, titanium t-butoxide, titanium n-nonyl oxide, titanium i-butoxide, titanium methoxypropoxide, titanium chlorotrioxide Isopropoxide, Titanium dichloride diethoxide, Titanium iodoisopropoxide, Titanium di-n-butoxide (bis-2,4-pentadionate), Titanium di-i-propoxide (bis-2,4-pentadionate), Titanium di Isopropoxide bis (tetramethylheptanedionate), titanium diisopropoxide bis (ethyl acetoacetate), titanium 2-ethylhexoxide, titanium oxide bis (pentadionate), titanium oxybis (te Lamethylheptanedionate), tetrakis (trimethylsiloxy) titanium, titanium allyl acetoacetate triisopropoxide, titanium bis (triethanolamine) diisopropoxide, titanium methacrylate triisopropoxide, (2-methacryloxyethoxy) triiso Propoxy titanate, titanium methacryloxyethyl acetoacetate triisopropoxide, titanium methylphenoxide, vanadium triisopropoxide oxide, vanadium triisobutoxide oxide, vanadium (III) 2,4-pentandionate, vanadium (IV) oxide bis (2,4-pentanedionate), vanadium (IV) oxybis (benzoylacetonate), zinc N, N-dimethylaminoethoxide Zinc methoxyethoxide, zinc 2,4-pentanedionate, zinc-2,2,6,6-tetramethyl 3,5-heptanedionate, strontium isopropoxide, strontium methoxypropoxide, strontium hexafluoropentanedio Strontium 2,4-pentanedionate, strontium 2,2,6,6-tetramethyl 3,5-heptanedionate, indium methoxyethoxide, indium isopropoxide, indium n-propoxide, indium n-butoxide, Indium t-butoxide, indium hexafluoropentanedionate, indium 2,4-pentanedionate, indiummethyl (trimethyl) acetylacetonate, indium trifluoropentanedi Onate, tin (II) methoxide, tin (II) ethoxide, tetraisopropoxytin, tetra-t-butoxytin, tetra-n-butoxytin, bis (2,4-pentandionate) dichlorotin, tin (II) 2,4 Pentanedionate, sodium tin ethoxide, tantalum (IV) methoxide, tantalum (IV) ethoxide, tantalum (IV) isopropoxide, tantalum (IV) n-propoxide, tantalum (IV) n-butoxide, tantalum (IV) Examples include t-butoxide, tantalum sodium methoxide, tantalum (V) trifluoroethoxide, tantalum (V) tetraethoxide pentanedionate, and the like.

  As the metal alkoxide condensate in the high refractive index composition of the present invention, a hydrolyzed metal alkoxide is used. That is, for example, adjustment is performed by adding water to a metal alkoxide solution as described above to perform hydrolysis, or by adding water to a coating solution containing the alkoxide for hydrolysis. The water used for the hydrolysis is preferably 1 to 10 mol, particularly 1 to 5 mol, per 100 mol of the metal alkoxide. In addition, it is preferable to use the catalyst used for sol-gel methods, such as hydrochloric acid, nitric acid, a metal chelate compound, for this hydrolysis.

〔但し、Ｍは、Ｔｉ，Ｓｉ，Ｚｒ，Ｓｎ及びＴａの群の中から選ばれた金属。Ｒ_a
，Ｒ_b ，Ｒ_c ，Ｒ_d は脂肪族炭化水素基。ｍは２以上の整数。〕
中でも、一般式〔Ｉ〕において、ＭがＴｉ，Ｓｉ，Ｚｒが特に好ましい。又、Ｒ_a ，Ｒ_b ，Ｒ_c ，Ｒ_d は炭素数１〜５の脂肪族炭化水素基であるものが特に好ましい。又、ｍは２〜３０の整数であるものが特に好ましい。 As the condensate of metal alkoxide in the composition for high refractive index of the present invention, a compound represented by the general formula [I] is particularly preferable.
Formula [I]

[However, M is a metal selected from the group consisting of Ti, Si, Zr, Sn and Ta. R _a
, R _b , R _c and R _d are aliphatic hydrocarbon groups. m is an integer of 2 or more. ]
Among these, in general formula [I], M is particularly preferably Ti, Si, or Zr. R _a , R _b , R _c and R _d are particularly preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Further, m is particularly preferably an integer of 2 to 30.

  The crosslinkable polymer in the composition for high refractive index of the present invention is a crosslinkable polymer having —CH═CH—CO— group in its main chain and / or side chain, or an azide group in its main chain and / or side chain. Crosslinkable polymers having are preferred. Among these, cinnamic acid resin is a preferable crosslinkable polymer. That is, since these crosslinkable polymers can be combined with the condensate of the metal alkoxide, the above problem can be solved more effectively.

〔但し、Ｘは、Ｏ又はＳ。〕 The cationic polymerization compound in the high refractive index composition of the present invention is preferably selected from the group consisting of an oxirane cyclic compound, an oxetane cyclic compound, a thiitan cyclic compound, and a thietan cyclic compound. The oxirane cyclic compound is a compound containing an oxirane ring represented by the general formula [II]. Any monomer, dimer, oligomer, or polymer may be used.
Formula [II]

[However, X is O or S. ]

〔但し、Ｘは、Ｏ又はＳ。〕 The oxetane cyclic compound is a compound containing an oxetane ring represented by the general formula [III]. Any monomer, dimer, oligomer, or polymer may be used.
General formula [III]

[However, X is O or S. ]

  A thiitan cyclic compound is a compound containing a thiitan ring. Any monomer, dimer, oligomer, or polymer may be used. A thietane cyclic compound is a compound containing a thietane ring. Any monomer, dimer, oligomer, or polymer may be used.

  Among such cationic polymerization compounds, bisphenol A type, bisphenol F type, bisphenol AD type, phenol novolac type, cresol novolac type, alicyclic type, aliphatic type, naphthalene skeleton type, and biphenyl type epoxy resins are preferable. The epoxy-based active energy ray-reactive compound in the composition for high refractive index of the present invention is an aromatic epoxy compound (polyglycidyl ether of polyhydric phenol) such as hydrogenated bisphenol A or a reaction product of bisphenol A and epichlorohydrin. Ethers, epoxy novolac resins, aliphatic epoxy compounds such as polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate, Typical examples of these are ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl. Ether, tripropylene glycol glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, nonanepropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin triglycidyl ether, diglycerol tri Glycidyl ether, diglycerol tetraglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, polyglycidyl ether of sorbitol, alicyclic epoxy compound such as 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxy Chlohexyl-5,5-spiro-3 ′, 4′-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, bis (3,4-epoxy-6-methyl) Cyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane) dicyclopentanediene diepoxide, ethylene glycol Di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), dicyclopentanediene diepoxyside, tris (2-hydroxyethyl) isocyanurate Cisidyl ether, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, polyglycidyl acrylate, polyglycidyl methacrylate, glycidyl acrylate or a copolymer of glycidyl methacrylate and other monomers, poly-2-glycidyloxyethyl acrylate, poly 2-glycidyloxyethyl methacrylate, 2-glycidyloxyethyl acrylate, 2-glycidyloxyethyl acrylate, or a copolymer of 2-glycidyloxyethyl methacrylate and other monomers, bis-2,2-hydroxycyclohexylpropane diglycidyl ether Etc. are used. Of course, it is not limited to these. Moreover, you may use not only one but two or more.

  The epoxy-based active energy ray-reactive compound of the present invention can be used by blending monoepoxides depending on the desired performance, in addition to those having two or more epoxy groups in the molecule. The active energy ray-reactive compound epoxy resin is not based on radical polymerization, but forms a polymerized, crosslinked structure or network structure by cationic polymerization. Unlike radical polymerization, it is preferable because it is not affected by oxygen in the reaction system.

  The polymerization initiator used together with the epoxy-based active energy ray-reactive compound is preferably one represented by the following general formula.

[(R ¹ ) _a (R ² ) _b (R ³ ) _c (R ⁴ ) _d Z] ^{+ w} [MeX _{v + w} ] ^−w
Here, in the general formula, the cation is onium, and Z is S, Se, Te, P, As, Sb, Bi, O, halogen (for example, I, Br, Cl) or N = N (diazo). , R ¹ , R ² , R ³ and R ⁴ are organic groups which may be the same or different. a, b, c, and d are each an integer of 0 to 3, and a + b + c + d is equal to the valence of Z. Me is a metal or metalloid which is a central atom of a halide complex, and is B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is halogen, w is the net charge of the halogenated complex ion, and v is the number of halogen atoms in the halogenated complex ion.

Specific examples of the anion [MeX _{v + w} ] ^{-w in} the above general formula include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₄ ⁻ ), hexafluoroantimonate (SbF ₄ ⁻ ), hexa Examples include fluoroarsenate (AsF ₄ ⁻ ) and hexachloroantimonate (SbCl ₄ ⁻ ). Furthermore, an anion of the general formula MX _n (OH) ⁻ can also be used. In addition, perchlorate ion (ClO ₄
^-), trifluoromethyl sulfite ion (CF ₃ SO ₃ ^-), fluorosulfonic acid ion (FSO ₃ ^-), toluenesulfonic acid ion, and even trinitrobenzene anions like.

  Among these onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator. Among them, those described in JP-A-50-151996, JP-A-50-158680, etc. Aromatic halonium salts, VIa group aromatic onium salts described in JP-A-50-151997, JP-A-52-30899, JP-A-59-55420, JP-A-55-125105, etc. Oxosulfoxonium salts described in JP-A-56-8428, JP-A-56-149402, JP-A-57-192429, etc., and aromatics described in JP-B-49-17040 Diazonium salts such as thiopyrilum salts described in US Pat. No. 4,139,655 are preferred. Moreover, an aluminum complex, a photodegradable silicon compound type | system | group polymerization initiator, etc. are mentioned. In addition, the cationic polymerization initiator may be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.

