JP2007264281A - Hard coat layer provided with antifouling property - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hard coat layer provided with both of antifouling property and a lubricating property. <P>SOLUTION: The hard coat layer used for an optical laminate comprises a silicon type compound, a fluorine type compound or a mixture of them as an antifouling agent and/or a lubricant, wherein, according to XPS analysis of the uppermost surface of the hard coat layer, the abundance ratio of silicon atom is at least 10% and/or the abundance ratio of fluorine atom is at least 20%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hard coat layer and an optical laminate comprising at least the hard coat layer.

  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 reflection due to light rays emitted from an external light source and to improve its visibility. On the other hand, by using an optical laminate (for example, an antireflection laminate) in which an antireflection layer is formed on a light transmissive substrate, reflection on the image display surface of the image display device is reduced and visibility is improved. It is generally made to improve.

  Conventionally, it has been pointed out that the outermost surface of an optical layered body is exposed to various use environments, is easily scratched, and easily adheres to dirt. On the other hand, Japanese Patent Application Laid-Open No. 10-104403 (Patent Document 1) proposes an optical laminate in which a hard coat layer is added with a stain proofing agent in order to improve the scratch resistance and contamination prevention of the image display surface. Has been.

  However, as a result of confirmation by the present inventors, an optical laminate having both antifouling properties and slipperiness in a hard coat layer formed on a light-transmitting substrate has not been proposed yet.

Japanese Patent Laid-Open No. 10-104403

  At the time of the present invention, the present inventors include a silicon compound, fluorine, or the like as an antifouling agent and / or slipperiness-imparting agent. The knowledge that a hard coat layer having both antifouling property and slipperiness can be formed by the silicon atom or fluorine atom contained in the system compound or the mixture thereof having a specific abundance ratio. Accordingly, an object of the present invention is to provide an optical laminated body in which antifouling properties and slip properties are imparted to a hard cord layer.

Therefore, the present invention is a hard coat layer used for an optical laminate,
As an antifouling agent and / or slipperiness imparting agent, comprising a silicon compound, a fluorine compound or a mixture thereof,
When the outermost surface of the hard coat layer is analyzed by XPS, the abundance of silicon atoms is 10% or more and / or the abundance of fluorine atoms is 20% or more.

1. The hard coat layer “hard coat layer” refers to a layer having a hardness of “H” or higher in a pencil hardness test defined by JIS 5600-5-4 (1999). The thickness of the hard coat layer (during curing) is in the range of 0.1 to 100 μm, preferably 0.8 to 20 μm. The hard coat layer is formed of a resin and an optional component.

XPS analysis When the outermost surface of this layer is analyzed by XPS, the hard coat layer according to the present invention has silicon atoms and fluorine atoms present in specific numerical values. XPS analysis is to measure a sample (hard coat layer or optical laminate) by angle, and specifically, it is performed by easily converting an angle profile to a depth profile by the “maximum entropy method”. Is. XPS is a method for analyzing elements present on the surface of a sample and the composition thereof by X-ray photoelectron spectroscopy. An example of the XPS measurement conditions is the use of Thermo Electron (VG Theta Probe) XPS (X-ray photoelectron spectroscopy) device, the X-ray source is Monochromated Al Kα, the X-ray output is 100 W, and the measurement area is 400 μmφ, the lens can be formed by Angle Resolved, and the measurement angle can be arbitrarily changed. In this invention, it carries out on the conditions of five steps (28 degrees, 38 degrees, 48 degrees, 58 degrees, 68 degrees).

  In the present invention, the XPS analysis can be performed using an XPS analyzer, and the analysis condition in that case is that the XPS analysis angle is arbitrarily changed with respect to the hard coat layer. Can do. In this invention, it carries out on the conditions of five steps (28 degrees, 38 degrees, 48 degrees, 58 degrees, 68 degrees). X-ray source is Monochromated Al Kα, X-ray output is 100 W, measurement area is 400 μmφ, lens is Angle Resolved, measurement angle is 6 steps (28 °, 38 °, 48 °, 58 °, 68 °) Can do.

  In the present invention, when the outermost surface of the hard coat layer is analyzed by XPS, the abundance of silicon atoms is 10% or more, preferably 20% or more, and the abundance of fluorine atoms is 20% or more, preferably It exists in 30% or more.

