KR20070017040A - Antireflection film, polarizing plate, and image display device - Google Patents

Abstract

An antireflection film comprising a low refractive index layer and a support prepared by coating a coating composition containing the following components: (A) The main chain consists of only carbon atoms, at least one fluorine-containing vinyl monomer polymerized unit and at least one hydroxyl group A fluorine-containing polymer containing a vinyl monomer-containing polymerizing unit and having a content of a hydroxyl group-containing vinyl monomer-polymerizing unit exceeding 20 mol%, but having no polysiloxane structure in the main chain; (B) a crosslinking agent capable of reacting with hydroxyl groups; And (C) a compound containing two or more (meth) acryloyl groups in one molecule.

Anti-reflection film, low refractive index layer, coating composition, polarizing plate, image display device

Description

Anti-reflective film, polarizer and video display device {ANTIREFLECTION FILM, POLARIZING PLATE, AND IMAGE DISPLAY DEVICE}

1 is a schematic cross-sectional view schematically showing a preferred embodiment of the film of the present invention.

2 is a schematic cross-sectional view schematically showing a preferred embodiment of the film of the present invention.

3 is a schematic cross-sectional view schematically showing a preferred embodiment of the film of the present invention.

4 is a schematic cross-sectional view schematically showing a preferred embodiment of the film of the present invention.

5 is a schematic cross-sectional view schematically showing a preferred embodiment of the film of the present invention.

The present invention relates to an antireflection film, a polarizing plate using an antireflection film, and an image display device using an antireflection film or a polarizing plate for the outermost surface of a display.

Generally, in image display devices such as a cathode ray tube display device (CRT), a plasma display (PDP), an electroluminescent display (ELD), and a liquid crystal display device (LCD), the contrast is reduced due to the reflection of external light. Alternatively, to prevent reflection of the image, the reflectance is reduced using the optical interference principle by placing the antireflective film on the outermost surface of the display.

In general, such antireflective films can be produced by forming on the support a low refractive index layer having a smaller refractive index than the support and having a suitable thickness. In order to achieve a low refractive index, it is preferable to use a material having as low a refractive index as possible in the low refractive index layer.

In addition, since the antireflection film is used on the outermost surface of the display, the scar resistance must be large. In the case of thin films having a thickness of about 100 nm, in order to realize high scar resistance, the films must have strength on their own and have adhesion to the underlying layer.

In addition, since the antireflective film is used on the outermost surface of the display device, it must have excellent resistance to adhesion of various stains centered on fingerprints in display or in daily use, or even in case of film stains, excellent stain removal characteristics (Hereinafter, collectively referred to as "antifouling" by combining the two characteristics).

In order to reduce the refractive index of the material, there are means such as (1) introduction of fluorine atoms and (2) reduction of density (pore introduction). However, in all the said means, there exists a tendency for the film strength or adhesive force of an interface surface to fall, and the scar resistance falls. Therefore, it was a difficult subject to make low refractive index and high scar resistance compatible with each other.

In addition, in order to increase the hardness of the film itself, it is important to allow the curing reaction to proceed sufficiently. By allowing the hydroxyl group of the fluorine-containing polymer to react with the curing agent by the action of an acid catalyst, a method of curing the low refractive index layer of the antireflective film is disclosed in Japanese Patent No. 3498381, JP-A-11-189621, JP-A -11-228631, JP-A-2004-307524 and JP-A-2003-26732.

Further, in order to improve antifouling properties, examples of the fluorine-containing polymer in which silicon is inserted into the polymer main chain are described in Japanese Patent Nos. 3498381, JP-A-11-189621, JP-A-11-228631 and JP-A-2004-307524 It is described in.

On the other hand, JP-A-62-174276, JP-A-1-259071, JP-A-2-173172 and JP-A-2-302477 propose curable compositions or paints based on the amine salt of sulfonic acid. .

Regarding curing, according to the techniques of Japanese Patent No. 3498381, JP-A-11-189621, JP-A-11-228631, JP-A-2004-307524 and JP-A-2003-26732, p-toluene Sulphonic acid is used as the acid catalyst. Although its curing activity is large, since the curing reaction partially proceeds upon storage, the stability of the coating solution is insufficient and the coating conditions are limited. Therefore, it is required to make the stability and curing activity of the coating solution compatible with each other.

In terms of improving the antifouling properties, the method of introducing silicon into the polymer backbone as described in Japanese Patent No. 3498381, JP-A-11-189621, JP-A-11-228631 and JP-A-2004-307524 is preferred. May weaken.

In addition, there is no embodiment in which the techniques described in JP-A-62-174276, JP-A-1-259071, JP-A-2-173172 and JP-A-2-302477 are applied to the antireflection film, No selection criteria were revealed.

It is an object of the present invention to provide an antireflection film having excellent scar resistance and antifouling properties while making the storage stability and curing activity of the coating solution compatible with each other. Another object of the present invention is to provide a polarizing plate and an image display device using such an antireflection film.

In order to overcome the above problems, the present inventors conducted extensive and intensive research. As a result, the present inventors have found that the above-mentioned object can be achieved by solving the above problems, thereby completing the present invention.

That is, this invention achieved the said objective by the following structures.

(1) an antireflection film comprising a low refractive index layer and a support prepared by coating a coating composition containing the following components:

(A) the main chain consists only of carbon atoms, contains at least one fluorine-containing vinyl monomer polymerized unit and at least one hydroxyl group-containing vinyl monomer polymerized unit, and has a content of 20 moles of hydroxyl group-containing vinyl monomer polymerized unit Fluorine-containing polymers having a percentage exceeding%, but having no polysiloxane structure in the main chain;

(B) a crosslinking agent capable of reacting with hydroxyl groups; And

(C) A compound containing two or more (meth) acryloyl groups in one molecule.

(2) an antireflection film comprising a low refractive index layer and a support prepared by coating a coating composition containing the following components:

(A) the main chain consists only of carbon atoms, contains at least one fluorine-containing vinyl monomer polymerized unit and at least one hydroxyl group-containing vinyl monomer polymerized unit, and has a content of 20 moles of hydroxyl group-containing vinyl monomer polymerized unit Fluorine-containing polymers having a percentage exceeding%, but having no polysiloxane structure in the main chain;

(B) a crosslinking agent capable of reacting with hydroxyl groups; And

(D) A composition containing at least one of an organosilane compound or a hydrolyzate of the organosilane compound and a partial condensate of the organosilane compound.

(3) an antireflection film comprising a low refractive index layer and a support prepared by coating a coating composition containing the following components:

(A) the main chain consists only of carbon atoms, contains at least one fluorine-containing vinyl monomer polymerized unit and at least one hydroxyl group-containing vinyl monomer polymerized unit, and has a content of 20 moles of hydroxyl group-containing vinyl monomer polymerized unit Fluorine-containing polymers having a percentage exceeding%, but having no polysiloxane structure in the main chain;

(B) a crosslinking agent capable of reacting with hydroxyl groups; And

(E) Inorganic particles having a particle size of 1 nm or more and 100 nm or less.

(4) The antireflection film according to the above (1) or (2), wherein the coating composition further contains inorganic particles having a (E) particle size of 1 nm or more and 100 nm or less.

(5) The polymerization according to any one of (1) to (4), wherein the fluorine-containing polymer has at least one graft site containing a polysiloxane repeating unit represented by the following formula (1) in a side chain: Antireflective film comprising the unit.

{In the above formula (1), R ¹ and R ² may be the same or different and each represents an alkyl group or an aryl group; p represents an integer of 10 to 500}.

(6) The coating composition according to any one of (1) to (5), further comprising a polysiloxane compound having a functional group capable of forming a bond by reacting with (F) a hydroxyl group or a hydroxyl group. Antireflective film.

(7) The antireflection film according to any one of the above (1) to (6), wherein the coating composition further contains at least one salt containing an organic base and an acid having a pKa of 5.0 to 10.5 of a conjugate acid.

(8) The antireflection film according to any one of the above (1) to (6), wherein the coating composition further contains at least one salt containing a nitrogen-containing organic base and an acid having a boiling point of 35 ° C. or higher and 85 ° C. or lower. .

(9) The antireflection film according to any one of (3) to (8), wherein the inorganic particles are hollow silica particles.