  The ratio of the metal alkoxide condensate and the crosslinkable polymer in the high refractive index composition of the present invention is preferably metal alkoxide condensate / crosslinkable polymer = 3 to 50 (mass ratio). That is, when the metal alkoxide condensate / crosslinkable polymer is less than 3, the refractive index of the film tends to be low, and the desired high refractive index film tends not to be obtained. On the other hand, when the metal alkoxide condensate / crosslinkable polymer exceeds 50, the film tends to be brittle, cracking occurs, adhesion to the adjacent layer is low, and a strong film tends not to be obtained. There is. Therefore, 3 to 50 (mass ratio) is preferable. More preferably, it is 5 or more. Further, it is more preferably 30 or less, particularly 20 or less.

  The ratio of the metal alkoxide condensate to the cationic polymerization compound in the composition for high refractive index of the present invention is preferably metal alkoxide condensate / cationic polymerization compound = 3 to 50 (mass ratio). . That is, when the metal alkoxide condensate / cationic polymerization compound is less than 3, the refractive index of the film tends to be low, and the desired high refractive index film tends not to be obtained. On the other hand, when the metal alkoxide condensate / cationic polymerization compound exceeds 50, the film becomes brittle, cracking occurs, adhesion with the adjacent layer is lowered, and a strong film is obtained. There is no tendency. Therefore, 3 to 50 (mass ratio) is preferable. More preferably, it is 5 or more. Further, it is more preferably 30 or less, particularly 20 or less.

  The ratio of the metal alkoxide and / or condensate thereof to the epoxy-based active energy ray-reactive compound is metal alkoxide and / or condensate / epoxy-based active energy ray-reactive compound = 3 to 50 (mass ratio). Is preferred. That is, when the metal alkoxide and / or its condensate / epoxy active energy ray reactive compound is less than 3, the refractive index of the film tends to be low, and the desired high refractive index film tends not to be obtained. . Conversely, when the metal alkoxide and / or its condensate / epoxy active energy ray reactive compound exceeds 50, the film becomes brittle, cracks occur, and adhesion to the adjacent layer is low. There is a tendency that a strong film cannot be obtained. Therefore, 3 to 50 (mass ratio) is preferable. More preferably, it is 5 or more. Further, it is more preferably 30 or less, particularly 20 or less.

  The ratio of the polymerization initiator to the epoxy-based active energy ray-reactive compound is preferably polymerization initiator / epoxy-based active energy ray-reactive compound = 0.1 to 15 (mass ratio). More preferably, it is 1 or more. More preferably, it is 10 or less. The high refractive index composition contains a catalyst and a curing agent for the purpose of promoting curing and improving hardness. For example, there are organometallic compounds such as metal chelate compounds and organic carboxylates, organosilicon compounds having amino groups, and photoacid generators.

  The composition for high refractive index can be made into a stable composition by reacting with a β-diketone to form a chelate compound for the preservation and stabilization of the paint. Examples of the β-diketone include methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, acetylacetone and the like. Of these, ethyl acetoacetate is preferred.

  The layer formed by using the high refractive index composition in the antireflection material of the present invention is formed by irradiating the applied layer of the high refractive index composition with active energy rays, particularly ultraviolet rays. Various materials can be used for the transparent substrate in the antireflection material of the present invention. However, when it is intended to be used for an LCD, particularly when it is intended to be used as a material for a polarizing plate, the transparent substrate is made of a material selected from the group consisting of cellulose lower fatty acid ester and uniaxially stretched polyethylene terephthalate. What was comprised is preferable. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms, and preferred examples of the lower fatty acid ester of cellulose include cellulose acetate, cellulose propionate, and cellulose butyrate. In addition, mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate can be used. The most preferred lower fatty acid ester of cellulose is cellulose triacetate. In particular, cellulose triacetate having an acetylation degree of 59 to 62%.

  The high refractive index composition of the present invention contains a metal alkoxide condensate, a crosslinkable polymer, and a solvent. Or the condensate of a metal alkoxide, a cationic polymerization compound, and a solvent are contained. Or a metal alkoxide and / or its condensate, an epoxy type active energy ray reactive compound, and a solvent are contained. Or a metal alkoxide and / or its condensate, an epoxy-type active energy ray reactive compound, a polymerization initiator, and a solvent are contained. Or a metal alkoxide and / or its condensate, an epoxy-type active energy ray reactive compound, a polymerization initiator, a solvent, and water are contained.

Various metal alkoxides and metal alkoxide condensates are used. However, the condensate of metal alkoxide is particularly represented by the above general formula [I]. In general formula [I], in particular, M is Ti or Zr. R _a , R _b , R _c and R _d are each an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Of these, a methyl group, an ethyl group, a propyl group, and a butyl group. m is an integer of 2-30. Especially, it is an integer of 2-10.

More specifically, when M is Ti, R _a , R _b , R _c and R _d are each an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, m Are 2, 3, 5, 7, and 10. When M is Zr, R _a , R _b , R _c , and R _d are aliphatic hydrocarbon groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, and butyl groups, and m is 2,7. .

  The crosslinkable polymer is a crosslinkable polymer having a —CH═CH—CO— group in its main chain and / or side chain, or a crosslinkable polymer having an azide group in its main chain and / or side chain. In particular, it is a cinnamic acid resin. The cationic polymerization compound is selected from the group of oxirane cyclic compounds, oxetane cyclic compounds, thiitan cyclic compounds, and thietan cyclic compounds.

〔式中、Ｒ₁ ，Ｒ₂ ，Ｒ₃ ，Ｒ₄ は、アルキル基、アリール基、アルコキシ基、アルケニル基、水素原子の群の中から選ばれるいずれかである。Ｒ₁ ，Ｒ₂ ，Ｒ₃ ，Ｒ₄ は同一でも異なるものでも良い。〕
具体的には、例えばフェニルグリシジルエーテル、４−ビニルシクロヘキセンジオキシド、二酸化リモネン、１，２−シクロヘキセンオキシド、グリシジルアクリレート、グリシジルメタクリレート、スチレンオキシド、アリルグリシジルエーテル等が挙げられる。 The oxirane cyclic compound is a compound containing an oxirane ring, particularly an oxirane ring represented by the above general formula [II]. Especially, it is a compound containing the oxirane ring represented by the following general formula [IIa].
Formula [IIa]

[Wherein R ₁ , R ₂ , R ₃ and R ₄ are any one selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, an alkenyl group and a hydrogen atom. R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. ]
Specific examples include phenyl glycidyl ether, 4-vinylcyclohexene dioxide, limonene dioxide, 1,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, and allyl glycidyl ether.

〔式中、Ｒ₅ ，Ｒ₆ ，Ｒ₇ ，Ｒ₈ ，Ｒ₉ ，Ｒ₁₀は、水素原子、ハロゲン原子、ハロアルキル基、アリールアルキル基、アリールアルキル基、アルコキシ基、アリルオキシ基、アセトキシ基の群の中から選ばれるいずれかである。Ｒ₅ ，Ｒ₆，Ｒ₇ ，Ｒ₈ ，Ｒ₉ ，Ｒ₁₀は、同一でも異なるものでも良い。〕
具体的には、例えば３，３−ビス（クロルメチル）オキセタン、３，３−ビス（ヨードメチル）オキセタン、３，３−ビス（メトキシメチル）オキセタン、３，３−ビス（フェノキシメチル）オキセタン、３−メチル−３−クロルメチルオキセタン、３，３−ビス（アセトキシメチル）オキセタン、３，３−ビス（フルオロメチル）オキセタン、３，３−ビス（ブロモメチル）オキセタン、３，３−ジメチルオキセタン等が挙げられる。 The oxetane cyclic compound is a compound containing an oxetane ring, particularly an oxetane ring represented by the above general formula [III]. Especially, it is a compound containing the oxetane ring represented by the following general formula [IIIa].
General formula [IIIa]

[Wherein R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ are a hydrogen atom, a halogen atom, a haloalkyl group, an arylalkyl group, an arylalkyl group, an alkoxy group, an allyloxy group, or an acetoxy group. It is one selected from. R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ may be the same or different. ]
Specifically, for example, 3,3-bis (chloromethyl) oxetane, 3,3-bis (iodomethyl) oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3- Examples include methyl-3-chloromethyloxetane, 3,3-bis (acetoxymethyl) oxetane, 3,3-bis (fluoromethyl) oxetane, 3,3-bis (bromomethyl) oxetane, and 3,3-dimethyloxetane. .

〔但し、Ｒ₁₁は水素原子またはメチル基。ｎは１〜１０の整数。〕 A thiitan cyclic compound is a compound containing a thiitan ring. For example, a homopolymer of 2,3-epithiopropyl acrylate or methacrylate, or a vinyl copolymer containing 2,3-epithiopropyl acrylate or methacrylate as one component may be used. A thietane cyclic compound is a compound containing a thietane ring. For example, a homopolymer of a monomer represented by the general formula [IV] or a vinyl copolymer containing a monomer represented by the following general formula [IV] as one component can be used.
Formula [IV]

[However, R ₁₁ is a hydrogen atom or a methyl group. n is an integer of 1-10. ]

  As the epoxy-based active energy ray-reactive compound, those described above are used. As the polymerization initiator, those described above are used. The ratio between the metal alkoxide condensate and the crosslinkable polymer is metal alkoxide condensate / crosslinkable polymer = 3 to 50 (mass ratio). In particular, it is 5 or more. In particular, it is 30 or less, and further 20 or less.

  The ratio of the metal alkoxide condensate and the cationic polymerization compound is metal alkoxide condensate / cationic polymerization compound = 3 to 50 (mass ratio). In particular, it is 5 or more. In particular, it is 30 or less, and further 20 or less. The ratio of a metal alkoxide and / or its condensate, and an epoxy-type active energy ray reactive compound is metal alkoxide and / or its condensate / epoxy-type active energy ray reactive compound = 3-50 (mass ratio). In particular, it is 5 or more. In particular, it is 30 or less, and further 20 or less.

  The ratio of a polymerization initiator and an epoxy type active energy ray reactive compound is polymerization initiator / epoxy type active energy ray reactive compound = 0.1-15 (mass ratio). In particular, it is 1 or more. In particular, it is 10 or less.

