JP2007264272A - High refractive index hard coat layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high refractive index hard coat layer. <P>SOLUTION: The high refractive index hard coat layer used for an optical laminate comprises: a monomer comprising at least two sulfur atoms; an at least three-functional urethane acrylate resin; and/or at least three-functional acrylate resin, wherein the monomer and the resin are hardened by a first polymerization initiator and a second polymerization initiator. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a high refractive index hard coat layer and an optical laminate having the same.

  An optical laminate including a hard coat layer is used for the purpose of suppressing light reflection in an image display unit of an optical device, a windshield of a vehicle, a special building material, or the like. In particular, an image display surface in an image display device such as a liquid crystal display (LCD) or a cathode ray tube display device (CRT) is required to reduce the reflection due to light rays emitted from an external light source and improve its visibility. On the other hand, by using an optical laminate (for example, an antireflection laminate) provided with a hard coat layer as a light-transmitting substrate, reflection on the image display surface of the image display device is reduced and visibility is improved. It is generally done to improve.

  The hard coat layer is generally formed using an organic material such as a curable resin instead of a glass material for reasons such as impact resistance and ease of manufacture. However, the curable resin (for example, acrylic resin) used for forming the hard coat layer has a desired hardness, but its refractive index n is about 1.5, and antireflection optics. It has been difficult to achieve a desired refractive index (n = 1.6 or more) as a laminate. For this reason, conventionally, metal oxide fine particles such as titanium and antimony having a high refractive index are generally added to the hard coat layer to increase the refractive index.

  However, although the addition of metal oxide fine particles can achieve a desired refractive index, the haze value of the optical laminate is increased, resulting in whitening of the optical laminate or total light of the optical laminate. It has often been pointed out that the transmittance decreases and the image visibility decreases. Further, metal oxides such as titanium and antimony are themselves rare metals, and are rare and expensive.

  Under such circumstances, Japanese Patent Application Laid-Open No. 2001-115087 (Patent Document 1) does not include a metal oxide and represents a benzoyl-substituted poly (p-phenylene) represented by a specific formula or a specific formula. A high refractive index hard coat layer formed using the represented benzoyl-substituted poly (p / m-phenylene) has been proposed. However, when an organic material is used, the hard coat layer may be colored or discolored due to changes over time or the weather (for example, sunlight).

  Therefore, it currently does not contain metal oxides, has a high refractive index, high scratch resistance obtained by appropriately curing an appropriate organic material, and does not color or discolor even when irradiated with light such as ultraviolet rays for a long time. A hard coat layer capable of realizing excellent coloration resistance has not been proposed.

JP 2001-115087 A

In the present invention, the present inventors set the refractive index of the hard coat layer to a high value of 1.6 or more by using a monomer containing a specific sulfur atom and a specific urethane acrylate (acrylate). And the knowledge that scratch resistance, weather resistance, anti-coloring property and the like can be achieved at a high level. The present invention has been made based on such findings.
Therefore, the hard coat layer used in the optical laminate according to the present invention is:
A monomer comprising at least two or more sulfur atoms;
A trifunctional or higher functional urethane acrylate resin and / or a trifunctional or higher functional acrylate resin,
The monomer and the resin are cured by a first polymerization initiator and a second polymerization initiator,
The first polymerization initiator has an extinction coefficient at 360 nm or more of 100 ml / g · cm or less;
The second polymerization initiator has an extinction coefficient exceeding 100 ml / g · cm at 360 nm or more.

Hard Coat Layer In the present invention, “hard coat layer” refers to a material that exhibits a hardness of “H” or higher in a pencil hardness test defined by JIS 5600-5-4 (1999). In the present invention, the “hard coat layer” includes any form such as a hard coat film, a hard coat plate, and a hard coat film. The hard coat layer has a layer thickness (at the time of curing) of 0.1 to 100 μm, preferably 0.8 to 20 μm.

で表されるものが挙げられる。 Monomer comprising at least 2 or more sulfur atoms As the monomer comprising at least 2 or more sulfur atoms, any monomer can be used, but preferably the following formula:

The thing represented by is mentioned.

  In the present invention, a commercially available product can be used as the monomer containing at least two or more sulfur atoms. Specifically, S2EG, MPSMA, MPS, MPT, BDS, MPV, MPG, PTD and the like ( Sumitomo Seika Chemicals Co., Ltd.); IUL2000, IUL3000, IUMS1010 and the like (Mitsubishi Gas Chemical Co., Ltd.); MPSMA can preferably be used.

Trifunctional or higher urethane acrylate resin Any trifunctional or higher functional urethane acrylate resin may be used, and specific examples include those composed of a polyol compound and a polyisocyanate compound. Specific examples of the polyol compound include ethylene glycol, propylene glycol, neopentyl glycol, tricyclodecane dimethylol, cyclohexane dimethylol, trimethylolpropane, glycerin, 1,3-propanediol, 1,4-butanediol, 1, 3-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, diethylene glycol, tripropylene glycol, 1, 9- Nonanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A polyethoxyglycol, polycarbonate polyol, pentaerythritol, sorbitol , Sucrose, quadroleol polybutadiene polyol, hydrogenated polybutadiene polyol, hydrogenated dimer diol pentaerythritol, etc .; trimethylolpropane, glycerin, pentaerythritol, sorbitol, sucrose, quadrole and other compounds containing a trivalent or higher hydroxyl group, Polyether polyol obtained by modifying with cyclic ether compounds such as ethylene oxide (EO), propylene oxide (PO), butylene oxide, tetrahydrofuran, etc .; polycaprolactone polyol obtained by modifying with caprolactone; consisting of dibasic acid and diol Mention may be made of polyester polyols obtained by modification with polyester; and mixtures of two or more thereof.

  More specifically, EO-modified trimethylolpropane, PO-modified trimethylolpropane, tetrahydrofuran-modified trimethylolpropane, caprolactone-modified trimethylolpropane, EO-modified glycerol, PO-modified glycerol, tetrahydrofuran-modified glycerin, caprolactone-modified glycerol, EO-modified pentaerythritol. , PO-modified pentaerythritol, tetrahydrofuran-modified pentaerythritol, caprolactone-modified pentaerythritol, EO-modified sorbitol, PO-modified sorbitol, caprolactone-modified sorbitol, EO-modified sucrose, PO-modified sucrose, EO-modified sucrose, EO-modified quadrole, etc. Can be mentioned.

  Specific examples of the polyisocyanate compound include 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4, 4-diphenylmethane diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, tetramethylxylylene diisocyanate, Biphenylene diisocyanate, 1,5-naphthylene diisocyanate, o-tolidine diisocyanate, hexamethylene diisocyanate, 4,4'-methylenebiscyclohexyl isocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, and Examples thereof include polycondensates such as burettes and nurates, and mixtures of two or more thereof. Particularly preferred are tolylene diisocyanate, xylylene diisocyanate and nurateated product of hexamethylene diisocyanate, isophorone diisocyanate, and more preferred are hexamethylene diisocyanate and isophorone diisocyanate.