(10) The method according to any one of the above (1) to (9), further comprising at least one layer having a larger refractive index than the low refractive index layer between the support and the low refractive index layer, wherein the at least one layer is an organosilane compound, or An antireflective film containing a composition containing at least one of a hydrolyzate of an organosilane compound and a partial condensate of the organosilane compound.

(11) A polarizing plate comprising the antireflective film described in any one of (1) to (10), wherein the antireflective film is provided in the polarizing plate as one of two protective films for polarizing films.

(12) An image display device comprising the antireflection film described in any one of (1) to (10) or the polarizing plate disclosed in (11), wherein the antireflection film or polarizing plate is used on the outermost surface of the display. Display device.

Although the antireflection film of the present invention has sufficient antireflection properties, it is excellent in both scar resistance and antifouling property. In addition, the antireflective film of the present invention has high production adaptability since it is produced using a coating solution in which storage properties and curing activities are compatible with each other. Furthermore, the image display device provided with the antireflective film of the present invention and the image display device provided with the polarizing plate using the antireflective film of the present invention have less visibility and background reflection by external light and have excellent visibility.

Hereinafter, the present invention will be described in more detail. In addition, in this specification, when a numerical value shows a physical property value, a characteristic value, etc., the expression "(value 1)-(value 2)" means "(value 1) or more and (value 2) or less". In addition, the term "(meth) acrylate" herein means "at least one of acrylate and methacrylate". The same applies to "(meth) acrylic acid" and the like.

1. Construction of the Anti-Reflection Film of the Present Invention:

First, the structure like the various compounds which can be used for the component layer and support body which comprise an antireflection film of this invention is demonstrated.

Binder component added as 1- (1) monomer:

The constituent layers of the film of the present invention may be formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. That is, the binder layer may be formed by coating a coating composition containing an ionizing radiation curable polyfunctional monomer or a polyfunctional oligomer on a transparent support, and crosslinking or polymerizing the polyfunctional monomer or polyfunctional oligomer. It is preferable that the binder component added as a monomer is contained in the coating composition for forming the hard coat layer and / or low refractive index layer which are mentioned later of the antireflection film of this invention.

As a functional group of an ionizing radiation curable polyfunctional monomer or a polyfunctional oligomer, a photopolymerizable functional group, an electron beam polymerizable functional group, and a radiation polymerizable functional group are preferable, and a photopolymerizable functional group is especially preferable.

Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as (meth) acryloyl group, vinyl group, styryl group and allyl group, and a (meth) acryloyl group is preferable. In particular, the following compounds containing two or more (meth) acryloyl groups in one molecule can be used as the component (C) of the low refractive index layer of the present invention.

Specific examples of the photopolymerizable polyfunctional monomer containing a photopolymerizable functional group which can be used include:

(Meth) acrylic acid diesters of alkylene glycols such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate and propylene glycol di (meth) acrylate;

(Meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) Acrylates;

(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate; And

(Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxydiethoxy) phenyl} propane and 2,2-bis {4- (acryloxypolyprop Foxy) phenyl} propane.

Moreover, epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate are also used suitably as a photopolymerizable polyfunctional monomer.

First of all, esters of polyhydric alcohols and (meth) acrylic acid are preferred; More preferred are polyfunctional monomers containing three or more (meth) acryloyl groups in one molecule. Specific examples thereof include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexane tetra (meth) acrylate, pentaglycerol triacrylate, and pentaerythritol tetra (Meth) acrylate, pentaerythritol tri (meth) acrylate, (di) pentaerythritol triacrylate, (di) pentaerythritol pentaacrylate, (di) pentaerythritol tetra (meth) acrylate, ( Di) pentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate and tripentaerythritol hexatriacrylate. In this specification, the terms "(meth) acrylate", "(meth) acrylic acid" and "(meth) acryloyl" refer to "acrylate or methacrylate", "acrylic acid or methacrylic acid" and "acrylic acid, respectively". Loyl or methacryloyl ”.

In order to control the refractive index of each layer, monomers having different refractive indices in terms of polymers can be used as the monomer used as the binder. In particular, examples of the high refractive index monomers include bis (4-methacryloylthiophenyl) sulfide, vinylnaphthalene, vinylphenyl sulfide and 4-methacryloxyphenyl-4'-methoxyphenyl thioether.

Dendrimers disclosed in, for example, JP-A-2005-76005 and JP-A-2005-36105, and norbornene ring-containing monomers, such as disclosed in, for example, JP-2005-60425, can also be used.

Two or more types of polyfunctional monomers can be used in combination.

The polymerization of the ethylenically unsaturated group-containing monomer can be carried out by irradiation with heating or ionizing radiation in the presence of a photo radical initiator or a thermal radical initiator.

For the polymerization reaction of the photopolymerizable polyfunctional monomer, it is preferable to use a photopolymerization initiator. As a photoinitiator, a radical photopolymerization initiator and a photocationic polymerization initiator are preferable, and a radical photopolymerization initiator is especially preferable.

Binder Component Added as 1- (2) Polymer:

In the present invention, a polymer or a crosslinked polymer can be used as the binder for the constituent layer. It is preferable that the crosslinked polymer contains an anionic group. The crosslinked anionic group-containing polymer has a structure in which the main chain of the anionic group-containing polymer is crosslinked. It is preferable that the binder component added as a polymer is contained in the coating composition for formation of the hard-coat layer and / or low refractive index layer mentioned later of the antireflection film of this invention.

Examples of the main chain of the polymer include polyolefins (saturated hydrocarbons), polyethers, polyurethanes, polyesters, polyamines, polyamides, and melamine resins. Among them, polyolefin backbone, polyether backbone and polyurea backbone are preferred; More preferred are polyolefin backbones and polyether backbones; Most preferred are polyolefin backbones.

The polyolefin backbone consists of saturated hydrocarbons. The polyolefin backbone is obtained, for example, by addition polymerization of unsaturated polymerizable groups. In the case of polyether backbones, the repeating units are bonded by ether bonds (-O-). A polyether main chain is obtained by ring-opening polymerization reaction of an epoxy group, for example. In the case of polyurea backbones, the repeating units are joined by urea bonds (-NH-CO-NH-). Polyurea backbones are obtained, for example, by polycondensation reactions between isocyanate and amino groups. In the case of a polyurethane backbone, the repeating units are joined by urethane bonds (-NH-CO-O-). Polyurethane backbones are obtained, for example, by polycondensation reactions between isocyanate groups and hydroxyl groups (including N-methylol groups). In the case of a polyester main chain, the repeating unit is bonded by an ester bond (-CO-O-). Polyester backbones are obtained, for example, by polycondensation reactions between carboxyl groups (including acid halide groups) and hydroxyl groups (including N-methylol groups). In the case of polyamine backbones, the repeating units are bound by imino bonds (-NH-). The polyamine main chain is obtained by, for example, a ring-opening polymerization reaction of ethyleneimine groups. In the case of polyamide backbones, the repeating units are obtained by amide bonds (-NH-CO-). Polyamide backbones are obtained, for example, by reaction between isocyanate groups and carboxyl groups (including acid halide groups). The melamine resin backbone is obtained by, for example, a polycondensation reaction between a triazine group (eg melamine) and an aldehyde (eg formaldehyde). In addition, in the case of melamine resin, the main chain itself has a crosslinked structure.

Anionic groups are bonded directly to the polymer backbone or to the backbone via a connecting group. It is preferred that the anionic group is bonded as a side chain to the main chain via a linking group.

Examples of the anionic group include a carboxyl group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono), and a sulfonic acid group and a phosphoric acid group are preferable.

The anionic group can be in a salt state. Alkali metal ions are preferable as the cation which forms a salt together with the anionic group. In addition, protons of the anionic group can be dissociated.

It is preferable that the linking group which couple | bonds an anionic group to a polymer main chain is a divalent group chosen from -CO-, -O-, an alkylene group, an arylene group, and a combination thereof.

In the crosslinked structure, chemical bonds (preferably covalent bonds) of two or more main chains occur, and preferably covalent bonds of three or more main chains occur. It is preferable that a crosslinked structure consists of a divalent or polyvalent group chosen from -CO-, -O-, -S-, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and a combination thereof.

The crosslinked anionic group-containing polymer is preferably a copolymer comprising an anionic group-containing repeat unit and a repeating unit having a crosslinked structure. The proportion of anionic group-containing repeat units in the copolymer is preferably from 2 to 96% by weight, more preferably from 4 to 94% by weight and most preferably from 6 to 92% by weight. The repeating unit may contain two or more anionic groups. The proportion of repeating units having a crosslinked structure in the copolymer is preferably 4 to 98% by weight, more preferably 6 to 96% by weight, most preferably 8 to 94% by weight.