  Examples of the solvent for the high refractive index composition include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene and xylene, ethylene glycol, Glycols such as propylene glycol and hexylene glycol, glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve and diethyl carbitol, organic solvents such as N-methylpyrrolidone and dimethylformamide, or water Is used. These can be used alone or in admixture of two or more. Among them, when a ketone, for example, a solvent having a carbonyl group such as acetone, methyl ethyl ketone, or cyclohexanone, and an alcohol having 4 or less carbon atoms such as methanol, ethanol, n-propanol, i-propanol, or butanol are used in combination, The amount of UV irradiation can be reduced, and productivity is improved, which is preferable. It is preferable to use an organic solvent and water.

  The composition for high refractive index contains a catalyst and a curing agent, for example, for the purpose of accelerating curing and improving hardness, if necessary. For example, there are organometallic compounds such as metal chelate compounds and organic carboxylates, organosilicon compounds having amino groups, and photoacid generators. In addition, a stable composition can be obtained by reacting with a β-diketone to obtain a chelate compound for the storage stability of the composition coating for high refractive index. Examples of the β-diketone include methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, acetylacetone and the like. Of these, ethyl acetoacetate is preferred.

  The antireflection material of the present invention is an antireflection material in which an antireflection layer is provided on a transparent substrate, and the antireflection layer is composed of a plurality of layers, and at least one of the plurality of layers is The above composition for high refractive index is used. Alternatively, it is an antireflection material in which an antireflection layer is provided on a transparent substrate, and the antireflection layer is composed of a plurality of layers, and at least one of the plurality of layers has the high refractive index. From the refractive index of the high refractive index layer on the upper side (the side far from the transparent substrate) of the high refractive index layer that is configured using the composition for a high refractive index. A low refractive index layer having a low refractive index is formed. Alternatively, an antireflection material in which an antireflection layer is provided on a transparent substrate, and the antireflection layer is composed of a plurality of layers, and at least one of the plurality of layers has the high refractive index. From the refractive index of the high refractive index layer on the upper side (the side far from the transparent substrate) of the high refractive index layer that is configured using the composition for a high refractive index. A low-refractive index layer having a low refractive index is formed, and the high-refractive index layer is formed under the high-refractive index layer (side close to the transparent substrate) formed using the high-refractive index composition. A medium refractive index layer having a refractive index lower than that of the low refractive index layer and higher than that of the low refractive index layer is formed.

  Various materials can be used for the transparent substrate. When it is intended for use in LCDs, particularly when it is intended for use as a material for polarizing plates, the transparent substrate is composed of a material selected from the group consisting of lower fatty acid esters of cellulose and uniaxially stretched polyethylene terephthalate. It is a thing. In particular, it is a transparent substrate composed of cellulose triacetate, especially cellulose triacetate having an acetylation degree of 59 to 62%.

  The high refractive index layer preferably has a refractive index in the range of 1.75 to 2.20 from the viewpoint of reflectance. The thickness is preferably from 0.01 to 0.20 μm (particularly from 0.03 μm to 0.15 μm) from the viewpoint of reflectivity. The medium refractive index layer preferably has a refractive index in the range of 1.55 to 1.95 (a value smaller than the refractive index of the high refractive index layer) from the viewpoint of reflectance. The thickness is preferably from 0.01 to 0.20 μm (particularly from 0.03 μm to 0.15 μm) from the viewpoint of reflectivity.

  From the viewpoint of reflectivity, the low refractive index layer has a refractive index of 1.50 or less, desirably 1.45 or less, more desirably 1.40 or less (less than the refractive index of the high refractive index layer or the middle refractive index layer). Value). The thickness is preferably from 0.01 to 0.20 μm (particularly from 0.03 μm to 0.15 μm) from the viewpoint of reflectivity.

〔Ｙ及びＺは、炭素数２〜１２の直鎖又は分岐型のアルキル基、炭素数４〜１２のシクロアルキル基、フッ素原子を有する炭素数２〜１２の直鎖又は分岐型のアルキル基、又はフッ素原子を有する炭素数４〜１２のシクロアルキル基。Ｙ及びＺは、同一であっても異なっていてもよい。但し、Ｙ及びＺの少なくとも一方の基はフッ素原子を含む。〕
一般式〔ＶＩＩＩ〕

〔Ｙ及びＺは、炭素数２〜１２の直鎖又は分岐型のアルキル基、炭素数４〜１２のシクロアルキル基、フッ素原子を有する炭素数２〜１２の直鎖又は分岐型のアルキル基、又はフッ素原子を有する炭素数４〜１２のシクロアルキル基。Ｙ及びＺは、同一であっても異なっていてもよい。但し、Ｙ及びＺの少なくとも一方の基はフッ素原子を含む。〕
一般式〔ＩＸ〕

〔Ｘ₁ 及びＸ₂ は、水素原子、又はメチル基。Ｘ₁ 及びＸ₂ は、同一であっても異なっていてもよい。Ｒf は、フッ素原子を３個以上有する炭素数２〜１２の直鎖又は分岐型のアルキル基、又はフッ素原子を４個以上有する炭素数４〜１２のシクロアルキル基。〕
特に、上記一般式〔Ｖ〕，〔ＶＩ〕，〔ＶＩＩ〕，〔ＶＩＩＩ〕の群の中から選ばれた少なくとも一つの含フッ素モノマーと、上記一般式〔ＩＸ〕の群の中から選ばれた少なくとも一つの含フッ素モノマーとを含む組成物を用いて構成される。 A high refractive index layer is comprised using said high refractive index composition. In contrast, the low refractive index layer includes, for example, two or more types of fluorine-containing monomers represented by the following general formulas [V], [VI], [VII], [VIII], and [IX]. At least two kinds of fluorine-containing monomers are constituted by using a composition containing one selected from different groups of the general formulas [V], [VI], [VII], [VIII], and [IX]. .
General formula [V]
CH ₂ = CX ₁ -COORf
[X ₁ is a hydrogen atom or a methyl group. Rf is a C2-C12 linear or branched alkyl group having 3 or more fluorine atoms, or a C4-C12 cycloalkyl group having 4 or more fluorine atoms. ]
Formula [VI]
YOOC-CH = CX ₁ -COOZ
[X ₁ is a hydrogen atom or a methyl group. Y and Z are a linear or branched alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, a linear or branched alkyl group having 2 to 12 carbon atoms having a fluorine atom, or A cycloalkyl group having 4 to 12 carbon atoms and having a fluorine atom. Y and Z may be the same or different. However, at least one group of Y and Z contains a fluorine atom. ]
General formula [VII]

[Y and Z are a C2-C12 linear or branched alkyl group, a C4-C12 cycloalkyl group, a C2-C12 linear or branched alkyl group having a fluorine atom, Or a C4-C12 cycloalkyl group which has a fluorine atom. Y and Z may be the same or different. However, at least one group of Y and Z contains a fluorine atom. ]
General formula [VIII]

[Y and Z are a C2-C12 linear or branched alkyl group, a C4-C12 cycloalkyl group, a C2-C12 linear or branched alkyl group having a fluorine atom, Or a C4-C12 cycloalkyl group which has a fluorine atom. Y and Z may be the same or different. However, at least one group of Y and Z contains a fluorine atom. ]
Formula [IX]

[X ₁ and X ₂ are a hydrogen atom or a methyl group. X ₁ and X ₂ may be the same or different. Rf is a C2-C12 linear or branched alkyl group having 3 or more fluorine atoms, or a C4-C12 cycloalkyl group having 4 or more fluorine atoms. ]
In particular, at least one fluorine-containing monomer selected from the group of the general formulas [V], [VI], [VII], and [VIII], and the group of the general formula [IX]. The composition includes at least one fluorine-containing monomer.

  The fluorine-containing monomer in the composition for a low refractive index layer is preferably one having 30 to 90% (particularly 40% or more and 80% or less) of fluorine atoms contained in the fluorine-containing monomer. In addition to the above-mentioned fluorine-containing monomer, the low refractive index layer composition contains a photopolymerization monomer.

  Examples of the fluorine-containing monomer represented by the general formula [V] include (meth) acrylic acid-2,2,2-trifluoroethyl, (meth) acrylic acid-2,2,3,3,3-penta. Fluoropropyl, (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 , 7,7,8,8,8-pentadecafluorooctyl, (meth) acrylic acid-2,2,3,3,4,4,5, , 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, (meth) acrylic acid-1-methyl -2,2,3,3,4,4,4-heptafluorobutyl, (meth) acrylic acid-2,2,3,3,4,4, -hexafluorocyclobutyl, (meth) acrylic acid-2 , 2,3,3,4,4,5,5-octafluorocyclopentyl, (Meth) acrylic acid-2,2,3,3,4,4,5,5,6,6-decafluorocyclohexyl, (meth) acrylic acid-2,2,3,3,4,4,5,5 , 6,6,7,7-dodecafluorocycloheptyl, (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradeca Fluorocyclooctyl, (meth) acrylic acid-2-trifluoromethylcyclobutyl, (meth) acrylic acid-3-trifluoromethylcyclobutyl, (meth) acrylic acid-2-trifluoromethylcyclopentyl, (meth) acrylic acid -3-trifluoromethylcyclopentyl, (meth) acrylic acid-2-trifluoromethylcyclohexyl, (meth) acrylic acid-3-trifluoromethylcyclohexyl, (meth) acrylic acid-4-tri Examples include fluoromethylcyclohexyl, (meth) acrylic acid-2-trifluoromethylcycloheptyl, (meth) acrylic acid-3-trifluoromethylcycloheptyl, and (meth) acrylic acid-4-trifluoromethylcycloheptyl. These monomers may be used alone or as a mixture. These monomers are obtained by an esterification reaction between (meth) acrylic acid and a fluorine-containing alcohol.