  A commercially available product can be used as the tri- or higher functional urethane acrylate resin, and specific examples include the purple light series manufactured by Nippon Gosei Co., Ltd., such as UV1700B, UV6300B, UV765B, UV7640B, and UV7600B; Art Resin series, such as Art Resin HDP, Art Resin UN 9000H, Art Resin UN 3320HA, Art Resin UN 3320HB, Art Resin UN 3320HC, Art Resin UN 3320HS, Art Resin UN 901M, Art Resin UN 902MS, Art Resin UN 903, etc .; UA100H, U4H, U6H, U15HA, UA32P, U6LPA, U324A, U9HAMI, etc. manufactured by the company; Ebecry manufactured by Daicel UCB Series, for example, 1290, 5129, 254, 264, 265, 1259, 1264, 4866, 9260, 8210, 204, 205, 6602, 220, 4450, etc .; Beam set series made by Arakawa Chemical, for example, 371 371S, 777, 577BV, 579AK, etc .; RQ series manufactured by Mitsubishi Rayon Co., Ltd .; Unidic series manufactured by Dainippon Ink Co., Ltd., etc .; DPHA40H (manufactured by Nippon Kayaku Co., Ltd.), CN9006 (thermer) For example, CN968). Among these, UV1700B (manufactured by Nippon Gosei Co., Ltd.), DPHA40H (manufactured by Nippon Kayaku Co., Ltd.), Art Resin HDP (manufactured by Negami Kogyo Co., Ltd.), Beam Set 371 (manufactured by Arakawa Chemical Co., Ltd.), U15HA (manufactured by Shin Nakamura Chemical Co., Ltd.) ) And the like.

Trifunctional or higher acrylate resin Specific examples of the trifunctional or higher acrylate resin include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol tetraacrylate, isocyanuric acid modified tri An acrylate etc. are mentioned. These acrylates may be modified in part of the molecular skeleton, such as those modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, etc. be able to.

  A tri- or higher functional acrylate resin may be a commercially available product. Specifically, KAYADAD, KAYAMER series manufactured by Nippon Kayaku Co., Ltd., for example, DPHA, PET30, GPO303, TMPTA, THE330, TPA330, D310, D330, PM2, PM21, DPCA20, DPCA30, DPCA60, DPCA120 and the like; Aronix series manufactured by Toagosei Co., Ltd., for example, M305, M309, M310, M315, M320, M327, M350, M360, M402, M408, M450, M7100 , M7300K, M8030, M8060, M8100, M8530, M8560, M9050, etc .; NK ester series manufactured by Shin-Nakamura Chemical Co., Ltd., for example, TMPT, A-TMPT, A-TMM -3, A-TMM3L, A-TMMT, A-TMPT-6EO, A-TMPT-3CL, A-GLY-3E, A-GLY-6E, A-GLY-9E, A-GLY-11E, A-GLY -18E, A-GLY-20E, A-9300, AD-TMP-4CL, AD-TMP, etc .; NK Economer series manufactured by Shin-Nakamura Chemical Co., Ltd., for example, ADP51, ADP33, ADP42, ADP26, ADP15, etc. New Frontier Series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., such as TMPT, TMP3, TMP15, TMP2P, TMP3P, PET3, TEICA and the like; Ebecryl series manufactured by Daicel UCB, Inc., such as TMPTA, TMPTAN, 160 , TMPEOTA, OTA480, 53, PETIA, 2047, 40, 40, 1140, PETAK, DPHA and the like; CD501, CD9021, CD9052, SR351, SR351HP, SR351LV, SR368, SR368D, SR415, SR444, SR454, SR454HP, SR492, SR4992, SR90012, manufactured by Thermar SR9020, SR9020HP, SR9035, CD9051, SR350, SR9009, SE9011, SR295, SR355, SR399, SR399LV, SR494, SR9041 and the like.

  The mixing ratio of 1) a monomer comprising at least two or more sulfur atoms and 2) a trifunctional or higher functional urethane acrylate resin and / or a trifunctional or higher functional acrylate resin may be determined as appropriate. Is from 1: 9 to 9: 1, preferably from 2: 8 to 8: 2. By setting the mixing ratio within the above range, the ratio of the high refractive index resin is increased, the desired high refractive index hard coat layer is formed, and the original characteristic of the hard coat layer is exhibited. Is possible.

Polymerization initiator In the present invention, the polymerization initiator is cured with a first polymerization initiator and a second polymerization initiator. A first polymerization initiator having a larger absorption coefficient than that of the second polymerization initiator is used. Specifically, the first polymerization initiator has an extinction coefficient at 360 nm or more of 100 ml / g · cm or less, preferably 90 ml / g · cm or less, and the second polymerization initiator is at 360 nm or more. An extinction coefficient of more than 100 ml / g · cm, preferably 120 ml / g · cm or more is used.

By using the first polymerization initiator and the second polymerization initiator, it is possible to have an optical laminate excellent in high hardness and transparency. When only the first polymerization initiator is used,
The optical laminate may be cloudy or may have fine irregularities formed on the surface of the optical laminate. As a result, a smooth and highly transparent optical laminate may not be obtained. Further, when only the second polymerization initiator is used, the hardness becomes insufficient, and coloring (for example, yellow discoloration) may occur if the amount of the second polymerization initiator added is increased to improve the hardness. It was. Further, when the amount of ultraviolet light is increased in the second polymerization initiator in order to improve the hardness, the produced optical laminate may be deformed. However, by using a combination of the first polymerization initiator and the second polymerization initiator, the reason is not clear, but an optical laminate that is remarkably excellent in high transparency and hardness can be obtained. .

  In the present invention, the “absorption coefficient” is an absorbance measured using a spectrophotometer, and the absorbance is proportional to the optical path length (L) and sample concentration (C) of the sample cell, and is expressed by the equation A = αLC, where α = The extinction coefficient can be determined. As the spectrophotometer for measuring the absorbance, for example, an infrared spectrophotometer, a visible spectrophotometer, or an ultraviolet spectrophotometer can be used according to the wavelength band of the light to be measured. The polymerization initiator in the present invention generates a radical which is an active species by absorbing light, and advances the polymerization reaction. An initiator having a higher extinction coefficient is more likely to generate radicals and has higher reactivity.

  1) a monomer comprising at least two or more sulfur atoms, and 2) a trifunctional or higher functional urethane acrylate resin and / or a trifunctional or higher functional acrylate resin, the first polymerization initiator and the second polymerization initiator It may be cured by either. According to a preferred embodiment of the present invention, 1) a monomer comprising at least two or more sulfur atoms is cured by a second polymerization initiator, and 2) a trifunctional or higher functional urethane acrylate resin and / or a trifunctional or higher functional acrylate resin. Is preferably cured by the first polymerization initiator.