The repeating units of the crosslinked anionic group-containing polymer may have both anionic groups and crosslinked structures. In addition, other repeating units (repeating units not having both anionic group and crosslinked structure) may be included.

As another repeating unit, the repeating unit containing an amino group or a quaternary ammonium group, and the repeating unit containing a benzene ring are also preferable. The amino group or quaternary ammonium group has a function of maintaining the dispersed state of the inorganic particles similar to the anionic group. In addition, even if an amino group, a quaternary ammonium group, or a benzene ring is included in the anionic group-containing repeating unit or a repeating unit having a crosslinked structure, the same effect can be obtained.

In repeating units containing amino or quaternary ammonium groups, the amino or quaternary ammonium groups are bonded directly to the polymer backbone or through the linking group to the backbone. It is preferred that an amino group or quaternary ammonium group is bonded as a side chain to the main chain via a linking group. The amino group or quaternary ammonium group is preferably a secondary amino group, tertiary amino group, or quaternary ammonium group, more preferably tertiary amino group or quaternary ammonium group. In the secondary amino group, tertiary amino group or quaternary ammonium group, the group bonded to the nitrogen atom is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, and most preferably an alkyl group having 1 to 6 carbon atoms. As the counterion of the quaternary ammonium group, halide ions are preferable. The linking group for bonding a secondary amino group, tertiary amino group or quaternary ammonium group to the polymer backbone is preferably a divalent group selected from -CO-, -NH-, -O-, an alkylene group, an arylene group, and a combination thereof. Do. When the crosslinked anionic group-containing polymer comprises repeating units containing amino groups or quaternary ammonium groups, the proportion of the repeating units is preferably 0.06 to 32% by weight, more preferably 0.08 to 30% by weight, most preferably Preferably 0.1 to 28% by weight.

1- (3) Fluorine-containing polymer binder [constituent (A) of low refractive index layer of the present invention]:

In the present invention, in the low refractive index layer, the main chain is formed of only carbon atoms, and includes at least one fluorine-containing vinyl monomer polymerization unit and at least one hydroxyl group-containing vinyl monomer polymerization unit, and the hydroxyl group-containing vinyl monomer Polymers having a content of polymerized units in excess of 20 mol% are used, provided the polymers do not have a polysiloxane structure in the main chain.

(Fluorine-containing vinyl monomer polymerization unit)

In the present invention, the structure of the fluorine-containing vinyl monomer polymerization unit included in the fluorine-containing polymer used to form the low refractive index layer is not particularly limited, and examples thereof include fluorine-containing olefins, perfluoroalkyl vinyl ethers, Polymerized units based on fluorine-containing alkyl group-containing vinyl ethers or (meth) acrylates and the like. In view of the properties required for production adaptability and low refractive index layer, such as refractive index and film strength, the fluorine-containing polymer is preferably a copolymer of fluorine-containing olefins and vinyl ethers, more preferably perfluoroolefins and vinyls. Copolymers of ethers. In addition, for the purpose of lowering the refractive index, perfluoroalkyl vinyl ether, fluorine-containing alkyl group-containing vinyl ether, (meth) acrylate and the like can be included as the copolymerization component.

As the perfluoroolefins, those having 3 to 7 carbon atoms are preferable; From the viewpoint of polymerization reactivity, perfluoropropylene and perfluorobutylene are preferable; From the viewpoint of availability, perfluoropropylene is particularly preferred.

The content of perfluoroolefins in the polymer is 25 to 75 mol%. In order to realize a low refractive index of the material, it is preferable to increase the introduction rate of the perfluoroolefin, but from the viewpoint of polymerization reactivity, in the general solution-based radical polymerization reaction, the introduction of about 50 to 70 mol% is the limit, and the range is Excessive introduction is difficult. In the present invention, the content is preferably 30 mol% to 70 mol%, more preferably 30 mol% to 60 mol%, more preferably 35 mol% to 60 mol%, particularly preferably 40 To 60 mol%.

In addition, in the fluorine-containing polymer used in the present invention, in order to realize a low refractive index, the fluorine-containing vinyl ether represented by M1 below can be copolymerized. The copolymer component can be introduced into the polymer in the range of 0 to 40 mol%, preferably 0 to 30 mol%, particularly preferably 0 to 20 mol%.

In M1, Rf ¹¹¹ represents a fluorine-containing alkyl group having 1 to 30 carbon atoms, preferably a fluorine-containing alkyl group having 1 to 20 carbon atoms, particularly preferably a fluorine-containing alkyl group having 1 to 15 carbon atoms; It may be linear (eg, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) _a H, and —CH ₂ CH ₂ (CF ₂ ) _a F (a: an integer from 2 to 12)}; May have a branched structure (eg, -CH (CF ₃ ) ₂ , -CH ₂ CF (CF ₃ ) ₂ , -CH (CH ₃ ) CF ₂ CF ₃ , and -CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H}; An alicyclic structure (preferably a 5-membered ring or a 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, and an alkyl group substituted with such a group); Ether linkages {eg, —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ (CF ₂ ) _b H, —CH ₂ CH ₂ OCH ₂ (CF ₂ ) _b F ( b: integer from 2 to 12), and -CH ₂ CH ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H}. In addition, the substituent represented by Rf ¹¹¹ should not be interpreted as being limited to the substituents listed herein.

The monomer represented by M1 is described, for example, in Macromolecules , Vol. 32 (21), p.7122 (1999)], JP-A-2-721 and the like, the fluorine-containing alcohol in the presence of a base catalyst is converted to a splitter-substituted alkyl vinyl ether such as vinyloxyalkyl sulfonate and A method of acting on vinyloxyalkyl chloride; As described in WO 92/05135, in which a fluorine-containing alcohol and a vinyl ether such as butyl vinyl ether are mixed to exchange vinyl groups in the presence of a palladium catalyst; And by reacting the fluorine-containing ketone and dibromoethane with each other in the presence of a potassium fluoride catalyst, as described in US Pat. No. 3,420,793, followed by a hydrogen bromide removal reaction with an alkaline catalyst. have.

Although the preferable example of the component represented by M1 is shown below, it should not be interpreted that this invention is limited to this.

In the fluorine-containing polymer used in the present invention, in order to realize a low refractive index, the perfluorovinyl ether represented by the following M2 can be copolymerized. The copolymer component can be introduced into the polymer in the range of 0 to 40 mol%, preferably 0 to 30 mol%, particularly preferably 0 to 20 mol%.

In M2, Rf ¹¹² is a fluorine-containing alkyl group having 1 to 30 carbon atoms, preferably a fluorine-containing alkyl group having 1 to 20 carbon atoms, particularly preferably a fluorine-containing alkyl group having 1 to 10 carbon atoms, more preferably A perfluoroalkyl group having 1 to 10 carbon atoms. In addition, the fluorine-containing alkyl group may have a substituent. Specific examples of Rf ¹¹² include -CF ₃ {M2- (1)}, -CF ₂ CF ₃ {M2- (2)}, -CF ₂ CF ₂ CF ₃ {M2- (3)}, and -CF ₂ CF (OCF ₂ CF ₂ CF ₃ ) CF ₃ {M3- (4)}.

(Hydroxyl group-containing vinyl monomer polymerization unit)

Fluorine-containing polymers used in the present invention are required to include hydroxyl group-containing vinyl monomer polymerized units having a content of more than 20 mol% in the polymer. Since the hydroxyl group has a function of curing upon reaction with the crosslinking agent, the content of the hydroxyl group is preferably high because it can form a hard film. Its content is preferably more than 20 mol% to 70 mol% or less, more preferably more than 20 mol% to 60 mol% or less, more preferably 25 mol% to 55 mol% or less.

The hydroxyl group-containing vinyl monomer may be used without particular limitation, so long as it is copolymerizable with the fluorine-containing vinyl monomer polymerized unit, examples of which include vinyl ether, (meth) acrylate, and styrene. For example, when using perfluoroolefin (for example, hexafluoropropylene) as a fluorine-containing vinyl monomer, it is preferable to use the hydroxyl group-containing vinyl ether with good copolymerizability. Specific examples thereof include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, 8-hydroxyoctyl vinyl ether, diethylene glycol vinyl ether, triethylene glycol vinyl ether, and 4 -(Hydroxymethyl) cyclohexylmethyl vinyl ether. However, the present invention should not be construed as being limited thereto.