  Examples of the fluorine-containing monomer represented by the general formula [VI] include fumaric acid-iso-propyl-2,2,2-trifluoroethyl, fumaric acid-iso-propyl-2,2,3,3,3. Pentafluoropropyl, fumaric acid-iso-propyl-2,2,3,3,4,4,4-heptafluorobutyl, fumaric acid-iso-propyl-2,2,3,3,4,4,5 , 5,5-nonafluoropentyl, fumaric acid-iso-propyl-2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl, fumaric acid-iso-propyl- 2,2,3,3,4,5,5,6,6,7,7,7-tridecafluoroheptyl, fumaric acid-iso-propyl-2,2,3,3,4,4,4 5,5,6,6,7,7,8,8,8-pentadecafluoro Octyl, fumaric acid-iso-propyl-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl, fumaric acid-iso-propyl-2,2 , 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-nonadecafluorodecyl, fumarate-iso-propyl-3,3 4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl, fumaric acid-iso-propyl-2-trifluoromethyl-3 , 3,3-trifluoropropyl, fumarate-iso-propyl-3-trifluoromethyl-4,4,4-trifluorobutyl, fumarate-iso-propyl-1-methyl-2,2,3,3 , 3-pentafluoropropyl, fumarate-iso-propyl-1-me -2,2,3,3,4,4,4-heptafluorobutyl, fumaric acid-tert-butyl-2,2,2-trifluoroethyl, fumaric acid-tert-butyl-2,2,3, 3,3-pentafluoropropyl, fumarate-tert-butyl-2,2,3,3,4,4,4-pentafluorobutyl, fumarate-tert-butyl-2,2,3,3,4 4,5,5,5-nonafluoropentyl, fumaric acid-tert-butyl-2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl, fumaric acid-tert -Butyl-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl, fumaric acid-tert-butyl-2,2,3,3,4 4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl , Fumaric acid-tert-butyl-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl, fumaric acid-tert-butyl-2,2 , 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecyl, fumaric acid-tert-butyl-3,3 4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl, fumaric acid-tert-butyl-2-trifluoromethyl-3 , 3,3-trifluoropropyl, fumaric acid-tert-butyl-3-trifluoromethyl-4,4,4-trifluorobutyl, fumaric acid-tert-butyl-1-methyl-2,2,3,3 , 3-pentafluoropropyl, fumaric acid-tert-butyl-1-methyl- , 2,3,3,4,4,4-heptafluorobutyl, fumaric acid-iso-propyl-2,2,3,3,4,4-hexafluorocyclobutyl, fumaric acid-iso-propyl-2, 2,3,3,4,4,5,5-octafluorocyclopentyl, fumarate-iso-propyl-2,2,3,3,4,4,5,5,6,6-decafluorocyclohexyl, fumarate Acid-iso-propyl-2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorocycloheptyl, fumaric acid-iso-propyl-2,2,3,3 4,4,5,5,6,6,7,7,8,8-tetradecafluorocyclooctyl, fumaric acid-iso-propyl-2-trifluoromethylcyclobutyl, fumaric acid-iso-propyl-3- Trifluoromethylcyclobutyl Fumaric acid-iso-propyl-2-trifluoromethylcyclopentyl, fumaric acid-iso-propyl-3-trifluoromethylcyclopentyl, fumaric acid-iso-propyl-2-trifluoromethylcyclohexyl, fumaric acid-iso-propyl-3 -Trifluoromethylcyclohexyl, fumaric acid-iso-propyl-4-trifluoromethylcyclohexyl, fumaric acid-iso-propyl-2-trifluoromethylcycloheptyl, fumaric acid-iso-propyl-3-trifluoromethylcycloheptyl, Fumarate-iso-propyl-4-trifluoromethylcycloheptyl, fumarate-bis (2,2,2-trifluoroethyl), fumarate-bis (2,2,3,3,3-pentafluoropropyl) , Fumarate-bis (2,2,3 , 3,4,4,4-heptafluorobutyl), fumarate-bis (2,2,3,3,4,4,5,5,5-nonafluoropentyl), fumarate-bis (2,2 , 3,3,4,4,5,5,6,6,6-undecafluorohexyl), fumaric acid-bis (2,2,3,3,4,4,5,5,6,6,6). 7,7,7-tridecafluoroheptyl), fumarate-bis (2,2,3,3,4,5,5,6,6,7,7,8,8,8-pentadecafluoro) Octyl), fumarate-bis (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl), fumarate-bis (2,2,3) , 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecyl), fumarate-bis (3,3,4, 4, 5, 5 6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl), or maleic acid-iso-propyl-2,2,2-trifluoroethyl, maleic acid-iso -Propyl-2,2,3,3,3-pentafluoropropyl, maleic acid-iso-propyl-2,2,3,3,4,4,4-heptafluorobutyl, maleic acid-iso-propyl-2 , 2,3,3,4,4,5,5,5-nonafluoropentyl, maleic acid-iso-propyl-2,2,3,3,4,4,5,5,6,6,6- Undecafluorohexyl, maleic acid-iso-propyl-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl, maleic acid-iso-propyl- 2, 2, 3, 3, 4, 4, 5, 5, 6, 6 7,7,8,8,8-pentadecafluorooctyl, maleic acid-iso-propyl-3,3,4,4,5,5,6,6,7,7,8,8,8-trideca Fluorooctyl, maleic acid-iso-propyl-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadeca Fluorodecyl, maleic acid-iso-propyl-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl, malee Acid-iso-propyl-2-trifluoromethyl-3,3,3-trifluoropropyl, maleic acid-iso-propyl-3-trifluoromethyl-4,4,4-trifluorobutyl, maleic acid-iso- Propyl-1-methyl-2,2,3,3,3-pentaph Fluoropropyl, maleic acid-iso-propyl-1-methyl-2,2,3,3,4,4,4-heptafluorobutyl, maleic acid-tert-butyl-2,2,2-trifluoroethyl, maleic acid -Tert-butyl-2,2,3,3,3-pentafluoropropyl, maleic acid-tert-butyl-2,2,3,3,4,4,4-pentafluorobutyl, maleic acid-tert-butyl -2,2,3,3,4,4,5,5,5-nonafluoropentyl, maleic acid-tert-butyl-2,2,3,3,4,4,5,5,6,6 6-Undecafluorohexyl, maleic acid-tert-butyl-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl, maleic acid-tert- Butyl-2,2,3,3 , 4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl, maleic acid-tert-butyl-3,3,4,4,5,5,6,6,7 , 7,8,8,8-tridecafluorooctyl, maleic acid-tert-butyl-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9 , 9,10,10,10-nonadecafluorodecyl maleate-tert-butyl-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10 , 10,10-heptadecafluorodecyl, maleic acid-tert-butyl-2-trifluoromethyl-3,3,3-trifluoropropyl, maleic acid-tert-butyl-3-trifluoromethyl-4,4 4-trifluorobutyl, maleic acid-tert-butyl-1-methyl-2, , 3,3,3-pentafluoropropyl, maleic acid-tert-butyl-1-methyl-2,2,3,3,4,4,4-heptafluorobutyl, maleic acid-iso-propyl-2,2 , 3,3,4,4-hexafluorocyclobutyl, maleic acid-iso-propyl-2,2,3,3,4,4,5,5-octafluorocyclopentyl, maleic acid-iso-propyl-2, 2,3,3,4,4,5,5,6,6-decafluorocyclohexyl, maleic acid-iso-propyl-2,2,3,3,4,4,5,5,6,6,7 , 7-dodecafluorocycloheptyl, maleic acid-iso-propyl-2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorocyclooctyl, malein Acid-iso-propyl-2-to Trifluoromethylcyclobutyl, maleic acid-iso-propyl-3-trifluoromethylcyclobutyl, maleic acid-iso-propyl-2-trifluoromethylcyclopentyl, maleic acid-iso-propyl-3-trifluoromethylcyclopentyl, maleic Acid-iso-propyl-2-trifluoromethylcyclohexyl, maleic acid-iso-propyl-3-trifluoromethylcyclohexyl, maleic acid-iso-propyl-4-trifluoromethylcyclohexyl, maleic acid-iso-propyl-2- Trifluoromethylcycloheptyl, maleic acid-iso-propyl-3-trifluoromethylcycloheptyl, maleic acid-iso-propyl-4-trifluoromethylcycloheptyl, maleic acid-bis (2,2, -Trifluoroethyl), maleic acid-bis (2,2,3,3,3-pentafluoropropyl), maleic acid-bis (2,2,3,3,4,4,4-heptafluorobutyl), Maleic acid-bis (2,2,3,3,4,4,5,5,5-nonafluoropentyl), maleic acid-bis (2,2,3,3,4,4,5,5,6) , 6,6-undecafluorohexyl), maleic acid-bis (2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl), maleic acid -Bis (2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl), maleic acid-bis (3,3,4, 4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl), maleic acid-bis (2,2,3,3) 4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecyl), maleic acid-bis (3,3,4,4,5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-heptadecafluorodecyl) and the like. These monomers may be used alone or as a mixture. These monomers are a combination of esterification reaction of fumaric acid or maleic acid and fluorine-containing alcohol, or introduction reaction of tert-butyl ester by reaction of fluorine-containing carboxylic acid and isobutene and cis-trans isomerization reaction. Obtained by the method.