  Specific examples of the first polymerization initiator include commercially available products such as Irgacure 184, Irgacure 250, Irgacure 651, IRGACURE 754, Irgacure 907, Irgacure 2959, Darocure 1173, Darocure EDB, Darocure EHA, etc. It is.

  Specific examples of the second polymerization initiator include commercially available products such as Irgacure OXE01, IRGACURE 369, Irgacure 784, Irgacure 819, Irgacure 907, Irgacure 1300, IRGACURE 1800, Darocure 1173, Darocure Tur, and DarocureTPur. Examples include Irgacure 819, Irgacure OXE01, and Darocur TPO.

Penetration solvent According to a preferred embodiment of the present invention, a hard coat layer can be formed using a penetration solvent. The permeable solvent is a solvent that is permeable to an optical layer such as a light-transmitting substrate or a hard coat layer. In the present invention, “permeability” of a permeable solvent is intended to include all concepts such as permeability, swelling, solubility, and wettability with respect to a light-transmitting substrate. Therefore, for example, by applying a composition for forming an optical layer (for example, a hard coat layer) containing a permeable solvent to a light-transmitting substrate, it is considered that the following behavior is exhibited. 1) The light-transmitting substrate is swollen by the penetrating solvent, and then both the penetrating solvent and the other optical layer forming composition penetrate into the light-transmitting substrate to form the light-transmitting substrate and the light-transmitting substrate. The interface with the optical layer is mixed. 2) The light-transmitting base material swells in the formed optical layer when the light-transmitting base material swells due to the permeable solvent and further dissolves the light-transmitting base material. The base material component and the optical layer forming composition are mixed at the interface. 3) The light-transmitting substrate is swollen by the penetrating solvent, and then the penetrating solvent or a mixture of the composition and the optical layer forming composition penetrates into the light-transmitting substrate. For the optical layer formation formed with the light-transmitting base material component, it is further dissolved by the penetrating solvent and is simultaneously lifted into the optical layer forming composition in which the light-transmitting base material component is formed. The composition is mixed at the interface.

  Specific examples of the permeable solvent include alcohols such as isopropyl alcohol, methanol, and ethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as methyl acetate, ethyl acetate, and butyl acetate; chloroform, methylene chloride, Halogenated hydrocarbons such as tetrachloroethane; or a mixture thereof, preferably esters and ketones.

  More specific examples of osmotic solvents include acetone, methyl acetate, ethyl acetate, butyl acetate, chloroform, methylene chloride, trichloroethane, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, nitromethane, 1,4-dioxane, dioxolane, N-methylpyrrolidone, N, N-dimethylformamide, methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol, diisopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, preferably methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone And cyclohexanone.

  The amount of penetrating solvent added can be determined as appropriate, and is, for example, 0.01 parts by weight or more and 50 parts by weight or less, preferably 0.1 parts by weight based on the total amount of the composition for hard coat layer. (More preferably 1 part by weight) or more, and the upper limit is 25 parts by weight (more preferably 15 parts by weight) or less.

Optional Components The hard coat layer according to the present invention is formed of the above-described components, but optional components may be added to enhance the optical characteristic function of the hard coat layer.

Stabilizer According to a preferred embodiment of the present invention, it is preferable to add a stabilizer to the hard coat composition. The stabilizer can suppress denaturation caused by weather or changes with time in the components constituting the hard coat layer. In particular, it is considered that by adding a stabilizer, the hard coat layer can suppress discoloration due to light or heat, particularly yellowing. When the stabilizer is mainly used for preventing discoloration, the stabilizer may be a discoloration preventing agent.

  Specific examples of the stabilizer include hindered amine (HALS), benzotriazole, hindered phenol, triazine, phosphorus antioxidant, thioether antioxidant, and preferably hindered amine (HALS). And benzotriazole series.

  Regardless of whether or not the stabilizer itself has a reactive group, the molecular weight of the stabilizer is not limited when the stabilizer is a polymer substance. When the stabilizer itself does not have a reactive group, a stabilizer having a molecular weight of 1000 or more is preferably used. A stabilizer having a molecular weight of 1000 or more can sufficiently exhibit the characteristics as a stabilizer in the hard coat layer.

  The addition amount of the stabilizer may be appropriately determined according to the purpose of use, but is preferably 20 parts by weight or less, preferably 5 parts by weight or less, with respect to the total amount of the composition for the hard coat layer. When the addition amount is within this range, the stabilizing effect by the stabilizer can be sufficiently exerted, and the resin in the hard coat layer can be sufficiently cured, and the hard coat layer can be hardened. The coat performance can be achieved.

  Commercially available stabilizers can be used, and specific examples thereof include RUVA93 (manufactured by Otsuka Chemical Co., Ltd.); Vanaresin UVA-1025S, VanaresinUVA-1050G, Vanaresin HAL-11025S (manufactured by Shin-Nakamura Chemical Co., Ltd.); FA711MN, FA712HM (Manufactured by Hitachi Chemical Co., Ltd.); RSA0113M (manufactured by Sannan Gosei Co., Ltd.); Adeka Stub series manufactured by Asahi Denka Co., Ltd., for example, AO22, AO30, AO40, AO50, AO60, AO70, AO80, AO330, A611, A612, A613, AO51, AO15, AO18, 328, AO37, PEP4C, PEP8, PEP8W, PEP24G, PEP36, PEP36Z, HP10, 2112, 260, 522, 1178, 1500, 135A, 3010, TPP, AO23, AO412S, AO503, L 32, LA36, 1413, LA51, LA52, LA57, LA62, LA63, LA67, LA77, LA82, LA87, LA501, LA502, LA503, LA601, LA602, etc .; TINUVIN series manufactured by Ciba Specialty Chemicals, for example TINUVIN-PS, TINUVIN99-2, TINUVIN109, TINUVIN328, TINUVIN384-2, TINUVIN400, TINUVIN411L, TINUVIN900, TINUVIN928, TINUVIN1130, TINUVIN111FDL, TINUVIN123, TINUVIN144, TINUVIN144, IRG ANOX245, IRGANOX259, IRGANOX565, IRGANOX1010, IRGANOX1076, IRGANOX1098, IRGANOX1222, IRGANOX1330, IRGANOX1425, IRGANOX3114, IRGANOX5057, IRGANOX1520, IRGANOX1135, IRGANOX1035 And mixtures of two or more thereof.

  Among these, RUVA93 (manufactured by Otsuka Chemical Co., Ltd.), Vanaresin UVA-1025S, VanaresinUVA-1050G (manufactured by Shin-Nakamura Chemical Co., Ltd.), FA711MN, FA712HM (manufactured by Hitachi Chemical Co., Ltd.), TINUVIN292, TINUVIN123 (Ciba Specialty) -Chemicals) etc. and a mixture of two or more of these.

The other agent hard coat layer may contain other agents such as an antistatic agent, an antifouling agent or an antiglare agent for the purpose of exerting desired optical properties. In this case, the hard coat layer can be formed by adding other agents to the hard coat layer composition.