  Further, in the present invention, when the outermost surface of the hard coat layer is wiped with a cloth and then the outermost surface of the hard coat layer is analyzed by XPS, the abundance of silicon atoms is 5% or more, preferably 15% or more. In other words, the presence of fluorine atoms is 15% or more, preferably 25% or more.

  The method for wiping the outermost surface of the hard cord layer with a cloth is not particularly limited. The fabric may be any material as long as it can wipe off dirt, and may be, for example, a woven fabric, a knitted fabric, or a nonwoven fabric. The material of the fabric may also be natural fiber, synthetic fiber, semi-synthetic fiber or a mixed fiber thereof. In the present invention, the number of times of wiping with the fabric may be about 10 reciprocations.

  In the present invention, the action of wiping with a cloth may be so-called dry wiping, and may be wiped with a cloth containing water, a lower alcohol (preferably ethanol) and a mixture thereof as necessary. Moreover, in this invention, you may use the organic solvent and detergent (aqueous type | system | group, non-aqueous type | system | group) which can remove a dirt in addition to a lower alcohol within the scope of the present invention.

According to a preferred embodiment of the present invention, the surface of the hard coat layer of the optical laminate is reciprocated 10 times while applying a load of 200 g / cm ² to a bem cotton in which 0.1 g of ethanol is preliminarily soaked. For example, 10 reciprocating dry wiping may be mentioned while applying a load of 200 g / cm ² to cotton.

According to a preferred embodiment of the present invention, the hard coat layer is
The total abundance of fluorine atoms obtained by XPS analysis of the entire hard coat layer is X _F %,
After wiping the outermost surface of the hard cord layer with a cloth, when the fluorine atom abundance obtained by XPS analysis of the outermost surface of the hard coat layer is Y _F %, the following formula (A):
Y _F / X _F ≧ 10 (preferably 15) (A)
And / or
The total abundance of silicon atoms obtained by XPS analysis of the entire hard coat layer is X _S %,
When the outermost surface of the hard cord layer is wiped with a cloth, and the abundance of silicon atoms obtained by XPS analysis of the outermost surface of the hard coat layer is Y _S %, the following formula (B):
Y _S / X _S ≧ 10 (preferably 15) (B)
Those satisfying these conditions are preferred.

According to a more preferred embodiment of the present invention, the hard coat layer is
The total abundance of fluorine atoms obtained by XPS analysis of the entire hard coat layer is X _F %,
Fluorine atoms obtained by XPS analysis of the outermost surface of the hard coat layer after wiping the outermost surface of the hard cord layer with a 0.1 g / cm ² cloth containing an alcohol-containing liquid by 10 reciprocations. When the abundance ratio is Y _F %, the following formula (A):
Y / X ≧ 10 (preferably 15) (A)
And / or
The total abundance of silicon atoms obtained by XPS analysis of the entire hard coat layer is X _S %,
After wiping off the outermost surface of the hard cord layer by 10 reciprocations with a 0.1 g / cm ² cloth containing an aqueous alcohol solution, the outermost surface of the hard coat layer was obtained by XPS analysis. When the abundance ratio is Y _S %, the following formula (B):
Y _S / X _S ≧ 10 (preferably 15) (B)
Those satisfying these conditions are preferred.

2) Antifouling agent and / or slipperiness-imparting agent Examples of the antifouling agent and / or slipperiness-imparting agent include silicon compounds, fluorine compounds, and mixed compounds thereof. The antifouling agent and the slipperiness imparting agent are 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.

（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.

Specific examples of the fluorine compound include the following 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.

  The antifouling agent and / or slipperiness imparting agent is available as a commercial product, and preferably used. Specific examples of the antifouling agent and / or slipperiness imparting agent not having a reactive group include Megafac series manufactured by Dainippon Ink, for example, MCF350-5, F445, F455, F178, F470, F475, F479, F477. , TF1025, F478, F178K, etc .; TSF series manufactured by Toshiba Silicone Co., Ltd .; X22 series, KF series manufactured by Shin-Etsu Chemical Co., Ltd., etc .;

  Specific examples of the antifouling agent and / or slipperiness imparting 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 ( Daicel UCB), UT3971 (Nippon Gosei Co., Ltd.), Daifensa TF3001 (Dainippon Ink), Difensa TF3000 (Dainippon Ink), Daifensa 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), Ebecryl 350 (manufactured by Daicel UCB), AC -1122 (manufactured by Nippon Paint Co., Ltd.) and the like.