  Examples of the fluorine-containing monomer represented by the general formula [VII] include itaconic acid-bis (2,2,2-trifluoroethyl), itaconic acid-bis (2,2,3,3,3-pentafluoro Propyl), itaconic acid-bis (2,2,3,3,4,4,4-heptafluorobutyl), itaconic acid-bis (2,2,3,3,4,4,5,5,5- Nonafluoropentyl), itaconic acid-bis (2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl), itaconic acid-bis (2,2,3,3) , 4,4,5,5,6,6,7,7,7-tridecafluoroheptyl), itaconate-bis (2,2,3,3,4,4,5,5,6,6) 7,7,8,8,8-pentadecafluorooctyl), itaconate-bis (3,3,4,4,5,5,6) 6,7,7,8,8,8-tridecafluoctyl), itaconate-bis (2,2,3,3,4,5,5,6,6,7,7,8,8) , 9,9,10,10,10-nonadecafluorodecyl), itaconate-bis (3,3,4,4,5,5,6,6,7,7,8,8,9,9, 10,10,10-heptadecafluorodecyl), itaconic acid-bis (2-trifluoromethyl-3,3,3-trifluoropropyl), itaconic acid-bis (3-trifluoromethyl-4,4,4) -Trifluorobutyl), itaconic acid-bis (1-methyl-2,2,3,3,3-pentafluoropropyl), itaconic acid-bis (1-methyl-2,2,3,3,4,4) , 4-Heptafluorobutyl), Itaconic acid-bis (2,2,3,3,4,4, -Hexafluoro) Chlorobutyl), itaconic acid-bis (2,2,3,3,4,4,5,5-octafluorocyclopentyl), itaconic acid-bis (2,2,3,3,4,4,5,5,5) 6,6-decafluorocyclohexyl), itaconic acid-bis (2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorocycloheptyl), itaconic acid-bis (2 , 2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorocyclooctyl), itaconic acid-bis (2-trifluoromethylcyclobutyl), itaconic acid -Bis (3-trifluoromethylcyclobutyl), itaconic acid-bis (2-trifluoromethylcyclobutyl), itaconic acid-bis (3-trifluoromethylcyclobutyl), itaconic acid-bis (2-trifluoromethyl) Cyclopen Til), itaconic acid-bis (3-trifluoromethylcyclopentyl), itaconic acid-bis (2-trifluoromethylcyclohexyl), itaconic acid-bis (3-trifluoromethylcyclohexyl), itaconic acid-bis (4-tri Fluoromethylcyclohexyl), itaconic acid-bis (2-trifluoromethylcycloheptyl), itaconic acid-bis (3-trifluoromethylcycloheptyl), itaconic acid-bis (4-trifluoromethylcycloheptyl), and the like. . These monomers may be used alone or as a mixture. These monomers are obtained by an esterification reaction of itaconic acid and a fluorinated alcohol.

  Examples of the fluorine-containing monomer represented by the general formula [VIII] include tetrahydrophthalic acid-bis (2,2,2-trifluoroethyl), tetrahydrophthalic acid-bis (2,2,3,3,3- Pentafluoropropyl), tetrahydrophthalic acid-bis (2,2,3,3,4,4,4-heptafluorobutyl), tetrahydrophthalic acid-bis (2,2,3,3,4,4,5, 5,5-nonafluoropentyl), tetrahydrophthalic acid-bis (2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl), tetrahydrophthalic acid-bis (2 , 2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl), tetrahydrophthalic acid-bis (2,2,3,3,4,4,5 , 5,6,6,7,7,8,8,8-pe Tadecafluorooctyl), tetrahydrophthalic acid-bis (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoctyl), tetrahydrophthalic acid-bis ( 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecyl), tetrahydrophthalic acid-bis ( 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl), tetrahydrophthalic acid-bis (2-trifluoro) Methyl-3,3,3-trifluoropropyl), tetrahydrophthalic acid-bis (3-trifluoromethyl-4,4,4-trifluorobutyl), tetrahydrophthalic acid-bis (1-methyl-2,2, 3,3,3-pentafluoropropyl), tetrahi Lophthalic acid-bis (1-methyl-2,2,3,3,4,4,4-heptafluorobutyl), tetrahydrophthalic acid-bis (2,2,3,3,4,4, -hexafluorocyclo Butyl), tetrahydrophthalic acid-bis (2,2,3,3,4,4,5,5-octafluorocyclopentyl), tetrahydrophthalic acid-bis (2,2,3,3,4,4,5, 5,6,6-decafluorocyclohexyl), tetrahydrophthalic acid-bis (2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorocycloheptyl), tetrahydrophthalic acid -Bis (2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorocyclooctyl), tetrahydrophthalic acid-bis (2-trifluoromethylcyclo) Butyl), tetrahydrophthal Luric acid-bis (3-trifluoromethylcyclobutyl), tetrahydrophthalic acid-bis (2-trifluoromethylcyclopentyl), tetrahydrophthalic acid-bis (3-trifluoromethylcyclopentyl), tetrahydrophthalic acid-bis (2- Trifluoromethylcyclohexyl), tetrahydrophthalic acid-bis (3-trifluoromethylcyclohexyl), tetrahydrophthalic acid-bis (4-trifluoromethylcyclohexyl), tetrahydrophthalic acid-bis (2-trifluoromethylcyclohexyl), tetrahydrophthal And acid-bis (3-trifluoromethylcyclohexyl), tetrahydrophthalic acid-bis (4-trifluoromethylcycloheptyl), and the like. These monomers may be used alone or as a mixture. These monomers are obtained by an esterification reaction of tetrahydrophthalic acid and a fluorinated alcohol.

  Examples of the fluorine-containing monomer represented by the general formula [IX] include di (meth) acrylic acid-2,2,2-trifluoroethylethylene glycol, di (meth) acrylic acid-2,2,3,3. , 3-pentafluoropropylethylene 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-undecafluorohexyl Ethylene 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 , 4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctylethylene glycol, di (meth) acrylic acid-3,3,4,4,5,5,6 , 6,7,7,8,8,8-tridecafluorooctylethylene 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-3,3,4,4,5,5,6,6,7,7,8 , 8,9,9,10,10,10-heptadecafluorodecylethylene glycol, di (meth) acrylic acid-2-trifluoromethyl-3,3,3-trifluoropropylethylene glycol, di (meth) acrylic Acid-3-trifluoromethyl-4,4,4-trifluoro Tylethylene glycol, di (meth) acrylic acid-1-methyl-2,2,3,3,3-pentafluoropropylethylene glycol, di (meth) acrylic acid-1-methyl-2,2,3,3 Examples include 4,4,4-heptafluorobutylethylene glycol. These monomers may be used alone or as a mixture. Such a di (meth) acrylic acid ester is, for example, a hydroxy (meth) acrylic acid ester and (meth) acrylic which can be obtained by a normal ring-opening reaction between the corresponding fluorine-containing epoxy and (meth) acrylic acid. Obtained by an esterification reaction with an acid.

  Examples of the photopolymerization monomer used together with the fluorine-containing monomer such as [V] to [IX] for constituting the low refractive index layer include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, penta Examples include erythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and acrylic-modified dipentaerythritol pentaerythritol. These monomers have high curability, small shrinkage, low odor, low toxicity, and relatively high safety.

  Examples of the photopolymerization initiator used together with the fluorine-containing monomer such as [V] to [IX] for constituting the low refractive index layer include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. And carbonyl compounds such as benzyl, benzophenone, acetophenone and Michler's ketone, azo compounds such as azobisisobutyronitrile and azodibenzoyl, and mixtures of α-diketones and tertiary amines.

  A low refractive index layer is formed by applying a solution in which the monomer or the like is dissolved onto the high refractive index layer and performing polymerization by light irradiation. Examples of the solvent to be used include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene and xylene, ethylene glycol, propylene glycol and hexylene glycol. Glycols such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, diethyl carbitol, etc., N-methylpyrrolidone, dimethylformamide, 1,1,2-trichloro-1,2, Examples thereof include organic solvents such as 2-trifluoroethane, trifluoromethylbenzene, 1,4-bis (trifluoromethyl) benzene, and other water. These may be used alone or in combination.

In addition, the low refractive index layer is formed by, for example, a silica film prepared from a hydrolyzate of tetraethoxysilane using a sol-gel method, a film in which silica sol is dispersed in a binder, or vapor deposition or sputtering. A film such as MgF or SiO ₂ can be used. The medium refractive index layer is a layer in which the refractive index is lowered by adjusting the ratio of the crosslinkable polymer or the cationic polymerization compound in the composition for a high refractive index layer of the present invention, or TiO ₂ , Sb ₂ O ₅ , ZnO, It can be composed of inorganic fine particles having a high refractive index such as SnO ₂ dispersed in a binder. In the case where the high refractive index layer and the medium refractive index layer are constituted by using the same type of composition, it is preferable because adhesion between both layers is increased. Even if the same composition is used, the refractive index can be controlled by controlling the amount of ultraviolet rays to be irradiated. For example, when the amount of irradiated ultraviolet rays is increased, the layer has a high refractive index.

  Further, a hard coat layer is provided between the transparent substrate and the high refractive index layer (particularly, the middle refractive index layer). The hard coat layer is a layer mainly composed of a resin that is cured through a crosslinking reaction by irradiation with active energy rays such as ultraviolet rays and electron beams. Typical resins that are cured by irradiation with active energy rays are ultraviolet curable resins and electron beam curable resins. Of course, it is not limited to this.

  As the ultraviolet curable resin, an ultraviolet curable polyol acrylate resin is particularly preferable. For example, photopolymerizable monomers such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, The thing using an oligomer is mentioned. These polyol acrylate resins are preferred because they are highly crosslinkable, have high curability, have low shrinkage, and have low odor, low toxicity, and high safety.

  These resins are used together with a photosensitizer. Photoinitiators can also be used as photosensitizers. Specific examples of the photosensitizer include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, tetramethyluram monosulfide, thioxanthone, and derivatives thereof. Further, when using an epoxy acrylate photoinitiator, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used.

  A sensitizer having an absorption maximum in the near ultraviolet region to the visible light region can be used. The photoreaction initiator or photosensitizer contained in the ultraviolet curable resin composition is 0.5 to 15 parts by weight with respect to 100 parts by weight of the composition. Particularly, it is 1 to 10 parts by weight. The hard coat layer used in the present invention preferably has a refractive index of 1.45 to 1.65 in order to obtain low reflectivity. The thickness is preferably 1 to 15 μm (especially 2 μm or more, 10 μm or less, particularly 8 μm or less) from the viewpoint of durability, impact resistance, flexibility, and the like.

In the production of the antireflection material, the antireflection material of the present invention is produced by applying the high refractive index composition and then irradiating it with active energy rays, particularly ultraviolet rays. The dose of ultraviolet rays, but also differs depending on the coating thickness is about 100~1000mJ / cm ² (in particular, 200 mJ / cm ² or more .500mJ / cm ² or less.).

  The polarizing plate protective film of the present invention is composed of the above-described antireflection material, particularly an antireflection material having a thickness of 30 to 100 μm. The polarizing plate of the present invention is obtained by laminating a film (polarizing plate protective film) made of the above-described antireflection material to a polarizer. The polarizer on which the polarizing plate protective film is laminated can be obtained by, for example, treating a polyvinyl alcohol film with a dichroic dye such as iodine and stretching it.