Conductive agent (antistatic agent)
By adding a conductive agent (antistatic agent), dust adhesion on the surface of the optical laminate can be effectively prevented. Specific examples of the conductive agent (antistatic agent) include quaternary ammonium salts, pyridinium salts, various cationic compounds having a cationic group such as first to third amino groups, sulfonate groups, sulfate ester bases, Anionic compounds having an anionic group such as phosphate ester base and phosphonate base, amphoteric compounds such as amino acid series and amino sulfate ester series, nonionic compounds such as amino alcohol series, glycerin series and polyethylene glycol series, tin and titanium And metal chelate compounds such as acetylacetonate salts thereof, and compounds obtained by increasing the molecular weight of the compounds listed above. In addition, a monomer or oligomer having a tertiary amino group, a quaternary ammonium group, or a metal chelate portion and polymerizable by ionizing radiation, or an organometallic compound such as a coupling agent having a functional group, etc. Polymerizable compounds can also be used as antistatic agents.

Examples of the antistatic agent include conductive fine particles. Specific examples of the conductive fine particles include those made of a metal oxide. Examples of such metal oxides include ZnO (refractive index 1.90, the numerical value in parentheses below represents the refractive index), CeO ₂ (1.95), Sb ₂ O ₂ (1.71), SnO. ₂ (1.997), indium tin oxide (1.95) often referred to as ITO, In ₂ O ₃ (2.00), Al ₂ O ₃ (1.63), antimony-doped tin oxide (abbreviation) ATO, 2.0), aluminum-doped zinc oxide (abbreviation: AZO, 2.0), and the like. The fine particles refer to those having a so-called submicron size of 1 micron or less, and preferably those having an average particle size of 0.1 nm to 0.1 μm.

  Examples of the antistatic agent include conductive polymers. Specific examples thereof include aliphatic conjugated polyacetylene, aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, Examples include atomic conjugated polyaniline and mixed conjugated poly (phenylene vinylene). Besides these, double-chain conjugated system having a plurality of conjugated chains in the molecule, and the above-mentioned conjugated polymer chain Examples thereof include a conductive composite which is a polymer grafted or block co-polymerized on a saturated polymer.

  The addition amount of the antistatic agent can be appropriately determined. For example, it is 0.01 part by weight or more and 50 parts by weight or less with respect to the total amount of the hard coat layer composition, and preferably the lower limit is 0.1 part by weight. The upper limit is 25 parts by weight or less.

Anti- glare agent Anti-glare agent includes fine particles, and the shape thereof may be spherical or elliptical, and preferably spherical. The fine particles include inorganic and organic particles. The fine particles exhibit anti-glare properties and are preferably transparent. Specific examples of the fine particles include silica beads for inorganic systems, and plastic beads for organic systems, and more preferably those having transparency. Specific examples of plastic beads include styrene beads (refractive index 1.59), melamine beads (refractive index 1.57), acrylic beads (refractive index 1.49), acrylic-styrene beads (refractive index 1.54), Examples thereof include polycarbonate beads and polyethylene beads.

  When the antiglare agent is added, it is preferable to add an antisettling agent. This is because by adding an anti-settling agent, precipitation of the resin beads can be suppressed and the resin beads can be uniformly dispersed in the solvent. Specific examples of the anti-settling agent include silica beads and polyethylene beads having a particle size of 0.5 μm or less, preferably about 0.1 to 0.25 μm.

  The addition amount of the antiglare agent can be appropriately determined. For example, it is 0.001 part by weight or more and 75 parts by weight or less, preferably 0.01 part by weight based on the total amount of the composition for hard coat layer. The upper limit is 50 parts by weight or less.

Antifouling agent The antifouling agent is mainly intended to prevent the outermost surface of the optical laminate from being stained, and can further impart scratch resistance to the optical laminate. Specific examples of the antifouling agent include a fluorine-based compound, a silicon-based compound, or a mixed compound thereof. Moreover, it does not ask | require whether antifouling agent itself has a reactive group.

Specific examples of the fluorine-based compound include a general formula:
(A) w- (B) x- (D) y-CF ₃
(In the above formula,
A represents one or more groups selected from the group consisting of CF ₂ , CFCF ₂ , and C (CF ₂ ) ₂ ;
B is OCF ₂ CF ₂ , OCF ₂ CF (CF ₂ ), OCF ₂ C (CF ₂ ) ₂ ,
OCF (CF ₂ ) CF (CF ₂ ), OCF (CF ₂ ) C (CF ₂ ) ₂ ,
Represents one or more groups selected from the group consisting of OC (CF ₂ ) ₂ CF (CF ₂ ), OC (CF ₂ ) ₂ C (CF ₂ ) ₂ ;
D represents one or more groups selected from the group consisting of OCH ₂ CH ₂ , OCH ₂ CH ₂ CH ₂ , OC (O) (CH ₂ ) z;
w, x, y, and z represent numbers greater than 0 and less than or equal to 50. )
The thing represented by is mentioned.

（上記式中、
Ｒは、疎水基として、メチル基、フッ素原子、アクリル基、又はメタクリル基であり、親水基として、水酸基、カルボキシル基、ポリエーテル基、又はエポキシ基であり、或いはこれらの混合基であってよく、
Ｒ^１はアルキル基、好ましくは炭素数１〜２０のアルキル基、より好ましくは炭素数１〜１０のアルキル基であり、
Ｘは０〜１２００であり、
Ｙは０〜１２００である。）
で表されるものが挙げられる。 In the present invention, the silicon compound is preferably a compound in which the terminal or side chain of the compound is modified. Examples of such silicon compounds include the following general formulas (I) to (III) or (IV):

(In the above formula,
R may be a methyl group, a fluorine atom, an acrylic group, or a methacryl group as a hydrophobic group, and may be a hydroxyl group, a carboxyl group, a polyether group, or an epoxy group as a hydrophilic group, or a mixed group thereof. ,
R ¹ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms,
X is 0 to 1200,
Y is 0-1200. )
The thing represented by is mentioned.

  The antifouling agent is available as a commercial product, and preferably it is used. Specific examples of the antifouling agent having no reactive group include Megafac series manufactured by Dainippon Ink, Inc., for example, MCF350-5, F445, F455, F178, F470, F475, F479, F477, TF1025, F478, F178K, etc. The TSF series manufactured by Toshiba Silicone Co., Ltd .; the X22 series manufactured by Shin-Etsu Chemical Co., Ltd., the KF series, etc .; the silaplane series manufactured by Chisso Co., Ltd., and the like.