  When the antifouling agent and / or slipperiness imparting agent is an organic compound, its 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. The upper limit is preferably 70,000 or less, more preferably 50,000 or less.

  According to a preferred embodiment of the present invention, the antifouling agent and / or slipperiness imparting agent is a bifunctional compound containing a polyorganosiloxane group, a polyorganosiloxane-containing graft polymer, a polyorganosiloxane-containing block polymer, a fluorinated alkyl group, and the like. What comprises the above polyfunctional acrylate is preferable. 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 and / or slipperiness imparting agent can be determined as appropriate, but is 0.001 part by weight or more and 90 parts by weight or less, preferably with respect to the total weight of the composition forming the hard coat layer. Has a lower limit of 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably an upper limit of 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 and / or slipperiness imparting agent is within the above range since a sufficient antifouling function is exhibited and the optical laminate has hardness.

3) 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 three types of thermosetting resin are mentioned, Preferably ionizing radiation-curable resin is mentioned.

  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. Examples thereof include oligomers or prepolymers such as resins, polythiol polyene resins, (meth) allylates of polyfunctional compounds such as polyhydric alcohols, and reactive diluents.

  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 ester, tetramethylchuram monosulfide, 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.

  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 transparent substrate is a cellulose resin such as TAC, as a preferred specific example of the thermoplastic resin, a cellulose resin such as nitrocellulose, acetylcellulose, cellulose acetate propionate, Examples thereof include ethyl hydroxyethyl cellulose.

  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, melanin-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.

4) Solvent In the present invention, a composition obtained by mixing a solvent 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.

  In the present invention, a permeable solvent can be used. As the permeable solvent, a solvent that is permeable to the light-transmitting substrate is used. In the present invention, the “permeability” of the osmotic solvent is intended to include all concepts such as osmosis, swelling, and wettability with respect to the light-transmitting substrate. 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.

5) Arbitrary component Although the hard-coat layer by this invention is formed by the above-mentioned component, in order to improve the optical characteristic function of a hard-coat layer, you may add an arbitrary component.
Initiator In the present invention, an initiator may be used when forming the hard coat layer. Any initiator can be used, but preferably, a polymerization initiator having an absorption coefficient of 100 (ml / gcm) or less at a long wavelength of 365 nm or more and an extinction coefficient of 100 (ml / gcm) at a long wavelength of 365 nm or more. It is preferred to use both consisting of a polymerization initiator greater than g cm). Specific examples of the polymerization initiator having an extinction coefficient of 100 (ml / g · cm) or less at a long wavelength of 365 nm or more include Irgacure 184, Irgacure 250, Irgacure 651, IRGACURE 754, Irgacure 907, Irgacure 2959, Darocure 1173D Ciba Chemical Co., Ltd.). Specific examples of polymerization initiators having an extinction coefficient of 100 (ml / g cm) at a long wavelength of 365 nm or more include commercially available products such as Irgacure OXE01, IRGACURE 369, Irgacure 784, Irgacure 819, Irgacure 907, Irgacure urDc CGI242 (manufactured by Ciba Chemical Co., Ltd.) and the like.

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 Co., Ltd.) and a mixture of two or more of these.

6) Other agents The 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. The content of the antifouling agent may be the same as described above.

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.
Hard coat layer The hard coat layer may be the same as described above.
Formation of Hard Coat Layer The hard coat layer may be formed by applying the hard coat layer composition to a light transmissive substrate. According to a preferred embodiment of the present invention, it is preferred to add a leveling agent such as fluorine or silicone to the hard coat layer composition. The composition for a hard coat layer to which a leveling agent has been added can effectively prevent inhibition of curing by oxygen on the surface of the coating film during application or drying, and can impart an effect of scratch resistance.

  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.

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.

1) 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 lower refractive index than the antiglare layer. According to a preferred embodiment of the present invention, the refractive index of the antiglare layer is 1.5 or more, and the refractive index of the low refractive index agent is less than 1.5, preferably 1.45 or less. Is preferred.

  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.

2) 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.

3) 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, slide coating, bar coating, roll coater, meniscus coater, flexographic printing, screen printing, and speed coater. Various methods such as a method 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

  The contents of the present invention will be described in detail by the following examples, but the scope of the present invention should not be construed as being limited to these examples.