  The thickness of the polarizer is 50 to 150 μm. The LCD employing the polarizing plate using the polarizing plate protective film of the present invention is resistant to scratches on the polarizing plate protective film, is highly durable, and has a uniform antireflection layer on the surface of the polarizing plate protective film. It has excellent visibility and anti-reflection effect, prevents reflection of external light, has a wide viewing angle, and has high light transmittance.

Hereinafter, specific examples will be described.
[Example 1]
As the transparent substrate, a cellulose triacetate film (Konicatak 80UVSF manufactured by Konica Corporation, thickness 80 μm) was used. The following ultraviolet curable resin composition A was applied to one surface of this cellulose triacetate film and dried at 80 ° C. for 5 minutes. Next, an 80 W / cm high pressure mercury lamp was irradiated for 4 seconds from a distance of 12 cm to be cured, and a hard coat layer was provided. The hard coat layer had a thickness of 5.0 μm and a refractive index of 1.50.

[Ultraviolet curable resin composition A]
Dipentaerythritol hexaacrylate monomer 600g
Dipentaerythritol hexaacrylate dimer 200g
200 g or more of dipentaerythritol hexaacrylate trimer
Diethoxybenzophenone UV initiator 20g
10g of silicone surfactant
Aerosil R-972 (Nippon Aerosil Co., Ltd.) 10g
Methyl ethyl ketone 500g
Ethyl acetate 500g
Isopropyl alcohol 500g

The composition was ultrasonically dispersed while stirring.
Next, the following composition C for a high refractive index layer was applied onto the hard coat layer with a bar coater and dried at 80 ° C. for 5 minutes. Next, using a high-pressure mercury lamp (80 W), UV rays were irradiated at 300 mJ / cm ² and cured to provide a high refractive index layer. The high refractive index layer had a thickness of 79 nm and a refractive index of 1.84. The film thickness and the refractive index are obtained by calculation from the measured values of the spectral reflectance with a spectrophotometer (U-4000 type manufactured by Hitachi, Ltd.). That is, after roughening the back surface of the cellulose triacetate film on the side where the high refractive index layer is not provided, a light absorption treatment is performed using a black spray to prevent reflection of light on the back surface of the film. Is measured under the condition of regular reflection of 5 degrees.
[Composition C for high refractive index layer]
Titanium polymer (Nippon Soda B-4) 125g
Cinnamic acid resin (C-101 made by Shinko Giken) 5g
Mixture of 5-nitroacenaphthene and N-acetyl-nitro-1-amino-naphthalene (1: 1) 0.1 g
γ-methacryloxypropyltrimethoxysilane 5g
1,200 g of butanol
Isopropyl alcohol 1200g

[Example 2]
In Example 1, C-102 (cinnamic acid resin) manufactured by Shinko Giken was used instead of C-101 (cinnamic acid resin) manufactured by Shinko Giken in the composition C for high refractive index layer. went. The high refractive index layer had a thickness of 78 nm and a refractive index of 1.85.

[Example 3]
In Example 1, C-103 (cinnamic acid resin) manufactured by Shinko Giken was used instead of C-101 (cinnamic acid resin) manufactured by Shinko Giken in the composition C for high refractive index layer. went. The high refractive index layer had a thickness of 80 nm and a refractive index of 1.84.

[Comparative Example 1]
In Example 1, 3 g of dipentaerythritol hexaacrylate monomer and 2 amounts of dipentaerythritol hexaacrylate instead of 5 g of C-101 (cinnamic acid resin) manufactured by Shinko Giken in the composition C for high refractive index layer 1 g of the product, 1 g of a dipentaerythritol hexaacrylate trimer or higher component, and di-diethyl instead of a mixture of 5-nitroacenaphthene and N-acetyl-nitro-1-amino-naphthalene (1: 1) The procedure was the same except that ethoxybenzophenone UV initiator was used. The high refractive index layer had a thickness of 79 nm and a refractive index of 1.85.

[Characteristic]
The films of Examples 1 to 3 and Comparative Example 1 were examined for adhesion, hardness, surface wear resistance, and durability of the high refractive index layer, and the results are shown in Table 1 below. .

Adhesion is based on a cross cut test in accordance with JIS K 5400. Specifically, 11 cuts are made vertically and horizontally at 1 mm intervals on the surface of the high refractive index layer, and 100 1 mm square grids are made, and a cellophane tape is pasted thereon, quickly at an angle of 90 degrees. Peeled off and displayed as the number of grids remaining without peeling.
Hardness was evaluated by pencil hardness at 1 kg load according to JIS K 5400.
Abrasion resistance of the surface of the wound steel wool back and forth direction 1cm per width after surface 30 reciprocate over a mass of 0.1kg per 1cm ² steel wool # 0000 (0.98N / cm ²⁾ generated The number was evaluated.
The durability was evaluated by a change in appearance by conducting a durability test for 500 hours in a high temperature and high humidity (80 ° C., 90% RH) environment.

Table-1
Adhesion Hardness Surface abrasion resistance Durability Example 1 100/100 2H 10 No change Example 2 100/100 2H 12 No change Example 3 100/100 2H 11 No change Comparative Example 1 100/100 H 22 part Crack

[Example 4]
As the transparent substrate, a cellulose triacetate film (Konicatak 80UVSF manufactured by Konica Corporation, thickness 80 μm) was used. The following ultraviolet curable resin composition A was applied to one surface of this cellulose triacetate film and dried at 80 ° C. for 5 minutes. Next, an 80 W / cm high pressure mercury lamp was irradiated for 4 seconds from a distance of 12 cm to be cured, and a hard coat layer was provided. The hard coat layer had a thickness of 5.0 μm and a refractive index of 1.50.

[Ultraviolet curable resin composition A]
Dipentaerythritol hexaacrylate monomer 600g
Dipentaerythritol hexaacrylate dimer 200g
200 g or more of dipentaerythritol hexaacrylate trimer
Diethoxybenzophenone UV initiator 20g
10g of silicone surfactant
Aerosil R-972 (Nippon Aerosil Co., Ltd.) 10g
Methyl ethyl ketone 500g
Ethyl acetate 500g
Isopropyl alcohol 500g

The composition was ultrasonically dispersed while stirring.
Next, the following composition B for medium refractive index layer was applied onto the hard coat layer with a bar coater and dried at 80 ° C. for 5 minutes. Subsequently, using a high-pressure mercury lamp (80 W), ultraviolet rays were irradiated by 300 mJ / cm ² and cured to provide a medium refractive index layer. The middle refractive index layer had a thickness of 82 nm and a refractive index of 1.63.

[Composition B for Medium Refractive Index Layer]
Titanium polymer (Nippon Soda B-4) 125g
20 g of cinnamic acid resin (C-101 made by Shinko Giken)
Mixture of 5-nitroacenaphthene and N-acetyl-nitro-1-amino-naphthalene (1: 1) 0.1 g
γ-methacryloxypropylpropyltrimethoxysilane 25 g
1,200 g of butanol
Isopropyl alcohol 1200g

On the middle refractive index layer, a similar high refractive index layer was provided using the high refractive index layer composition C of Example 1.
Thereafter, the following composition D for a low refractive index layer was applied on the high refractive index layer with a bar coater and dried at 80 ° C. for 5 minutes. Next, using a high-pressure mercury lamp (80 W), the resin was cured by irradiation with ultraviolet rays at 500 mJ / cm ² to provide a low refractive index layer. The low refractive index layer had a thickness of 90 nm and a refractive index of 1.37.

[Composition D for low refractive index layer]
Methacrylic acid-3,3,4,4,5,5,6,6-octafluorohexyl 45g
Diacrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononylethylene glycol 45 g
Dipentaerythritol hexaacrylate (photopolymerizable monomer) 10g
Diethoxybenzophenone (polymerization initiator) 0.2g
Surfactant (F-177, manufactured by Dainippon Ink Co., Ltd.) 1g
Cyclohexanone 3500g
Isopropyl alcohol 7700g

  As described above, a polarizing plate protective film comprising a triacetylcellulose film-hard coat layer-medium refractive index layer-high refractive index layer-low refractive index layer was obtained.

[Example 5]
In Example 4, C-102 (cinnamate resin) manufactured by Shinko Giken was used instead of the cinnamic acid resin (C-101 manufactured by Shinko Giken) in the composition B for medium refractive index layer. Then, a polarizing plate protective film comprising triacetyl cellulose film-hard coat layer-medium refractive index layer (thickness is 83 nm, refractive index is 1.64) -high refractive index layer-low refractive index layer was obtained.

[Example 6]
In Example 4, C-103 (cinnamate resin) manufactured by Shinko Giken was used instead of the cinnamic acid resin (C-101 manufactured by Shinko Giken) in the composition B for medium refractive index layer. Then, a polarizing plate protective film comprising triacetyl cellulose film-hard coat layer-medium refractive index layer (thickness is 82 nm, refractive index is 1.64) -high refractive index layer-low refractive index layer was obtained.

[Example 7]
In Example 5, C-102 (cinnamate resin) manufactured by Shinko Giken was used instead of the cinnamic acid resin (C-101 manufactured by Shinko Giken) in the composition C for high refractive index layer. Then, a polarizing plate protective film comprising a triacetyl cellulose film-hard coat layer-medium refractive index layer-high refractive index layer (thickness is 78 nm, refractive index is 1.85) -low refractive index layer was obtained.

[Example 8]
In Example 6, except that C-103 (cinnamic acid resin) manufactured by Shinko Giken was used instead of the cinnamic acid resin (C-101 manufactured by Shinko Giken) in the composition C for high refractive index layer. Then, a polarizing plate protective film comprising a triacetyl cellulose film-hard coat layer-medium refractive index layer-high refractive index layer (thickness is 80 nm, refractive index is 1.84) -low refractive index layer was obtained.