  Specific examples of the antifouling agent having a reactive group include SUA1900L10 (weight average molecular weight 4200; manufactured by Shin-Nakamura Chemical Co., Ltd.), SUA1900L6 (weight average molecular weight 2470; manufactured by Shin-Nakamura Chemical Co., Ltd.), Ebecryl 1360 (manufactured by Daicel UCB), UT3971 (Nippon Gosei Co., Ltd.), Difensa TF3001 (Dainippon Ink), Difensa TF3000 (Dainippon Ink), Difensa TF3028 (Dainippon Ink), KRM7039 (Daicel UCB), Light Procoat AFC3000 (manufactured by Kyoeisha Chemical), KNS5300 (manufactured by Shin-Etsu Silicone), UVHC1105 (manufactured by GE Toshiba Silicone), UVHC8550 (manufactured by GE Toshiba Silicone), Ebecryl350 (manufactured by Daicel UCB), ACS-1122 (Japan Payne) Company, Ltd.) and the like.

  When the antifouling agent is an organic compound, the number average molecular weight is not limited, but is 500 or more and 100,000 or less, preferably the lower limit is 750 or more, more preferably 1000 or more, and preferably the upper limit is 70,000. Or less, more preferably 50,000 or less.

  According to a preferred embodiment of the present invention, the antifouling agent comprises a polyfunctional acrylate having two or more functional groups containing a polyorganosiloxane group, a polyorganosiloxane-containing graft polymer, a polyorganosiloxane-containing block polymer, a fluorinated alkyl group, and the like. Is preferred. Examples of the polyfunctional acrylate include tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and 1,3-butane. Diol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, 1,6-hexanediol di (meth) acrylate 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, neopentyl glycol di (meth) acrylate, Lopoxylated neopentyl glycol di (meth) acrylate, pentaerythritol diacrylate monostearate, isocyanuric acid ethoxy modified di (meth) acrylate (isocyanuric acid EO modified di (meth) acrylate), bifunctional urethane acrylate, bifunctional polyester acrylate, etc. Is mentioned. Trifunctional acrylates include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, ethoxylated trimethylolpropane tri Examples include (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate, and trifunctional polyester acrylate. Examples of the tetrafunctional acrylate include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and ethoxylated pentaerythritol tetra (meth) acrylate. Examples of the pentafunctional or higher acrylate include dipentaerythritol hydroxypenta (meth) acrylate and dipentaerythritol hexaacrylate.

  The addition amount of the antifouling agent can be appropriately determined, but is 0.001 part by weight or more and 90 parts by weight or less with respect to the total weight of the composition forming the hard coat layer, and preferably the lower limit is 0.01 part by weight. Part or more, more preferably 0.1 part by weight or more, preferably the upper limit is 70 parts by weight or less, more preferably 50 parts by weight or less. It is preferable that the addition amount of the antifouling agent is within the above range since a sufficient antifouling function is exhibited and the optical laminate has hardness.

Formation of Hard Coat Layer The hard coat layer may be adjusted by mixing and dispersing the components described above. For mixing and dispersing, it is possible to appropriately disperse with a paint shaker or a bead mill. The dispersion-treated composition for each layer may then be filtered. You may form by apply | coating this composition for hard-coat layers to a forming board or a light-transmissive base material.

  Examples of the method for forming the hard coat layer composition on the light transmissive substrate include coating methods such as a roll coating method, a Miya bar coating method, and a gravure coating method. After application of the hard coat layer composition, drying and UV curing are performed. Specific examples of the ultraviolet light source include ultrahigh pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black light fluorescent lamps, and metal halide lamp lamps. As the wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm can be used. Specific examples of the electron beam source include various types of electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type.

Use of Hard Coat Layer The hard coat layer according to the present invention is used for an optical laminate (optical functional film), and is specifically used for the purpose of suppressing light reflection and used for articles. More specifically, it is used in an optical lens (film), an image display unit of an optical device, a windshield of a vehicle, or a special building material. Preferably, it is used for the image display part of an optical apparatus, for example, can be used for the image display surface in an image display apparatus [a liquid crystal display (LCD) or a cathode ray tube display apparatus (CRT) etc.].

2. Optical Laminate According to another aspect of the present invention, an optical laminate in which a hard coat layer according to the present invention is formed on a light transmissive substrate is proposed.

Light-transmitting base material The light-transmitting base material preferably has transparency, smoothness and heat resistance and is excellent in mechanical strength. Specific examples of the material forming the light-transmitting substrate include polyester, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, polyester, polyamide, polyimide, polyethersulfone, polysulfone, polypropylene, polymethylpentene, and polychlorinated. Examples thereof include thermoplastic resins such as vinyl, polyvinyl acetal, polyether ketone, polymethyl methacrylate, polycarbonate, and polyurethane, preferably polyester and cellulose triacetate, and more preferably cellulose triacetate.

  The thickness of the light transmissive substrate is 20 μm or more and 300 μm or less, preferably the upper limit is 200 μm or less, and the lower limit is 30 μm or more. When the light-transmitting substrate is a plate-like body, the thickness may exceed these thicknesses. In addition, when forming an optical property layer on the optically transparent substrate, in order to improve adhesion, in addition to physical treatment such as corona discharge treatment and oxidation treatment, a paint called an anchor agent or primer is used. Application may be performed in advance.

Arbitrary Layers The optical layered body according to the present invention may form other layers for the purpose of exhibiting desired optical properties. According to a preferred embodiment of the present invention, it is preferable to further comprise a low refractive index layer on the hard coat layer. Moreover, according to another preferable aspect, the thing further equipped with the antistatic layer, the glare-proof layer, or the antifouling layer between the layers which comprise an optical laminated body, or the outermost surface of an optical laminated body is preferable. It is preferable to further include an antistatic layer under the hard coat layer.

Low Refractive Index Layer The low refractive index layer may be formed of a low refractive index agent and a resin.
Low Refractive Index Agent The low refractive index agent has a refractive index of less than 1.5, preferably 1.45 or less.

  Specific examples of the low refractive index agent include a silicone-containing vinylidene fluoride copolymer, and examples thereof include a monomer composition containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene. Examples thereof include a composition comprising 100 parts by weight of a fluorine-containing copolymer having a fluorine content ratio of 60 to 70% by weight and 80 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group.

  Examples of the fluorine-containing copolymer include a copolymer obtained by copolymerizing a monomer composition containing vinylidene fluoride and hexafluoropropylene. The proportion of each component in the monomer composition is 30 to 90% by weight of vinylidene fluoride, preferably 40 to 80% by weight, particularly preferably 40 to 70% by weight, or 5 to 50% by weight of hexafluoropropylene. , Preferably 10 to 50% by weight, particularly preferably 15 to 45% by weight. This monomer composition may further contain 0 to 40% by weight, preferably 0 to 35% by weight, particularly preferably 10 to 30% by weight of tetrafluoroethylene.

  The monomer composition for obtaining this fluorine-containing copolymer contains other copolymer components in an amount of, for example, 20% by weight or less, preferably 10% by weight or less as required. May be. Specific examples of this copolymer include fluoroethylene, trifluoroethylene, chlorotrifluoroethylene, 1, 2-dichloro-1, 2-difluoroethylene, 2-bromo-3, 3, 3-trifluoroethylene, 3- Polymerization having fluorine atoms such as bromo-3, 3-difluoropropylene, 3, 3, 3-trifluoropropylene, 1, 1, 2-trichloro-3, 3, 3-trifluoropropylene, α-trifluoromethacrylic acid, etc. Mention may be made of monomers.