(Structural unit having a polysiloxane structure)

In order to impart antifouling property, it is also preferable that the fluorine-containing polymer used for this invention contains the structural unit which has a polysiloxane structure. Fluorine-containing polymers having a polysiloxane structure useful in the present invention include (a) at least one fluorine-containing vinyl monomer polymerization unit, (b) at least one hydroxyl group-containing vinyl monomer polymerization unit and (c) a side chain. Listed are fluorine-containing polymers comprising at least one polymerized unit having a graft moiety comprising a polysiloxane repeating unit represented by 1), wherein the main chain is formed solely of carbon atoms.

In formula (1), R ¹ and R ² may be the same or different, and each represents an alkyl group or an aryl group. The alkyl group preferably has 1 to 4 carbon atoms, examples of which include a methyl group, trifluoromethyl group, and ethyl group. The aryl group preferably has 6 to 20 carbon atoms, examples of which include a phenyl group and a naphthyl group. Among these, methyl group and phenyl group are preferable; Methyl groups are particularly preferred. p represents an integer of 10 to 500, preferably 10 to 350, particularly preferably 10 to 250.

The polymer having a polysiloxane structure represented by the general formula (1) in the side chain has a corresponding reactive group at one terminal in relation to the polymer containing a reactive group (for example, an epoxy group, a hydroxyl group, a carboxyl group, and an acid anhydride group). (For example, with respect to an epoxy group or an acid anhydride group, a polysiloxane comprising an amino group, a mercapto group, a carboxyl group and a hydroxyl group) (e.g., SILAPLANE series (manufactured by Chisso Corporation)) is described, for example, in [ J. Appl. Polym. Sci ., 78 , 1955 (2000) and JP-A-56-28219; And a method of polymerizing a polysiloxane-containing silicon macromonomer, preferably both of the above methods can be used. In this invention, the method of polymerizing and introducing a silicon macromonomer is more preferable.

As silicon macromonomers, any silicon macromonomer containing a polymerizable group copolymerizable with a fluorine-containing olefin is useful. The structure represented by any one of following General formula (2)-(5) is preferable.

In the above formulas (2) to (5), R ¹ , R ² and p have the same meaning as in formula (1); Their preferred range is also the same. Each of R ³ to R ⁵ independently represents a substituted or unsubstituted monovalent organic group or a hydrogen atom. Above all, alkyl groups having 1 to 10 carbon atoms (eg, methyl, ethyl and octyl groups), alkoxy groups having 1 to 10 carbon atoms (eg, methoxy, ethoxy and propyloxy groups), and carbon Aryl groups having a number of 6 to 20 (eg, phenyl group and naphthyl group) are preferable; Especially preferred are alkyl groups having 1 to 5 carbon atoms. R ⁶ represents a hydrogen atom or a methyl group. L ₁ represents an arbitrary linking group having 1 to 20 carbon atoms; Examples thereof include substituted or unsubstituted, linear, branched or alicyclic alkylene groups and substituted or unsubstituted arylene groups. First of all, unsubstituted linear alkylene groups having 1 to 20 carbon atoms are preferred; Ethylene groups and propylene groups are particularly preferred. Such a compound can be synthesized by, for example, a method as described in JP-A-6-322053.

Preferably, all of the compounds represented by the formulas (2) to (5) can be used in the present invention. Above all, the compound having a structure represented by the formula (2), (3) or (4) is particularly preferable from the viewpoint of copolymerization with the fluorine-containing olefin. The polysiloxane moiety preferably comprises from 0.01 to 20% by weight, more preferably from 0.05 to 15% by weight and particularly preferably from 0.5 to 10% by weight in the graft copolymer.

The amount of the polysiloxane structure-containing structural unit with respect to the molecular weight of the total fluorine-containing polymer of the present invention is preferably 0.01 to 2 mol%, more preferably 0.01 to 1 mol%, even more preferably 0.01 to 2 mol%, Especially preferably, it is 0.05-2 mol%.

Preferred examples of polymerized units of polymer grafted moieties containing polysiloxane moieties in the side chains useful in the present invention are given below, but should not be construed as limiting the invention thereto.

S- (36) SILAPLANE FM-0711 (manufactured by Chisso Corporation)

            Number average molecular weight: 1000

S- (37) SILAPLANE FM-0721 (manufactured by Chisso Corporation)

            Number average molecular weight: 6000

S- (38) SILAPLANE FM-0725 (manufactured by Chisso Corporation)

            Number average molecular weight: 14000

By introducing a polysiloxane structure, not only the antifouling and dust removing properties are imparted to the film, but also the slipperiness is imparted to the film surface. This is also advantageous with regard to scar resistance.

(Other polymerization units)

The other copolymerization component which can form a polymerized unit can be suitably selected from various viewpoints, for example, hardness, adhesiveness to a board | substrate, solubility in a solvent, and transparency. Examples thereof include vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether and isopropyl vinyl ether; And vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl cyclohexanecarboxylate. The amount of such copolymerization component introduced is in the range of 0 to 40 mol%, preferably 0 to 30 mol%, particularly preferably 0 to 20 mol%.

(Preferred arrangement of fluorine-containing polymer)

Particularly preferred polymers of the present invention are arrays represented by the following general formula (7).

In formula (7), Rf ¹¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms. With regard to the site represented by -CF ₂ CF (Rf ¹¹ ), the above description with regard to perfluoroolefins can be applied, for example. In formula (7), Rf ¹² is the same as defined above for the fluorine-containing vinyl ether (Rf ¹¹² in the compound represented by formula M2 above); The preferred range thereof is also the same. Each of A ¹¹ and B ¹¹ represents a hydroxyl group-containing vinyl monomer polymerized unit or an optional structural unit. A ¹¹ is the same as defined above for the hydroxyl group-containing vinyl monomer polymerization unit. B ¹¹ is not particularly limited, but vinyl ether or vinyl ester is preferable from the viewpoint of copolymerization. Specifically, the above-listed monomers (other polymerization units) and the monomers represented by the general formula (M1) are listed.

Y ¹¹ represents a structural unit having a polysiloxane structure; The constitution may be a polymer unit having a graft moiety including the polysiloxane repeating unit represented by the general formula (1) in the side chain. Its definition and preferred range are the same as in the above-defined (structural unit having a polysiloxane structure).

each of a to d represents the mole fraction (%) of each of the constituents; (a + b + c + d) is 100. They satisfy the following relationship: 30 ≦ a ≦ 70 (more preferably 30 ≦ a ≦ 60, more preferably 35 ≦ a ≦ 60), 0 ≦ b ≦ 40 (more preferably 0 ≦ b ≦ 30, More preferably 0 ≦ b ≦ 20, 20 ≦ c ≦ 70 (more preferably 20 ≦ c ≦ 60, more preferably 25 ≦ c ≦ 55), and 0 ≦ d ≦ 40 (more preferably 0 ≤ d ≤ 30).

y represents the weight fraction (%) of the polysiloxane-containing structural unit with respect to the molecular weight of the entire fluorine-containing polymer. This satisfies the following relationship: 0.01 ≦ y ≦ 20 (more preferably 0.05 ≦ y ≦ 15, more preferably 0.5 ≦ y ≦ 10).

In the present invention, the number average molecular weight of the fluorine-containing polymer (preferably, the fluorine-containing polymer represented by the general formula (7) shown above) used to form the low refractive index layer is preferably 5,000 to 1,000,000, more preferably 8,000 to 500,000, particularly preferably 10,000 to 100,000.

Here, the number average molecular weight is a GPC analyzer using TSKgel GMHxL, TSKgel G4000HxL and TSKgel G2000HxL (all are trademarks of Tosoh Corporation), which are molecular weights converted to polystyrene by detection with a differential refractometer in THF as a solvent.

One of the particularly preferred polymers in the present invention has a structure represented by the following formula (8).