Preparation of composition for hard coat layer The components of the following composition table (composition 1 to composition 18) were sufficiently mixed in a mixer, and then filtered through a polypropylene filter having a pore size of 30 μm to prepare a composition for hard coat layer.

Composition 1
Urethane acrylate (UV1700B; manufactured by Nippon Gosei Co., Ltd.) 9.0 parts by weight Fluorine antifouling agent (Defensa TF3001; manufactured by Dainippon Ink & Co.) 1.0 part by weight Polymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 0.4 Parts by weight methyl ethyl ketone 10 parts by weight

Composition 2
Urethane acrylate (UV1700B; manufactured by Nippon Gosei Co., Ltd.) 9.5 parts by weight Fluorine antifouling agent (Defensa TF3001; manufactured by Dainippon Ink Co., Ltd.) 0.5 parts by weight Polymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 0.4 Parts by weight methyl ethyl ketone 10 parts by weight

Composition 3
Urethane acrylate (UV1700B; manufactured by Nihon Gosei) 9.0 parts by weight Silicone antifouling agent (UT3971; manufactured by Nihon Gosei) 1.0 part by weight Polymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 0.4 part by weight Methyl ethyl ketone 10 parts by weight

Composition 4
Urethane acrylate (UV1700B; made by Nihon Gosei) 9.5 parts by weight Silicone antifouling agent (UT3971; made by Nihon Gosei) 0.5 parts by weight Polymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 0.4 parts by weight Methyl ethyl ketone 10 parts by weight

Composition 5
Urethane acrylate (UV1700B; manufactured by Nippon Gosei Co., Ltd.) 9.0 parts by weight Fluorine antifouling agent (Defensa TF3028; manufactured by Dainippon Ink) 1.0 part by weight Polymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 0.4 weight Methyl ethyl ketone 10 parts by weight

Composition 6
Urethane acrylate (UV1700B; manufactured by Nippon Gosei Co., Ltd.) 9.5 parts by weight Fluorine antifouling agent (Defensa TF3004; manufactured by Dainippon Ink) 0.5 part by weight Polymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 0.4 weight Methyl ethyl ketone 10 parts by weight

Composition 7
Urethane acrylate (UV1700B; manufactured by Nihon Gosei) 9.5 parts by weight Silicone antifouling agent (SUA1900L6; manufactured by Shin-Nakamura Chemical) 0.5 parts by weight Polymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 0.4 parts by weight 10 parts by weight of methyl ethyl ketone

Composition 8
Urethane acrylate (UV1700B; manufactured by Nihon Gosei) 9.5 parts by weight Silicone antifouling agent (Ebecryl 350; manufactured by Daicel UCB) 0.5 parts by weight Polymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 0.4 parts by weight Methyl ethyl ketone 10 parts by weight

Composition 9
Urethane acrylate (UV1700B; manufactured by Nihon Gosei) 9.5 parts by weight Fluorine antifouling agent (Megafac MCF350; manufactured by Dainippon Ink) 0.5 parts by weight Polymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 0.4 Parts by weight methyl ethyl ketone 10 parts by weight

Composition 10
Urethane acrylate (UV1700B; manufactured by Nihon Gosei) 9.9 parts by weight Fluorine-based antifouling agent (Defensa TF3027; manufactured by Dainippon Ink) 0.1 part by weight Polymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 0.4 weight Methyl ethyl ketone 10 parts by weight

Composition 11
Urethane acrylate (UV1700B; manufactured by Nippon Gosei Co., Ltd.) 9.0 parts by weight Fluorine antifouling agent (Defensa TF3025; manufactured by Dainippon Ink) 1.0 part by weight Polymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 0.4 weight Methyl ethyl ketone 10 parts by weight

Composition 12
Urethane acrylate (UV1700B; manufactured by Nihon Gosei) 9.9 parts by weight Silicone antifouling agent (TSF4460; GE Toshiba Silicone) 0.1 part by weight Polymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 0.4 part by weight Methyl ethyl ketone 10 parts by weight

Composition 13
Urethane acrylate (UV1700B; manufactured by Nippon Gosei Co., Ltd.) 9.5 parts by weight Silicone antifouling agent (UVHC1105; GE Toshiba Silicone) 0.5 part by weight Polymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 0.4 part by weight Methyl ethyl ketone 10 parts by weight

Composition 14
Urethane acrylate (UV1700B; manufactured by Nihon Gosei) 5.0 parts by weight Silicone antifouling agent (UVHC8550; GE Toshiba Silicone) 5.0 parts by weight Polymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 0.4 parts by weight Methyl ethyl ketone 10 parts by weight

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.