  The fluorine content of the fluorine-containing copolymer obtained from such a monomer composition is preferably 60 to 70% by weight, more preferably 62 to 70% by weight, and particularly preferably 64 to 68% by weight. When the addition ratio is in such a range, it has good solubility in the solvent. Alternatively, by including a fluorine-containing copolymer as a component, it is possible to form an optical laminate having excellent adhesion, high transparency, low refractive index, and excellent mechanical strength. It becomes.

  The molecular weight of the fluorine-containing copolymer is preferably 5,000 to 200,000, particularly 10,000 to 100,000, in terms of polystyrene-equivalent number average molecular weight. By using a fluorine-containing copolymer having such a molecular weight, the viscosity of the resulting fluorine-based resin composition becomes a suitable size, and therefore surely has a suitable coating property. It can be.

  The refractive index of the fluorine-containing copolymer itself is 1.45 or less, preferably 1.42 or less, more preferably 1.40 or less. When the refractive index is in this range, the antireflection effect of the formed optical laminate is preferable.

  The amount of the resin added is 30 to 150 parts by weight, preferably 35 to 100 parts by weight, particularly preferably 40 to 70 parts by weight, based on 100 parts by weight of the fluorine-containing copolymer. Moreover, it is preferable that the fluorine content rate in the total amount of the polymer formation component containing a fluorine-containing copolymer and resin is 30 to 55 weight%, Preferably it is 35 to 50 weight%.

  When the addition amount or the fluorine content is in the above-described range, the adhesion of the surface adjustment layer to the base material becomes good, and a high antireflective effect with a high refractive index can be obtained.

  According to a preferred embodiment of the present invention, it is preferable to use “fine particles having voids” as the low refractive index agent. The “fine particles having voids” can reduce the refractive index while maintaining the layer strength of the surface adjustment layer. In the present invention, the term “fine particles having voids” refers to a structure in which a gas is filled with gas and / or a porous structure containing gas, and the gas in the fine particle is compared with the original refractive index of the fine particle. It means fine particles whose refractive index decreases in inverse proportion to the occupation ratio. The present invention also includes fine particles capable of forming a nanoporous structure inside and / or at least part of the surface depending on the form, structure, aggregation state, and dispersion state of the fine particles inside the coating film. It is.

  As specific examples of the inorganic fine particles having voids, silica fine particles prepared by using the technique disclosed in Japanese Patent Application Laid-Open No. 2001-233611 are preferably exemplified. Since silica fine particles having voids are easy to manufacture and have high hardness, when a low refractive index layer is formed by mixing with a binder, the layer strength is improved and the refractive index is 1.20-1. It is possible to prepare within the range of about 45. In particular, as specific examples of the organic fine particles having voids, hollow polymer fine particles prepared by using the technique disclosed in JP-A-2002-80503 are preferably exemplified.

  The fine particles capable of forming a nanoporous structure inside and / or at least part of the surface of the coating film are manufactured for the purpose of increasing the specific surface area in addition to the silica fine particles, and the packing column and the surface porosity Examples include controlled release materials that adsorb various chemical substances in the mass part, porous fine particles used for catalyst fixation, or dispersions and aggregates of hollow fine particles intended to be incorporated into heat insulating materials and low dielectric materials. it can. As such a specific example, an aggregate of porous silica fine particles and a silica fine particle manufactured by Nissan Chemical Industries, Ltd. were linked in a chain form from the product names Nippon and Nippon manufactured by Nippon Silica Kogyo Co., Ltd. as commercial products. From the colloidal silica UP series (trade name) having a structure, those within the range of the preferable particle diameter of the present invention can be used.

  The average particle diameter of the “fine particles having voids” is 5 nm or more and 300 nm or less, preferably the lower limit is 8 nm or more and the upper limit is 100 nm or less, more preferably the lower limit is 10 nm or more and the upper limit is 80 nm or less. When the average particle diameter of the fine particles is within this range, excellent transparency can be imparted to the low refractive index layer.

The resin resin is preferably transparent, and specific examples thereof include an ionizing radiation curable resin that is a resin curable by ultraviolet rays or an electron beam, a mixture of an ionizing radiation curable resin and a solvent-drying resin, or a heat There are three types of curable resins, preferably ionizing radiation curable resins.

  Specific examples of the ionizing radiation curable resin include those having an acrylate functional group, for example, a polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene having a relatively low molecular weight. Resins, polythiol polyene resins, oligomers or prepolymers such as (meth) allylates of polyfunctional compounds such as polyhydric alcohols, and reactive diluents, and specific examples thereof include ethyl (meth) acrylate, ethylhexyl (meta ) Monofunctional monomers such as acrylate, styrene, methylstyrene, N-vinylpyrrolidone and polyfunctional monomers such as polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) Acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. .

  When using an ionizing radiation curable resin as an ultraviolet curable resin, it is preferable to use a photopolymerization initiator. Specific examples of the photopolymerization initiator include acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime esters, and thioxanthones. Further, it is preferable to use a mixture of photosensitizers, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine and the like. Moreover, when using ionizing radiation curable resin as an ultraviolet curable resin, a photoinitiator or a photoinitiator can be added. As the photopolymerization initiator, in the case of a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether and the like are used alone or in combination. In the case of a resin system having a cationic polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metatheron compound, a benzoin sulfonic acid ester or the like is used alone or as a mixture as a photopolymerization initiator. . The addition amount of a photoinitiator is 0.1-10 weight part with respect to 100 weight part of ionizing radiation-curable compositions.

  The solvent-drying resin used by mixing with the ionizing radiation curable resin mainly includes a thermoplastic resin. As the thermoplastic resin, those generally exemplified are used. By adding the solvent-drying resin, coating film defects on the coated surface can be effectively prevented. According to a preferred embodiment of the present invention, when the material of the light-transmitting substrate is a cellulose resin such as TAC, preferred specific examples of the thermoplastic resin include cellulose resins such as nitrocellulose, acetylcellulose, and cellulose acetate propio. Nate, ethyl hydroxyethyl cellulose and the like.

  Specific examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin. And polysiloxane resin. When a thermosetting resin is used, a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like can be further added as necessary.

When forming the polymerization initiator low refractive index layer, a photopolymerization initiator can be used, and specific examples thereof include 1-hydroxy-cyclohexyl-phenyl-ketone. This compound is commercially available, and examples thereof include trade names Irgacure 184, Irgacure 907, Irgacure 369, Irgacure 819, DAROCUR TPO (manufactured by Ciba Specialty Chemicals).