In Formula 8, a1, c1, and d1 each represent a mole fraction (%) of each component, and a1 + b1 + c1 = 100. Each preferably satisfies each of the following relations: 30 ≦ al ≦ 70 (more preferably 30 ≦ al ≦ 60, even more preferably 35 ≦ a1 ≦ 60, most preferably 40 ≦ a1 ≦ 55); 20 ≦ c1 ≦ 50 (more preferably 20 ≦ c1 ≦ 45, even more preferably 25 ≦ c1 ≦ 40, most preferably 30 ≦ c1 ≦ 40); And 0 ≦ d1 ≦ 30 (more preferably 5 ≦ d1 ≦ 30, even more preferably 10 ≦ d1 ≦ 25, most preferably 10 ≦ d1 ≦ 20).

In Formula 8, Y ¹² represents a structural unit having a polysiloxane structure represented by Formula 2, and preferably has a number average molecular weight of 1000 to 40000, more preferably 3000 to 20000, and even more preferably 5000 to 15000. . As a preferred embodiment for Y ¹² , S- (1), S- (2), S- (7), S- (37) or S- (38) may be mentioned. Among them, S- (1), S- (2), S- (37) or S- (38) are more preferable, and S- (2), S- (37) or S- (38) are more preferable. More preferred.

y1 represents the mass fraction (%) of the polysiloxane-containing structural unit with respect to the total molecular weight of the fluorine-containing polymer, and satisfies the following relationship; 0.01 ≦ y1 ≦ 20 (more preferably 1 ≦ y1 ≦ 15, even more preferably 2 ≦ y1 ≦ 10, most preferably 3 ≦ y1 ≦ 7).

The number average molecular weight of the fluorine-containing polymer represented by Formula 8 is preferably 5,000 to 500,000, more preferably 6,000 to 100,000, particularly preferably 7,000 to 50,000. Note that this number average molecular weight is the same as indicated by the polystyrene-conversion value mentioned above.

In Tables 1-5, the specific example of the fluorine-containing polymer in this invention is shown. However, the present invention should not be interpreted as being limited thereto. Tables 1 to 5 show combinations of polymerized units in fluorine-containing polymers.

For use in the present invention, the fluorine-containing polymers shown in Tables 1 to 5 above contain fluorine-containing polymer components (fluorine-containing vinyl monomer polymerization units and hydroxyl group-containing vinyl monomer polymerization units) and silicon-containing components (polysiloxanes). Structure unit). The fluorine-containing polymer component represents the mole fraction (%) of each component, while the silicon-containing component represents the mass% of the silicon-containing component, respectively, relative to the total molecular weight of the fluorine-containing polymer. The structural unit (silicone-containing component) having a polysiloxane structure has a large molecular weight, and the contribution of the mole fraction of each unit in the fluorine-containing polymer is as small as 2 mol% or less. Thus, the mole fraction was calculated without the silicon-containing component. The symbols outlined in the table are as follows.

HFP: Hexafluoropropylene

HEVE: 2-hydroxyethyl vinyl ether

HBVE: 4-hydroxybutyl vinyl ether

HOVE: 8-hydroxyoctyl vinyl ether

DEGVE: diethylene glycol vinyl ether

HMcHVE: 4- (hydroxymethyl) cyclohexylmethyl vinyl ether

EVE: ethyl vinyl ether

cHVE: cyclohexyl vinyl ether

tBuVE: t-butyl vinyl ether

VAc: Vinyl Acetate

In the present invention, as the fluorine-containing polymer represented by P1 to P59, P2, P3, P10-P12, P14, P17, P18, P20, P22-P26, P29, P38, P39, P41, P42, P44, P45, And P49-P59 are preferred, P14, P17, P18, P20, P22-P24, P38, P39, P41, P42, P44, P45 and P49-P59 are more preferred, and P49-P59 are even more preferred.

Synthesis of the fluorine-containing polymer used in the present invention can be carried out by various polymerization methods, for example, solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, block polymerization, and emulsion polymerization. In addition, the synthesis can be carried out with known operations such as batch operation, semi-continuous operation and continuous operation.

Examples of the polymerization initiation method include a method of using a radical initiator and a method of irradiating light or radiation. Such polymerization methods and polymerization initiation methods are described, for example, in Teiji Tsuruta, Kobunshi Gosei Hoho (Polymer Synthesis Methods, Rev. (issued by Nikkan Kogyo Shimbun Ltd., 1971)); and Takayuki Otsu and Masayoshi Kinoshita, Kobunshi Gosei no Jikkenho (Exerimental Methods of Polymer Synthesis), published by Kagaku-dojin Publishing Company, Inc., pages 124-125 (1972).

Of the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable. Examples of solvents used in the solution polymerization method include various solvents such as ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol and 1-butanol. Such organic solvents may be used alone or in combination of two or more of these, or as a mixed solvent with water.

The polymerization temperature should be set in relation to the molecular weight of the polymer to be formed, the type of initiator, and the like. The polymerization can be carried out below 0 ° C. or above 100 ° C., but it is preferred to carry out the polymerization at a temperature in the range from 40 to 100 ° C.

The reaction pressure may be appropriately selected, but the reaction pressure is usually about 0.01 to 10 MPa, preferably about 0.05 to 5 MPa, more preferably about 0.1 to 2 MPa. The reaction time is about 5 to 30 hours.

With regard to the polymer obtained, the reaction solution can be used as is for the use of the present invention as it is, or after purification by reprecipitation or liquid separation operation.

1- (4) organosilane compound [constituent component (D) of the low refractive index layer of the film of the present invention]:

From the point of view of scar resistance, the organosilane compound or the hydrolyzate of the organosilane compound and / or its partial condensate (the solution of the reaction components will hereinafter sometimes be referred to as the "sol component") is a low refractive index layer of the film of the present invention. It is preferable that contained in.

Such compounds act as binders, such that after coating, the curable composition is condensed in a drying and heating step to form a cured material. In addition, when the polyfunctional acrylate polymer is contained, a binder having a three-dimensional structure is formed upon irradiation with actinic light.

The organosilane compound is preferably represented by the following general formula [A].

Formula [A]

(R ¹⁰ ) _m -Si (X) _4-m

In said general formula [A], R <^10> represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, hexyl, decyl and hexadecyl. Carbon number of an alkyl group becomes like this. Preferably it is 1-30, More preferably, it is 1-16, Especially preferably, it is 1-6. Examples of aryl groups include phenyl and naphthyl. Among these, a phenyl group is preferable.

X represents a hydroxyl group or a hydrolyzable group. Examples of hydrolyzable groups include alkoxy groups (preferably alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups), halogen atoms (eg, Cl, Br and I), and R ² COO ( Wherein R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; examples thereof include CH ₃ COO and C ₂ H ₅ COO). Among these, an alkoxy group is preferable; Especially preferred are methoxy and ethoxy groups.

m is an integer of 1 to 3, preferably 1 or 2, particularly preferably 1.

When a plurality of R ¹⁰ or X are present, the plurality of R ¹⁰ or X may be the same or different.

Substituents contained in R ¹⁰ are not particularly limited, and examples thereof include halogen atoms (eg, fluorine, chlorine and bromine), hydroxyl groups, mercapto groups, carboxyl groups, epoxy groups, alkyl groups (eg, methyl, Ethyl, isopropyl, propyl and t-butyl), aryl groups (eg phenyl and naphthyl), aromatic heterocyclic groups (eg furyl, pyrazolyl and pyridyl), alkoxy groups (eg , Methoxy, ethoxy, isopropoxy and hexyloxy), aryloxy groups (eg phenylthio), alkylthio groups (eg methylthio and ethylthio), arylthio groups (eg , Phenylthio), alkenyl groups (e.g. vinyl and 1-propenyl), acyloxy groups (e.g. acetoxy, acryloyloxy and methacryloyloxy), alkoxycarbonyl groups (e.g. Methoxycarbonyl and ethoxycarbonyl), aryloxycarbonyl groups (e.g. phenoxycarbonyl), carbamo Groups (e.g. carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl and N-methyl-N-octylcarbamoyl), and acylamino groups (e.g. acetylamino, benzoyl Amino, acrylamino and methacrylamino). Such substituents may be further substituted.

When a plurality of R ^{10 's} are present, at least one of them is preferably a substituted alkyl group or a substituted aryl group.

Among the organosilane compounds represented by the general formula [A], vinyl polymerizable substituent-containing organosilane compounds represented by the following general formula [B] are preferable.

In said general formula [B], R <^1> represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. Among these, a hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom and a chlorine atom are preferable; More preferably a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom and a chlorine atom; Especially preferred are hydrogen atoms and methyl groups.