[Comparative Example 2]
In Example 4, 10 g of dipentaerythritol hexaacrylate monomer and 2 amounts of dipentaerythritol hexaacrylate instead of 20 g of the cinnamic acid resin (C-101 made by Shinko Giken) in the composition B for medium refractive index layer 5 g and 5 g of dipentaerythritol hexaacrylate trimer or more, and di-diethyl instead of a mixture of 5-nitroacenaphthene and N-acetyl-nitro-1-amino-naphthalene (1: 1) Using ethoxybenzophenone UV initiator, 3 g of dipentaerythritol hexaacrylate monomer instead of 5 g of C-101 (cinnamic acid resin) manufactured by Shinko Giken in the composition C for high refractive index layer, dipenta 1g of erythritol hexaacrylate dimer, dipentaerythritol hexaacrylate Except for using 1 g of the component above the monomer, and using a diethoxybenzophenone UV initiator instead of the mixture (1: 1) of 5-nitroacenaphthene and N-acetyl-nitro-1-amino-naphthalene. It carried out similarly and obtained the polarizing plate protective film which consists of a triacetyl cellulose film-hard-coat layer-medium refractive index layer-high refractive index layer-low refractive index layer.

[Characteristic]
About the polarizing plate protective film of the said Examples 4-8 and the comparative example 2, since the minimum reflectance, adhesiveness, and durability (a test method is the same as the above) were investigated, the result is shown in following Table-2. Show.

Table-2
Minimum reflectance Adhesion Durability Example 4 0.2% 100/100 No change Example 5 0.2% 100/100 No change Example 6 0.2% 100/100 No change Example 7 0.2% 100/100 No change Example 8 0.2% 100/100 No change Comparative Example 2 0.2% 80/100 Partially cracked

[Example 9]
Cotton linter and wood triacetate cellulose triacetate are mixed at a weight ratio of 85/15, 2% by weight of triphenyl phosphate as plasticizer, 3% by weight of ethylphthalyl glycolate, tinuvin 326 and tinuvin 328 as UV absorbers (Ciba A cellulose triacetate film having a thickness of 50 μm and containing 0.5% by weight of each (specialty chemicals) was used as a transparent substrate.

On one surface of this cellulose triacetate film, the following conductive coating composition was applied at 15 ml / m ² and dried at 80 ° C. for 5 minutes to provide a conductive layer. Next, on this conductive layer, the following ultraviolet curable resin composition was applied at 15 ml / m ² and dried at 80 ° C. for 5 minutes, and then irradiated with 90 mJ / cm ^{2 of a} high-pressure mercury lamp. Cured to provide a hard coat layer. The conductive layer had a thickness of 0.2 μm, and the hard coat layer had a thickness of 5 μm.

プロピレングリコールメチルエーテル ６５ｍｌ
メチルエチルケトン ２０ｍｌ
メタノール １０ｍｌ
乳酸エチル ５ｍｌ [Conductive paint composition]
Polymethylmethacrylate 0.5g
0.5 g of a compound represented by the following formula

65 ml of propylene glycol methyl ether
20 ml of methyl ethyl ketone
10 ml of methanol
5 ml of ethyl lactate

[Ultraviolet curable resin composition]
Dipentaerythritol hexaacrylate monomer 20g
Dipentaerythritol hexaacrylate dimer 7.5g
7.5g or more of dipentaerythritol hexaacrylate trimer
Diethoxybenzophenone (UV initiator) 0.5g
Aerosil R-972 (Nippon Aerosil Co., Ltd.) 0.5g
Methyl ethyl ketone 38ml
Propylene glycol methyl ether 38ml

Next, the following composition E for a high refractive index layer was applied onto the hard coat layer with a bar coater and dried at 80 ° C. for 5 minutes. Subsequently, using a high-pressure mercury lamp (80 W), ultraviolet rays were irradiated at 300 mJ / cm ² and cured to provide a high refractive index layer. The high refractive index layer had a thickness of 82 nm and a refractive index of 1.81.

[Composition E for high refractive index layer]
Titanium polymer (Nippon Soda B-4) 125g
Bisphenol type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) 5g

4,4′-bis [di (β-hydroxyethoxy) phenylsulfonyl] phenyl sulfide-bis-hexafluoroantimonate 0.3 g
γ-glycidoxypropyltrimethoxysilane 5g
1,200 g of butanol
Isopropyl alcohol 1200g

[Example 10]
In Example 9, Araldite CY179 (alicyclic epoxy resin manufactured by Ciba-Geigy Corporation of Japan) was used in place of Epicoat 828 (bisphenol type epoxy resin) manufactured by Yuka Shell Epoxy Co. in the composition E for high refractive index layer. Did the same. The high refractive index layer had a thickness of 81 nm and a refractive index of 1.82.

[Example 11]
In Example 9, EHPE-3158 (an alicyclic epoxy resin manufactured by Daicel Chemical Industries) was used instead of Epicoat 828 (bisphenol type epoxy resin) manufactured by Yuka Shell Epoxy in the composition E for high refractive index layer. I went in the same way except. The high refractive index layer had a thickness of 82 nm and a refractive index of 1.82.

[Example 12]
In Example 9, it carried out similarly except having used KR500 of Asahi Denka Kogyo Co., Ltd. instead of Epicoat 828 (bisphenol type epoxy resin) by the oil-ized shell epoxy company in the composition E for high refractive index layers. The high refractive index layer had a thickness of 81 nm and a refractive index of 1.83.

[Example 13]
In Example 12, it carried out similarly except having used the tetrabutoxy titanium instead of the titanium polymer (Nippon Soda B-4) in the composition E for high refractive index layers. The high refractive index layer had a thickness of 81 nm and a refractive index of 1.84.

[Example 14]
In Example 13, it carried out similarly except having added 2 mol of water with respect to 1 mol of tetrabutoxy titanium of the composition E for high refractive index layers. The high refractive index layer had a thickness of 80 nm and a refractive index of 1.85.

[Comparative Example 3]
In Example 9, 3 g of dipentaerythritol hexaacrylate monomer and dipentaerythritol hexaacrylate were used in place of 5 g of Epicoat 828 (bisphenol type epoxy resin) manufactured by Yuka Shell Epoxy in the composition E for high refractive index layer. 1 g of dimer and 1 g of dipentaerythritol hexaacrylate trimer or more are used, and instead of a mixture (1: 1) of 5-nitroacenaphthene and N-acetyl-nitro-1-amino-naphthalene The same procedure was carried out except that diethoxybenzophenone UV initiator was used. The high refractive index layer had a thickness of 81 nm and a refractive index of 1.83.

[Characteristic]
Since the films of Examples 9 to 14 and Comparative Example 3 were examined for the adhesion, hardness, surface wear resistance, durability (test method is the same as above), and durability adhesion of the high refractive index layer. The results are shown in Table 3 below.
Durability adhesion was stored for 500 hours in a high-temperature and high-humidity (80 ° C., 90% RH) environment, and evaluated by the same method as adhesion.

Table-3
Adhesion Hardness Surface wear resistance Durability Durability Adhesion Example 9 100/100 2H 12 No change 92/100
Example 10 100/100 2H 11 No change 93/100
Example 11 100/100 2H 10 No change 91/100
Example 12 100/100 2H 8 No change 99/100
Example 13 100/100 2H 8 No change 95/100
Example 14 100/100 2H 8 No change 94/100
Comparative Example 3 100/100 H 22 Partially cracked 85/100

[Example 15]
The transparent substrate (cellulose triacetate film) used in Example 9 was used. And the ultraviolet curable resin composition used in Example 9 was similarly applied to one surface of this cellulose triacetate film to provide a similar hard coat layer. The following composition F for medium refractive index layer was applied onto this hard coat layer with a bar coater and dried at 80 ° C. for 5 minutes. Subsequently, using a high-pressure mercury lamp (80 W), it was cured by irradiation with ultraviolet rays of 300 mJ / cm ² to provide an intermediate refractive index layer. The middle refractive index layer had a thickness of 84 nm and a refractive index of 1.65.

[Composition F for Medium Refractive Index Layer]
Titanium polymer (Nippon Soda B-4) 125g
Bisphenol type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) 20 g
4,4′-bis [di (β-hydroxyethoxy) phenylsulfonyl] phenyl sulfide-bis-hexafluoroantimonate 0.3 g
γ-glycidoxypropylpropyltrimethoxysilane 20 g
1,200 g of butanol
Isopropyl alcohol 1200g

On this medium refractive index layer, the high refractive index layer composition E of Example 9 was applied with a bar coater to provide a similar high refractive index layer.
Thereafter, the following composition D for a low refractive index layer was applied on the high refractive index layer with a bar coater and dried at 80 ° C. for 5 minutes. Next, using a high-pressure mercury lamp (80 W), the resin was cured by irradiation with ultraviolet rays at 500 mJ / cm ² to provide a low refractive index layer. The low refractive index layer 9 had a thickness of 90 nm and a refractive index of 1.37.

[Composition D for low refractive index layer]
Methacrylic acid-3,3,4,4,5,5,6,6-octafluorohexyl 45g
Diacrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononylethylene glycol 45 g
Dipentaerythritol hexaacrylate (photopolymerizable monomer) 10g
Diethoxybenzophenone (polymerization initiator) 0.2g
Surfactant (F-177, manufactured by Dainippon Ink Co., Ltd.) 1g
Cyclohexanone 3500g
Isopropyl alcohol 7700g
As described above, a polarizing plate protective film comprising a triacetyl cellulose film-conductive layer-hard coat layer-medium refractive index layer-high refractive index layer-low refractive index layer was obtained.

[Example 16]
In Example 15, except for using Araldite CY179 (an alicyclic epoxy resin manufactured by Ciba Geigy Japan) in place of Epicoat 828 (bisphenol type epoxy resin) manufactured by Yuka Shell Epoxy in the composition F for medium refractive index layer Is carried out in the same manner, and a polarizing plate comprising a triacetyl cellulose film-conductive layer-hard coat layer-medium refractive index layer (thickness is 83 nm, refractive index is 1.65) -high refractive index layer-low refractive index layer A protective film was obtained.