Examples 2-8
Optical laminates of Examples 2 to 8 were obtained in the same manner as in Example 1 except that the composition for hard coat layer was changed to compositions 2 to 8.

Comparative Examples 1-6
In the formation of the hard coat layer, optical laminates of Comparative Examples 1 to 6 were obtained in the same manner as in Example 1 except that the composition for hard coat layer was changed to compositions 9 to 14.

The optical laminates of the evaluation test examples and comparative examples were evaluated based on the following evaluation criteria, and the results are shown in Table 1 below.
In addition, the abundance of silicon and fluorine on the hard coat layer surface of each example and comparative example was measured using an XPS (X-ray photoelectron spectroscopy) apparatus manufactured by Thermo Electron (VG Theta Probe). X-ray source is Monochromated Al Kα, X-ray output is 100W, measurement area is 400μmφ, lens is Angle Resolved, measurement angle is 5 steps (28 °, 38 °, 48 °, 58 °, 68 °) It was.
The measurement after wiping off the surface was measured by the same measurement method as described above after lightly wiping once with a cloth.
Evaluation 1: Antifouling property test The contact angle between water and an artificial fingerprint liquid (JIS K2246) was measured on the surface of the hard coat layer of the optical laminate. As the artificial fingerprint liquid (JIS K 2246), a solution in which water (500 ml), methanol (500 ml), sodium chloride (7 g), urea (1 g) and lactic acid (4 g) were mixed was used.
Evaluation criteria 1: Contact angle evaluation with water A: The contact angle of water was 90 ° or more.
Evaluation x: The contact angle of water was less than 90 °.
Evaluation Criteria 2) Contact Angle Evaluation with Artificial Fingerprint Liquid A: The contact angle with the artificial fingerprint liquid was 40 ° or more.
Evaluation x: The contact angle of the artificial fingerprint liquid was 40 ° or less.

Evaluation 2: Hardness evaluation test The surface of the hard coat layer of the optical laminate was subjected to 10 reciprocating frictions using # 0000 steel wool while applying a load of 600 g / cm ² to evaluate the presence or absence of scratches.
Evaluation criteria Evaluation A: No scratches could be confirmed.
Evaluation x: Scratches were confirmed.

Claims (8)

A hard coat layer used in an optical laminate,
As an antifouling agent and / or slipperiness imparting agent, comprising a silicon compound, a fluorine compound or a mixture thereof,
A hard coat layer having a silicon atom abundance of 10% or more and / or a fluorine atom abundance of 20% or more when the outermost surface of the hard coat layer is analyzed by XPS. After wiping the outermost surface of the hard cord layer with a cloth,
The hard coat according to claim 1, wherein when the outermost surface of the hard coat layer is analyzed by XPS, the abundance of silicon atoms is 5% or more and / or the abundance of fluorine atoms is 15% or more. layer. The total abundance of fluorine atoms obtained by XPS analysis of the entire hard coat layer is X _F %,
When the abundance of fluorine atoms obtained by wiping the outermost surface of the hard cord layer with a cloth and then XPS analysis of the outermost surface of the hard coat layer is Y _F %, the following formula (A):
Y _F / X _F ≧ 10 (A)
And / or
The total abundance of silicon atoms obtained by XPS analysis of the entire hard coat layer is X _S %,
After wiping the outermost surface of the hard cord layer with a cloth, when the silicon atom abundance obtained by XPS analysis of the outermost surface of the hard coat layer is Y _S %, the following formula (B):
Y _S / X _S ≧ 10 (B)
The hard coat layer according to claim 1 or 2, which satisfies the above. 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 1-3.   The optical laminate according to claim 4, further comprising a low refractive index layer, an antistatic layer or an antifouling layer between layers constituting the optical laminate or on the outermost surface of the optical laminate.   The optical laminate according to claim 4 or 5, 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 layered body according to any one of claims 1 to 6 on a surface opposite to the surface on which the hard coat layer is present in the optical layered body. 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 1-6, or the polarizing plate as described in Claim 7 on the surface of the said image display body.