Y represents a single bond, * -COO-**, * -CONH-**, or * -O-**. Among these, single bonds, * -COO-** and * -CONH-** are preferable; Single bonds and * -COO-** are more preferred; * -COO-** is particularly preferred. Where * represents a binding position to ═C (R ¹ ); ** indicates the binding position to L.

L represents a divalent linking chain. Specific examples thereof include a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group containing a linking group (eg, ether, ester and amide) therein, and a substitution containing a linking group therein, or Unsubstituted arylene groups are included. Among these, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and an alkylene group containing a linking group therein are preferable; More preferably an unsubstituted alkylene group, an unsubstituted arylene group and an alkylene group containing an ether or ester linking group therein; Especially preferred are unsubstituted alkylene groups and alkylene groups containing ether or ester linking groups therein. Examples of the substituent include halogen, hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group and aryl group. Such substituents may be further substituted.

n represents 0 or 1, Preferably it is 0.

R ¹⁰ to R ¹⁰ are the same, and preferably in the general formula [A] is a substituted or unsubstituted alkyl group or an unsubstituted aryl group, more preferably an unsubstituted alkyl group or an unsubstituted aryl group.

X is the same as X in general formula [A]. Especially, a halogen atom, a hydroxyl group, and an unsubstituted alkoxy group are preferable; More preferred are a chlorine atom, a hydroxyl group and an alkoxy group having 1 to 6 carbon atoms; Even more preferred are a hydroxyl group and an alkoxy group having 1 to 3 carbon atoms; Methoxy groups are particularly preferred. When there are a plurality of X's, the plurality of X's may be the same or different.

Compounds of formula [A] or formula [B] can be used in combination of two or more thereof. When using a compound together, it is preferable to use together the compound containing a polymeric group, such as a vinyl polymerizable group, and the compound which does not contain a polymeric group. Specific examples of the compound represented by the formula [A] or the formula [B] will be given below, but the present invention should not be construed as being limited thereto.

Among these, (M-1), (M-2), (M-5) and (M-11) are especially preferable. When using a compound together, it is preferable to use together the compound containing the vinyl polymerizable group like M-1, and the compound which does not contain the polymerizable group like M-11, for example.

In general, hydrolysates of the organosilane compound and / or partial condensates thereof are then prepared by treating the organosilane compound in the presence of a catalyst. Examples of catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; Organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; Inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; Organic bases such as triethylamine and pyridine; Metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; And metal chelate compounds containing metals (eg, Zr, Ti and Al) as the center metal. In the present invention, it is preferable to use a metal chelate compound or an acid catalyst such as an inorganic acid and an organic acid. Hydrochloric acid and sulfuric acid are preferred as the inorganic acid; The acid dissociation constant (pKa value (at 25 ° C)) in water is preferably 4.5 or less as the organic acid. More preferred are hydrochloric acid, sulfuric acid, and an organic acid having an acid dissociation constant of 3.0 or less; Even more preferred are hydrochloric acid, sulfuric acid, and an organic acid having an acid dissociation constant of 2.5 or less; Particular preference is given to organic acids having an acid dissociation constant of 2.5 or less in water. Specifically, methanesulfonic acid, oxalic acid, phthalic acid and malonic acid are preferable, and oxalic acid is particularly preferable.

Examples of the metal chelate compound include a metal selected from Zr, Ti, and Al as the central metal, and an alcohol represented by the formula R ³ OH (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms) and a formula R ⁴ COCH ₂ COR ^The compound represented by ⁵ (wherein R ⁴ represents an alkyl group having 1 to 10 carbon atoms; R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms) functions as a ligand, without being particularly limited. Can be used. Two or more metal chelate compounds may be used together within the above range. The metal chelate compounds used in the present invention are preferably of the formula Zr (OR ³ ) _p1 (R ⁴ COCHCOR ⁵ ) _p2 , Ti (0R ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 and Al (OR ³ ) _r1 (R ⁴ COCHCOR ⁵ ) selected from the group of compounds represented by _r2 , and serves to accelerate the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.

In the metal chelate compound, R ³ and R ⁴ may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group and phenyl group. In addition, R ⁵ represents the same alkyl group having 1 to 10 carbon atoms or alkoxy group having 1 to 10 carbon atoms as described above. Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group and t-butoxy group. In addition, in the metal chelate compound, p1, p2, q1, q2, r1 and r2 each satisfy the relation: (p1 + p2) = 4, (q1 + q2) = 4 and (r1 + r2) = 3 The determined integer is shown.

Specific examples of such metal chelate compounds include zirconium chelate compounds such as zirconium tri-n-butoxyethylacetoacetate, zirconium di-n-butoxybis (ethylacetoacetate), zirconium n-butoxytris (ethylacetoacetate) Zirconium tetrakis (n-propylacetoacetate), zirconium tetrakis (acetylacetoacetate) and zirconium tetrakis (ethylacetoacetate); Titanium chelate compounds such as titanium diisopropoxy bis (ethylacetoacetate), titanium diisopropoxy bis (acetylacetate) and titanium diisopropoxy bis (acetylcetone); And aluminum chelate compounds such as aluminum diisopropoxyethylacetoacetate, aluminum diisopropoxyacetylacetate, aluminum isopropoxybis (ethylacetoacetate), aluminum isopropoxybis (acetylacetonate), aluminum tris (ethylaceto Acetate), aluminum tris (acetylacetonate) and aluminum monoacetylacetonato bis (ethylacetoacetate).

Among these metal chelate compounds, zirconium tri-n-butoxyethylacetoacetate, titanium diisopropoxybis (acetylacetonate), aluminum diisopropoxyethylacetoacetate and aluminum tris (ethylacetoacetate) are preferable. These metal chelate compounds may be used alone or in mixture of two or more thereof. Partial hydrolysates of such metal chelate compounds can also be used.

Moreover, in this invention, it is preferable to add a (beta) -diketone compound and / or (beta) -ketoester compound further to the said curable composition. This will be described further below.

The compounds used in the present invention are β-diketone compounds and / or β-ketoester compounds represented by the general formula R ⁴ COCH ₂ COR ⁵ and act as stability enhancers for the curable compositions used in the present invention. R ⁴ represents an alkyl group having 1 to 10 carbon atoms; R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. That is, when the compound coordinates with a metal atom in a metal chelate compound (eg, zirconium, titanium and / or aluminum compound), it is a hydrolyzate of the organosilane compound and / or partial condensation thereof by this metal chelate compound. By inhibiting the accelerated action of the condensation reaction of water, it is believed to act to improve the storage stability of the resulting composition. R ⁴ and R ⁵ constituting the β-diketone compound and / or β-ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

Specific examples of the β-diketone compound and / or β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, sec-butyl aceto Acetate, t-butyl acetoacetate, 2,3-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione and t- Methylhexane-dione is included. Among these, ethyl acetoacetate and acetylacetone are preferable; Acetyl acetone is particularly preferred. These β-diketone compounds and / or β-ketoester compounds may be used alone or in mixture of two or more thereof. In the present invention, the β-diketone compound and / or the β-ketoester compound is used in an amount of preferably 2 moles or more, more preferably 3 to 20 moles per 1 mole of the metal chelate compound. When the amount of the β-diketone compound and / or the β-ketoester compound is less than 2 moles, there is a possibility that the storage stability of the resulting composition is deteriorated, and therefore this is not preferable.

The blending amount of the organosilane compound or its hydrolyzate and / or partial condensate thereof is preferably 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, most preferably 1 to 1 of the total solids of the low refractive index layer. 20 wt%.

The organosilane compound may be added directly to the curable composition (e.g., a coating solution for an anti-glare layer or low refractive index layer), but the organosilane compound may be pretreated in the presence of a catalyst to hydrolyzate the organosilane compound and It is preferred to prepare a partial condensate thereof and to produce the curable composition using the resulting reaction solution (sol solution). In the present invention, by first preparing a composition containing a hydrolyzate and / or partial condensate of the organosilane compound and a metal chelate compound, and then adding a β-diketone compound and / or β-ketoester compound to the composition The resulting solution is preferably contained in the coating solution for at least one of the anti-glare layer or the low refractive index layer, followed by coating.

Silicon-containing compounds as described in (a), (b) or (c) below may be further added to component (D).