In order to form the solvent low refractive index layer, a composition in which a solvent is mixed with the above components can be used. Specific examples of the solvent include alcohols such as isopropyl alcohol, methanol and ethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; toluene, xylene and the like Aromatic hydrocarbons; or a mixture thereof, preferably ketones and esters. Moreover, you may use the permeable solvent demonstrated by the hard-coat layer.

Antistatic layer The antistatic layer may be formed of an antistatic agent and a resin. The antistatic agent may be the same as that described for the hard coat layer, and the resin may be the same as that described for the low refractive index layer. The antistatic layer comprises an antistatic agent, a resin and a solvent. The thickness of the antistatic layer is preferably about 30 nm to 1 μm. In forming the antistatic layer, it is preferable that the surface resistance value of the antistatic layer is 5 × 10 ⁷ Ω / □ or less.

Antiglare layer The antiglare layer may be formed of an antiglare agent and a resin. The antiglare agent may be the same as described in the previous hard coat layer, and the resin and solvent may be the same as described in the previous low refractive index layer.
Method for producing optical laminate
The adjustment hard coat layer of the composition for each layer may be the same as described above. The composition of other optional layers may be adjusted by mixing and dispersing the components described above according to general preparation methods. For mixing and dispersing, it is possible to appropriately disperse with a paint shaker or a bead mill. The dispersion-treated composition for each layer may then be filtered.

Specific examples of methods for forming each layer include spin coating, dipping, spraying, die coating, bar coating, roll coater, meniscus coater, flexographic printing, screen printing, and speed coater. Various methods such as these can be used. As a curing method of the curable resin composition, it is cured by irradiation with an electron beam or ultraviolet rays. In the case of electron beam curing, an electron beam having energy of 100 KeV to 300 KeV is used. In the case of ultraviolet curing, ultraviolet rays or the like emitted from light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp are used.

Applications of the optical laminate The optical laminate according to the present invention has the following uses.
According to another aspect of the polarizing plate present invention, it is possible to provide a polarizing element, a polarizing plate formed and an optical laminate according to the present invention. Specifically, a polarizing plate is provided on the surface of a polarizing element, the optical layered body according to the present invention being provided on a surface opposite to the surface where an optical functional layer such as a hard coat layer is present in the optical layered body. Can do.

  As the polarizing element, for example, a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer saponified film, which is dyed with iodine or a dye and stretched can be used. In the laminating process, it is preferable to saponify the light-transmitting substrate (preferably a triacetyl cellulose film) in order to increase adhesion or prevent electricity.

According to yet another aspect of the image display device the present invention, it is possible to provide an image display device, the image display device includes a transmissive display body, a light source device for irradiating the transparent display member from the back The optical laminated body according to the present invention or the polarizing plate according to the present invention is formed on the surface of the transmissive display body. The image display device according to the present invention may basically be composed of a light source device (backlight), a display element, and an optical laminate according to the present invention. The image display device is used for a transmissive display device, and is particularly used for display display of a television, a computer, a word processor, or the like. In particular, it is used on the surface of high-definition image displays such as CRTs and liquid crystal panels.

  When the image display device according to the present invention is a liquid crystal display device, the light source of the light source device is irradiated from the lower side of the optical laminate according to the present invention. Note that in the STN liquid crystal display device, a retardation plate may be inserted between the liquid crystal display element and the polarizing plate. An adhesive layer may be provided between the layers of the liquid crystal display device as necessary.

Mode of implementation

EXAMPLES The contents of the present invention will be described in detail by the following examples, but the contents of the present invention are not construed as being limited by the examples.

Preparation of composition for hard coat layer The components in the following composition table were sufficiently mixed in a mixer and then filtered to prepare a composition for hard coat layer.
Composition 1
Bis [(2-methacryloylthio) ethyl] sulfide 5 parts by weight (manufactured by Sumitomo Seika Co., Ltd .; S2EG)
Urethane acrylate (UV1700B, Nippon Gosei Co., Ltd., 10 functional) 5 parts by weight Polymerization initiator: IRGACURE 184 0.4 part by weight Polymerization initiator: DAROCUR TPO 0.4 part by weight Methyl ethyl ketone (hereinafter referred to as “MEK”) 10 parts by weight

Composition 2
Bis [(2-methacryloylthio) ethyl] sulfide 5 parts by weight (manufactured by Sumitomo Seika Co., Ltd .; S2EG)
Urethane acrylate (UV1700B, Nippon Gosei Co., Ltd., 10 functional) 5 parts by weight Polymerization initiator: IRGACURE 184 0.4 part by weight Polymerization initiator: IRGACURE 819 0.4 part by weight MEK 10 parts by weight

Composition 3
Bis [(2-methacryloylthio) ethyl] sulfide 5 parts by weight (manufactured by Sumitomo Seika Co., Ltd .; S2EG)
Urethane acrylate (UV1700B, Nippon Gosei Co., Ltd., 10 functional) 5 parts by weight Polymerization initiator: IRGACURE 651 0.4 part by weight Polymerization initiator: DAROCUR TPO 0.4 part by weight MEK 10 parts by weight

Composition 4
Bis [(2-methacryloylthio) ethyl] sulfide 5 parts by weight (manufactured by Sumitomo Seika Co., Ltd .; S2EG)
Dipentaerythritol hexaacrylate (DPHA, hexafunctional) 5 parts by weight Polymerization initiator: IRGACURE 184 0.4 part by weight Polymerization initiator: DAROCUR TPO 0.4 part by weight MEK 10 parts by weight

Composition 5
9 parts by weight of bis [(2-methacryloylthio) ethyl] sulfide (manufactured by Sumitomo Seika Co., Ltd .; S2EG)
Urethane acrylate (UV1700B, Nippon Gosei Co., Ltd., 10 functional) 1 part by weight Polymerization initiator: IRGACURE 184 0.08 part by weight Polymerization initiator: DAROCUR TPO 0.72 part by weight MEK 10 parts by weight

Composition 6
Bis [(2-methacryloylthio) ethyl] sulfide 1 part by weight (manufactured by Sumitomo Seika Co., Ltd .; S2EG)
Urethane acrylate (UV1700B, Nippon Gosei Co., Ltd., 10 functional) 9 parts by weight Polymerization initiator: IRGACURE 184 0.72 parts by weight Polymerization initiator: DAROCUR TPO 0.08 parts by weight MEK 10 parts by weight

Composition 7
Bis [(2-methacryloylthio) ethyl] sulfide 5 parts by weight (manufactured by Sumitomo Seika Co., Ltd .; S2EG)
Urethane acrylate (UV1700B, Nippon Gosei Co., Ltd., 10 functional) 5 parts by weight Polymerization initiator: IRGACURE 184 0.4 part by weight Polymerization initiator: DAROCUR TPO 0.4 part by weight Stabilizer: RUVA93 (manufactured by Otsuka Chemical Co., Ltd.) 0. 4 parts by weight MEK 10 parts by weight