[Example 17]
In Example 15, EHPE-3158 (an alicyclic epoxy resin manufactured by Daicel Chemical Industries) was used instead of Epicoat 828 (bisphenol type epoxy resin) manufactured by Yuka Shell Epoxy in the composition F for medium refractive index layer. In the same manner, a triacetyl cellulose film-conductive layer-hard coat layer-medium refractive index layer (thickness is 84 nm, refractive index is 1.64) -high refractive index layer-low refractive index layer A polarizing plate protective film was obtained.

[Example 18]
In Example 16, it carried out similarly except having used the composition for high refractive index layers of Example 10 as a high refractive index layer, a triacetyl cellulose film-conductive layer-hard coat layer-medium refractive index layer-high refractive index. A polarizing plate protective film comprising an index layer and a low refractive index layer was obtained.

[Example 19]
In Example 17, it carried out similarly except having used the composition for high-refractive-index layers of Example 11 as a high-refractive-index layer. A polarizing plate protective film comprising an index layer and a low refractive index layer was obtained.

[Example 20]
In Example 15, KR500 of Asahi Denka Kogyo Co., Ltd. was used in place of Epicoat 828 (bisphenol type epoxy resin) manufactured by Yuka Shell Epoxy Co. in Composition F for Medium Refractive Index Layer and Composition E for High Refractive Index Layer. A medium refractive index layer (thickness is 85 nm and a refractive index is 1.66) and a high refractive index layer (thickness is 81 nm and a refractive index is 1.83) are formed in the same manner except that they are used. A polarizing plate protective film comprising an acetylcellulose film, a conductive layer, a hard coat layer, a medium refractive index layer, a high refractive index layer, and a low refractive index layer was obtained.

[Example 21]
In Example 20, the same procedure was followed except that titanium butoxide was used instead of the titanium polymer (B-4 manufactured by Nippon Soda Co., Ltd.) in the medium refractive index layer composition F, and 15 g of water was further added. The intermediate refractive index layer (thickness is 80 nm) except that titanium butoxide is used in place of the titanium polymer (B-4 manufactured by Nippon Soda Co., Ltd.) and 10 g of water is further added. , Refractive index 1.67) and high refractive index layer (thickness is 79 nm, refractive index 1.86), triacetyl cellulose film-conductive layer-hard coat layer-medium refractive index layer-high A polarizing plate protective film comprising a refractive index layer-low refractive index layer was obtained.

[Comparative Example 4]
In Example 15, 10 g of dipentaerythritol hexaacrylate monomer and 10 g of dipentaerythritol hexaacrylate instead of 20 g of Epicoat 828 (bisphenol type epoxy resin) manufactured by Yuka Shell Epoxy in the composition B for medium refractive index layer Using 5 g of dimer and 5 g of dipentaerythritol hexaacrylate trimer or more, instead of a mixture (1: 1) of 5-nitroacenaphthene and N-acetyl-nitro-1-amino-naphthalene In addition, dipentaerythritol hexaacrylate monomer is used instead of 5 g of Epicoat 828 (bisphenol type epoxy resin) manufactured by Yuka Shell Epoxy Co., Ltd. in the composition E for high refractive index layer. 3g, dipentaerythritol hexaac 1 g of a rate dimer, 1 g of a dipentaerythritol hexaacrylate trimer or more, and a mixture (1: 1) of 5-nitroacenaphthene and N-acetyl-nitro-1-amino-naphthalene Instead, a polarizing plate protective film comprising a triacetyl cellulose film, a hard coat layer, a medium refractive index layer, a high refractive index layer and a low refractive index layer was obtained in the same manner except that a diethoxybenzophenone UV initiator was used.

[Comparative Example 5]
In Example 15, tetrabutoxy titanium was used in place of the titanium polymer (B-4 manufactured by Nippon Soda Co., Ltd.) in the medium refractive index layer composition B, and the oiled shell epoxy company in the high refractive index layer composition E. Instead of 5 g of Epicoat 828 (bisphenol type epoxy resin) made of 3 g of dipentaerythritol hexaacrylate monomer, 1 g of dipentaerythritol hexaacrylate dimer, 1 g of dipentaerythritol hexaacrylate trimer or higher component Triacetylcellulose, except that diethoxybenzophenone UV initiator was used instead of the mixture (1: 1) of 5-nitroacenaphthene and N-acetyl-nitro-1-amino-naphthalene. From film-hard coat layer-medium refractive index layer-high refractive index layer-low refractive index layer That to obtain a polarizing plate protective film.

[Characteristic]
About the polarizing plate protective film of the said Examples 15-21 and Comparative Examples 4 and 5, since the minimum reflectance, adhesiveness, durability, and durable adhesiveness (the test method is the same as the above) were investigated, the result was Shown in Table-4 below.

Table-4
Minimum reflectance Adhesion Durability Durability Adhesion Example 15 0.2% 100/100 No change 91/100
Example 16 0.2% 100/100 No change 92/100
Example 17 0.2% 100/100 No change 91/100
Example 18 0.2% 100/100 No change 93/100
Example 19 0.2% 100/100 No change 92/100
Example 20 0.2% 100/100 No change 98/100
Example 21 0.2% 100/100 No change 97/100
Comparative Example 4 0.2% 80/100 Partially cracked 72/100
Comparative Example 5 0.2% 70/100 Many cracks 63/100

  As can be seen, the polarizing plate protective film according to the present invention has excellent optical properties, and an excellent polarizing plate can be obtained. Moreover, it is excellent in adhesiveness with a polarizer and is also excellent in durability.

Schematic diagram of polarizing plate Schematic of polarizing plate protective film

Explanation of symbols

5 Triacetylcellulose film (transparent substrate)
6 Hard coat layer 7 Middle refractive index layer 8 High refractive index layer 9 Low refractive index layer

Representative Katsumi Udaka

Claims (19)

An antireflection material in which an antireflection layer is provided on a transparent substrate,
The antireflection layer is composed of a plurality of layers,
At least one of the plurality of layers is composed of a composition containing a condensate of metal alkoxide, a crosslinkable polymer, and a solvent,
The crosslinkable polymer has an —CH═CH—CO— group in its main chain and / or side chain. An antireflection material in which an antireflection layer is provided on a transparent substrate,
The antireflection layer is composed of a plurality of layers,
At least one of the plurality of layers is composed of a composition containing a condensate of metal alkoxide, a crosslinkable polymer, and a solvent,
The anti-reflective material, wherein the crosslinkable polymer has an azide group in the main chain and / or side chain. An antireflection material in which an antireflection layer is provided on a transparent substrate,
The antireflection layer is composed of a plurality of layers,
At least one of the plurality of layers is composed of a composition containing a condensate of metal alkoxide, a crosslinkable polymer, and a solvent,
The ratio of the metal alkoxide condensate and the crosslinkable polymer is metal alkoxide condensate / crosslinkable polymer = 3 to 50 (mass ratio).   The antireflective material according to claim 3, wherein the crosslinkable polymer has a -CH = CH-CO- group in its main chain and / or side chain.   4. The antireflection material according to claim 3, wherein the crosslinkable polymer has an azide group in the main chain and / or side chain.   The ratio of the metal alkoxide condensate and the crosslinkable polymer is metal alkoxide condensate / crosslinkable polymer = 3 to 50 (mass ratio), the antireflection material according to claim 1 or 2. An antireflection material in which an antireflection layer is provided on a transparent substrate,
The antireflection layer is composed of a plurality of layers,
At least one of the plurality of layers is composed of a composition containing a metal alkoxide condensate, a cationic polymerization compound, and a solvent,
The ratio of the metal alkoxide condensate and the cationic polymerization compound is a metal alkoxide condensate / cationic polymerization compound = 3 to 50 (mass ratio).   The antireflective material according to claim 7, wherein the cationic polymerization compound is selected from the group consisting of an oxirane cyclic compound, an oxetane cyclic compound, a thiitan cyclic compound, and a thietan cyclic compound.   9. The antireflection material according to claim 1, wherein the composition containing the metal alkoxide condensate further contains an epoxy-based active energy ray-reactive compound.   The composition containing a metal alkoxide condensate further contains an epoxy-based active energy ray-reactive compound and a polymerization initiator, and the antireflection material according to any one of claims 1 to 9.   The antireflection material according to any one of claims 1 to 8, wherein the composition containing the condensate of metal alkoxide further contains an epoxy-based active energy ray-reactive compound, a polymerization initiator, and water. Comprising the constituent requirements of the antireflective material of any one of claims 1 to 11,
The refractive index is higher than the refractive index of the layer composed of the composition containing the metal alkoxide condensate above the layer composed of the composition containing the metal alkoxide condensate in the antireflection material layer. An antireflective material comprising a low refractive index layer having a low refractive index. Comprising the constituent requirements of the antireflective material of any one of claims 1 to 11,
The refractive index is higher than the refractive index of the layer composed of the composition containing the metal alkoxide condensate above the layer composed of the composition containing the metal alkoxide condensate in the antireflection material layer. Low refractive index layer is constructed,
Refraction is lower than the refractive index of the layer composed of the composition containing the metal alkoxide condensate below the layer composed of the composition containing the metal alkoxide condensate in the antireflection material layer. An antireflection material comprising a middle refractive index layer having a low refractive index and a refractive index higher than that of the low refractive index layer.   The layer formed of a composition containing a metal alkoxide condensate is formed by irradiating active energy rays to a layer of the applied composition. The antireflection material according to any one of Items 11.   The antireflection material according to any one of claims 1 to 14, wherein the transparent substrate is composed of a material selected from the group consisting of a lower fatty acid ester of cellulose and a uniaxially stretched polyethylene terephthalate.   The antireflection material according to claim 1, wherein the transparent substrate is composed of cellulose triacetate. It is a manufacturing method of the antireflection material in any one of Claims 1-16,
A method for producing an antireflective material, comprising: applying a composition containing a metal alkoxide condensate according to any one of claims 1 to 16 and then irradiating the composition with active energy rays.   A polarizing plate protective film comprising the antireflection material according to claim 1. A polarizing plate comprising a film made of the antireflection material according to any one of claims 1 to 16 and bonded to a polarizer.

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