(a) silicon alkoxide:

Silicon alkoxides are compounds represented by R _m Si (OR ') _n , wherein R and R' each represent an alkyl group having 1 to 10 carbon atoms; m and n each represent an integer satisfying the relation: (m + n) = 4. Examples of silicon alkoxides include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert- Butoxysilane, tetrapentaethoxysilane, tetrapentaisopropoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-part Methoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxy Silane, dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane and hexyltrimethoxysilane.

(b) silane coupling agent:

Examples of the silane coupling agent include γ- (2-amino-ethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethoxysilane hydrochloride, γ-gly Cidoxypropyltrimethoxysilane, aminosilane, methyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3-trimethoxysilyl) propyl] ammonium chloride, methyltrichlorosilane and dimethyldichlorosilane.

(c) ionizing radiation curable silicon compounds:

Examples of ionizing radiation curable silicon compounds include organosilicon compounds having a molecular weight of 5,000 or less, which contain a plurality of groups which can be reacted and crosslinked by ionizing radiation, for example polymerizable double bond groups. Examples of such reactive organosilicon compounds include single-terminal vinyl functional polysilanes, both-terminal vinyl functional polysilanes, single-terminal vinyl functional polysiloxanes and both-terminal vinyl functional polysiloxanes; And vinyl functional polysilanes or vinyl functional polysiloxanes produced from the reaction of the compounds.

Examples of other compounds include (meth) acryloxysilane compounds such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropylmethyldimethoxysilane.

For example, the following reactive organosilicon compounds described in JP-A-2003-39586 can be used with the binder. The reactive organosilicon compound is used in an amount ranging from 10 to 100% by weight based on the sum of the ionizing radiation curable resin and the reactive organosilicon compound. In particular, in the case of using the ionizing radiation curable organosilicon compound (c), it is possible to form a conductive layer by using only the compound as a resin component.

1- (5) Initiator:

The polymerization of various ethylenically unsaturated group-containing monomers can be carried out by irradiation with ionizing radiation or by heating in the presence of a photo radical initiator or a thermal radical initiator.

In film manufacture of this invention, a photoinitiator and a thermal initiator can be used together.

<Photoinitiator>

Examples of the radical photopolymerization initiator include acetophenones, benzoin, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds and peroxides (for example, JP-A-2001 -139663), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, ropin dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes and Coumarins are included.

Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethyl phenyl ketone, 1-hydroxy-dimethyl-p-isopropyl Phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) buta Non, 4-phenoxydichloroacetophenone and 4-t-butyl-dichloroacetophenone.

Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzenesulfonic acid ester, benzoin toluenesulfonic acid ester, benzoin methyl ether, benzoin ethyl ether and Benzoin isopropyl ether. Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone, p-chlorobenzophenone, 4 , 4'-dimethylaminobenzophenone (Michler's ketone) and 3,3 ', 4,4'-tetra (t-butyl peroxycarbonyl) benzophenone.

Examples of borate salts include Japanese Patent No. 2764769, JP-A-2002-116539 and Kunz and Martin, Red Tech '98. Proceedings, April, pages 19-22 (1998), Chicago, are included. For example, the compounds as described in paragraphs [0022] to [0027] of JP-A-2002-116539 are listed. In addition, specific examples of other organoboron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527 and JP-A-7-292014. Organoboron transition metal-coordination complexes as described. Specific examples thereof also include ionic complexes with cationic dyes.

Examples of phosphine oxides include 2,4,6-trimethylbenzoyl diphenylphosphine oxide.

Examples of active esters include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], sulfonic acid esters and cyclic active ester compounds.

Specifically, compounds 1 to 21 as described in the working examples of JP-A-2000-80068 are particularly preferable.

Examples of oniums include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.

As active halogens, Wakabayashi et al. , Bull Chem. Soc. Japan, Vol. 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-5-27830 and in MP Hutt, Journal of Heterocyclic Chemistry, Vol. 1 (No. 3), 1970], specifically s-triazine compound and oxazole compound in which trihalomethyl group is substituted thereon are specifically listed. More suitably, s-triazine derivatives in which one or more mono-, di- or trihalogen-substituted methyl groups are bonded to the s-triazine ring are listed. Specific examples include 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-bromo-4-di (ethyl acetate) amino) phenyl S-tri comprising 4,6-bis (trichloromethyl) -s-triazine and 2-trihalomethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole Azine or oxathiazole compounds are known. Specifically, compounds as described in pages 14 to 30 of JP-A-58-15503 and pages 6 to 10 of JP-A-55-77742; And compound numbers 1 to 8 as described on page 287 of JP-B-60-27673, compound numbers 1 to 17 as described on pages 443 to 444 of JP-A-60-239736, and US Pat. No. 4,701,399 There are numbers 1 to 19;

Examples of inorganic complexes include bis- (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium do.

Examples of coumarins include 3-ketocoumarin.

These initiators may be used alone or in admixture.

Various examples are described in Saishin UV Koka Gijutsu (Latest UV Curing Technologies), Technical Information Institute Co., Ltd. 159 (1991) and Kiyoshi Kato, Shigaisen Koka Shisuternu (Ultraviolet Ray Curing Systems), published by Sogo Gijutsu Center, pages 65-148 (1988), which are useful for the present invention.

As for commercially available photoradical polymerization initiators, Nippon Kayaku Co., Ltd. KAYACURE series (e.g., DETX-S, BP-1OO, BDMK, CTX, BMS, 2-FAQ, ABQ, CPTX, EPD, ITX, QTX, BTC and MCA) manufactured by IRGACURE manufactured by Ciba Specialty Chemicals Series (e.g., 651, 184, 500, 819, 907, 369, 1173, 1870, 2959, 4265, and 4263), Sartmer Company Inc. ESACURE series (e.g., KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150 and TZT), and combinations thereof, manufactured by

The photopolymerization initiator is preferably used in an amount in the range of 0.1 to 15 parts by weight with respect to 100 parts by weight of the polyfunctional monomer, more preferably in the range of 1 to 10 parts by mass. In particular, by incorporating the photopolymerization initiator into the low refractive index layer of the present invention in the range of 0.1 to 5 parts by weight, crosslinking of the low refractive index layer itself and bonding at the interface can be enhanced, thereby improving the scratch resistance.

<Photoresist>

In addition to a photoinitiator, a photosensitive agent can be used. Specific examples of photosensitizers include n-butylamine, triethylamine, tri-n-butyl phosphine, Michler's ketone and thioxanthone.

In addition, one or more auxiliary such as azide compounds, thiourea compounds and mercapto compounds can be used in combination.

For commercial photosensitizers, Nippon Kayaku Co., Ltd. KAYACURE series (e.g., DMBI and EPA) manufactured by

<Thermal initiator>

Examples of thermal initiators that can be used include organic or inorganic peroxides and organic azo or diazo compounds.

Specifically, examples of the organic peroxide include benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide and butyl hydroperoxide; Examples of inorganic peroxides include hydrogen peroxide, ammonium persulfate and potassium persulfate; Examples of azo compounds include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (propionitrile) and 1,1'-azobis (cyclohexanecarbonitrile); Examples of diazo compounds include diazoaminobenzenes and p-nitrobenzene diazonium.

1- (6) crosslinking compound [constituent component (B) of low refractive index layer of the present invention]

[Curing agent]

In the present invention, a low refractive index layer using a curable composition containing a fluorine-containing polymer containing a hydroxyl group and a compound (curing agent) capable of reacting with a hydroxyl group in the fluorine-containing polymer, that is, a so-called curable resin composition It is preferable to form The curing agent preferably comprises two or more, more preferably four or more sites capable of reacting with hydroxyl groups.

The structure of the curing agent is not particularly limited as long as it contains the aforementioned number of functional groups capable of reacting with hydroxyl groups. Examples thereof include block polyisocyanate compounds having isocyanate groups blocked by a blocking agent such as phenol, such as polyisocyanates, partial condensates or polymers of isocyanate compounds, adducts with polyhydric alcohols, low molecular weight polyester films, and the like. , Aminoplasts and polybasic acids or anhydrides thereof.

Among them, in the present invention, aminoflavor which can cause a crosslinking reaction with a hydroxyl group-containing polymer under acidic conditions in terms of making the storage stability and the action of the crosslinking reaction compatible with each other and in terms of the strength of the formed film. Is preferred. An aminoplast is a compound containing an amino group capable of reacting with a hydroxyl group in a fluorine-containing polymer, ie, a hydroxyalkylamino group or an alkoxyalkylamino group, or a carbon atom adjacent to a nitrogen atom and substituted with an alkoxy group. Specific examples thereof include melamine compounds, urea compounds and benzoguanamine compounds.