Composition 8
9.8 parts by weight of bis [(2-methacryloylthio) ethyl] sulfide (Sumitomo Seika Co., Ltd .; S2EG)
Urethane acrylate (UV1700B, Nippon Gosei Co., Ltd., 10 functional) 0.2 parts by weight Polymerization initiator: IRGACURE 184 0.8 part by weight MEK 10 parts by weight

Composition 9
Bis [(2-methacryloylthio) ethyl] sulfide 0.2 parts by weight (Sumitomo Seika Co., Ltd .; S2EG)
Urethane acrylate (UV1700B, Nippon Gosei Co., Ltd., 10 functional) 9.8 parts by weight Polymerization initiator: DAROCURE TPO 0.8 part by weight MEK 10 parts by weight

Composition 10
Bis [(2-methacryloylthio) ethyl] sulfide 5 parts by weight (manufactured by Sumitomo Seika Co., Ltd .; S2EG)
1,6-hexadiol-diacrylate (HDDA: bifunctional) 5 parts by weight Polymerization initiator: IRGACURE 184 0.8 part by weight Polymerization initiator: DAROCUR TPO 0.8 part by weight MEK 10 parts by weight

Composition 11
Urethane acrylate (UV1700B, Nippon Gosei Co., Ltd., 10 functional) 10 parts by weight Polymerization initiator: IRGACURE 184 0.8 part by weight Polymerization initiator: DAROCUR TPO 0.8 part by weight MEK 10 parts by weight

Preparation of composition for low refractive index layer The components in the composition table below were sufficiently mixed in a mixer and then filtered to prepare a composition for a hard coat layer.
Composition- treated void silica sol fine particles ^* ) 14.3 parts by weight Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 parts by weight Modified silicone oil X22-176F 0.15 parts by weight (Shin-Etsu Chemical Co., Ltd.)
Methyl isobutyl ketone 83.5 parts by weight *) A voided silica sol was treated using a 20% methyl isobutyl ketone solution.

Preparation of optical laminate
Example 1
Formation of Hard Coat Layer The composition for hard coat layer of Composition 1 was applied on one side of a cellulose triacetate film (thickness 80 μm) at a wet weight of 20 g / m ² (dry weight 10 g / m ² ). It dried for 30 seconds at 50 degreeC, and irradiated the ultraviolet-ray 100mJ / cm < ² > (high refractive index), and formed the hard-coat layer.
Formation of low refractive index layer The composition of the low refractive layer is irradiated on the surface of the hard coat layer with an ultraviolet irradiation device (Fusion UV System Japan, Inc., light source H bulb) at an irradiation dose of 192 mJ / m ^2. The film thickness after drying (40 ° C. × 1 minute) is 0.1 μm, and the film thickness is formed so that the minimum value of the reflectance is around 550 nm to form a low refractive index layer. Thus, an optical laminate was obtained.

Examples 2-7
In the formation of the hard coat layer, optical laminates of Examples 2 to 9 were obtained in the same manner as in Example 1 except that the composition for hard coat layer was changed to compositions 2 to 6.

Examples 1-4
In the formation of the hard coat layer, optical laminates of Examples 1 to 4 were obtained in the same manner as in Example 1 except that the composition for hard coat layer was changed to compositions 8 to 11.

The evaluation test examples and the optical laminates of the examples were evaluated based on the following evaluation criteria, and the results are shown in Table 1 below.
Evaluation 1: Scratch resistance evaluation test The surface of the hard coat layer of the optical laminate was subjected to 10 reciprocating rubs using # 0000 steel wool with a predetermined friction load of 300 g / cm ² , and then the coating film was peeled off. The presence or absence was visually observed and evaluated according to the following evaluation criteria.
Evaluation Criteria Evaluation A: There was no peeling of the coating film.
Evaluation x: There was peeling of the coating film.

Evaluation 2: Measurement of reflectance Paste black tape to prevent back reflection, and from the surface of the hard coat layer, using a spectral reflectance measuring machine PC-3100 manufactured by Shimadzu Corporation, the minimum reflectance in the wavelength range of 380 to 780 nm Was measured.
Evaluation Criteria Evaluation A: The target low-reflection optical film was obtained. Evaluation ×: The target low-reflection optical film was not achieved.

Evaluation 3: Transparency evaluation The coated surface of the optical laminate was visually observed and evaluated according to the following evaluation criteria.
Evaluation standard evaluation A: Transparency was good.
Evaluation x: Transparency was poor.

Table 1
Example / Evaluation Evaluation 1 Evaluation 2 Evaluation 3
Example 1 ◎ ◎ ◎
Example 2 ◎ ◎ ◎
Example 3 ◎ ◎ ◎
Example 4 ◎ ◎ ◎
Example 5 ◎ ◎ ◎
Example 6 ◎ ◎ ◎
Example 7 ◎ ◎ ◎
Example 1 × ◎ ×
Example 2 ◎ × ◎
Example 3 × ◎ ◎
Example 4 ◎ × ◎

Claims (12)

A hard coat layer used in an optical laminate,
A monomer comprising at least two or more sulfur atoms;
A trifunctional or higher functional urethane acrylate resin and / or a trifunctional or higher functional acrylate resin,
The monomer and the resin are cured by a first polymerization initiator and a second polymerization initiator,
The first polymerization initiator has an extinction coefficient at 360 nm or more of 100 ml / g · cm or less;
The hard coat layer, wherein the second polymerization initiator has an extinction coefficient at 360 nm or more exceeding 100 ml / g · cm. The monomer comprising at least two or more sulfur atoms has the following formula:

The hard-coat layer of Claim 1 represented by these.   The hard coat layer according to claim 1, further comprising a stabilizer.   The mixing ratio of the monomer comprising at least two or more sulfur atoms and the tri- or more functional urethane acrylate resin and / or the tri- or more functional acrylate resin is 1: 9 or more and 9: 1 or less. Hard coat layer in any one of 1-3.   The hard coat layer according to claim 1, further comprising a permeable solvent.   The hard coat layer according to any one of claims 1 to 5, further comprising an antistatic agent, an antifouling agent or an antiglare agent. An optical laminate comprising a hard coat layer on a light transmissive substrate,
The optical laminated body whose said hard-coat layer is what was described in any one of Claims 1-6.   The optical laminate according to claim 7, further comprising a low refractive index layer on the hard coat layer.   The optical laminate according to claim 7 or 8, further comprising an antistatic layer or an antifouling layer provided between the layers constituting the optical laminate or on the outermost surface of the optical laminate.   The optical laminate according to any one of claims 8 to 9, which is used as an antireflection laminate. A polarizing plate comprising a polarizing element,
A polarizing plate comprising, on the surface of the polarizing element, the optical laminate according to any one of claims 7 to 10 on a surface opposite to a surface on which the hard coat layer is present. An image display device comprising a transmissive display and a light source device that irradiates the transmissive display from the back,
The image display apparatus which comprises the optical laminated body as described in any one of Claims 7-10, or the polarizing plate as described in Claim 11 on the surface of the said transparent display body.