The melamine-based compound is generally known as a compound having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples thereof include melamine, alkoxylated melamine, methylolmelamine and alkylated methylmelamine. Among them, methylolated melamine, alkoxylated methylmelamine and derivatives thereof obtained by reacting melamine with formaldehyde under basic conditions are preferable; In view of storage stability, alkoxylated methylmelamine is particularly preferred. In addition, there are no particular limitations on the methylolated melamine and the alkoxylated methylmelamine, and are obtained by the method as described, for example, in Plastic Material Course [8]: Urea-melamine Resins (issued by Nikkan Kogyo Shimbun Ltd.). Various resins can be used.

As the above-mentioned urea compound, in addition to urea, a compound having a 2-imidazolidinone skeleton or a glycol uril skeleton as a polymethylolated urea and alkoxylated methylurea as its derivative and a cyclic urea structure is preferable. Regarding amino compounds such as the urea derivatives, see the above reference [ Urea.melamine Resins ] Various resins, such as those described, can be used.

In this invention, as a compound used suitably as a crosslinking agent, a melamine compound or a glycol uril compound is especially preferable from a compatibility with a fluorine-containing copolymer. Among them, the crosslinking agent is preferably a compound containing a nitrogen atom in its molecule, containing two or more carbon atoms adjacent to the nitrogen atom and substituted with an alkoxy group. Examples of particularly preferred compounds include compounds having structures represented by the following H-1 or H-2 and partial condensates thereof. In the following formulae, R represents an alkyl group or hydroxyl group having 1 to 6 carbon atoms.

The amount of aminoplast added to the fluorine-containing polymer is 1 to 50 parts by weight, preferably 3 to 40 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the copolymer. When the added amount of aminoplast is 1 part by weight or more, the durability as a thin film, which is a characteristic feature of the present invention, can be sufficiently exhibited. When the addition amount is 50 parts by weight or less, when used for optical applications, the low refractive index, which is a characteristic of the low refractive index layer in the present invention, can be maintained. In view of keeping the low refractive index uniform by adding a curing agent, a curing agent having a small increase in refractive index even when added is preferable. From this point of view, among the above-mentioned compounds, a compound having a skeleton represented by H-2 is more preferable.

1- (7) Curing Catalyst:

In the film of this invention, a film is hardened by crosslinking-reacting, heating the hydroxyl group of a fluorine-containing polymer and the hardening | curing agent mentioned above. In the above system, since curing is promoted by an acid, it is preferable to add an acidic substance in the curable resin composition. However, when the conventional acid is added, the crosslinking reaction proceeds even in the coating solution, causing defects (for example, nonuniformity and cissing). Therefore, in order for the storage stability and the curing action to be compatible with each other in the thermal curing system, it is more preferable to add a compound capable of generating an acid by heating as a curing catalyst.

The curing catalyst is preferably a salt consisting of an acid and an organic base. Examples of the acid include organic acids such as sulfonic acid, phosphonic acid and carboxylic acid; And inorganic acids such as sulfuric acid and phosphoric acid. In view of compatibility with the polymer, organic acids are more preferred; Sulfonic and phosphonic acids are even more preferred; Sulfonic acid is most preferred. Preferred examples of sulfonic acids include p-toluenesulfonic acid (PTS), benzenesulfonic acid (BS), p-dodecylbenzenesulfonic acid (DBS), p-chlorobenzenesulfonic acid (CBS), 1,4-naphthalenedisulfonic acid (NDS), Methanesulfonic acid (MsOH) and nonafluorobutane-1-sulfonic acid (NFBS). All of these compounds can be preferably used. (The expressions in brackets are abbreviations.)

The curing catalyst depends greatly on the basicity and boiling point of the organic base combined with the acid. The curing catalysts preferably used in the present invention will be described below from individual viewpoints.

The basicity of an organic base is demonstrated. Organic bases having a low basicity have high acid production efficiency upon heating and are preferable in view of the curing action. However, when the basicity is too low, the storage stability becomes insufficient. Therefore, it is preferable to use an organic base having an appropriate basicity. When the basicity is expressed as the pKa of the conjugated acid as an index, the pKa of the organic base used in the present invention should be 5.0 to 10.5, preferably 6.0 to 10.0, even more preferably 6.5 to 10.0. Regarding the pKa value of the organic base, the value in the aqueous solution is described in The Chemical Handbook Basic Edition (revised edition, 5th edition, edited by The Chemical Society of Japan, published by Maruzen Co., Ltd.), Vol. 2, II, pages 334 to 340, and among these, an organic base having an appropriate pKa can be selected. Moreover, even if it is not described in the target reference document, the compound which has a suitable pKa from a structural point can be used preferably. In addition, compounds having suitable pKa as described in the subject reference will be presented in Table 6 below, but the present invention should not be considered to be limited thereto.

                                                                pKa b-1 N, N-dimethylaniline 5.1 b-2 Benzimidazole 5.5 b-3 Pyridine 5.7 b-4 3-methylpyridine 5.8 b-5 2,9-dimethyl-1,10-phenanthroline 5.9 b-6 4,7-dimethyl-1,10-phenanthroline 5.9 b-7 2-methylpyridine 6.1 b-8 4-methylpyridine 6.1 b-9 3- (N, N-dimethylamino) pyridine 6.5 b-10 2,6-dimethylpyridine 7.0 b-11 Imidazole 7.0 b-12 2-methyl imidazole 7.6 b-13 N-ethylmorpholine 7.7 b-14 N-methylmorpholine 7.8 b-15 Bis (2-methoxyethyl) amine 8.9 b-16 2,2'-iminodieethanol 9.1 b-17 N, N-dimethyl-2-aminoethanol 9.5 b-18 Trimethylamine 9.9 b-19 Triethylamine 10.7

The boiling point of an organic base is demonstrated. An organic base having a low boiling point has a high acid generating efficiency upon heating and is preferable in view of a curing action. Therefore, preference is given to using organic bases having suitable boiling points. The boiling point of the base is preferably 120 ° C. or less.

Examples of compounds which can be preferably used as organic bases in the present invention will be given below, but the present invention should not be considered to be limited thereto. Expressions in brackets indicate boiling points.

b-3: pyridine (115 ° C), b-14: 4-methylmorpholine (115 ° C), b-20: diallylmethylamine (111 ° C), b-19: triethylamine (88.8 ° C), b -21: t-butylmethylamine (67-69 degreeC), b-22: dimethylisopropylamine (66 degreeC), b-23: diethylmethylamine (63-65 degreeC), b-24: dimethylethylamine (36 to 38 ° C), b-18: trimethylamine (3 to 5 ° C)

The boiling point of the organic base used in the present invention is particularly preferably 35 ° C. or higher and 85 ° C. or lower. By using an organic base having a specific range of boiling point, a coating solution having good curing activity, scar resistance and stability can be obtained. The boiling point is more preferably 45 ° C or more and 80 ° C or less, and most preferably 55 ° C or more and 75 ° C or less.

When used as the acid catalyst of the present invention, the salt consisting of an acid and an organic salt can be isolated and used. Alternatively, a solution obtained by mixing an acid with an organic salt that forms a salt in the solution can be used. In addition, one type of acid and organic base may be used, respectively, and various types of acid and organic base may be mixed and used. In the case where a mixture of an acid and an organic base is used, the equivalent ratio of the acid and the organic base is preferably 1 / 0.9 to 1 / 1.5, more preferably 1 / 0.95 to 1 / 1.3, even more preferably 1 / 1.0 to It is preferable to mix so as to be 1 / 1.1.

The proportion of the acid catalyst to be used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, even more preferably based on 100 parts by weight of the fluorine-containing polymer in the above-mentioned cured resin composition. 0.2 to 3 parts by weight.

<Photosensitive acid generator and photo acid generator>

In the present invention, in addition to the above-mentioned heat acid generator, a compound capable of generating an acid upon light irradiation, that is, a photosensitive acid generator may be further added. Photoacid generators that can be used in the present invention will be described in detail below.

Examples of acid generators are known compounds such as photoinitiators of photo cationic polymerization, for photo decoloring agents, photo discoloring agents and microresists of dyes. Known acid generators, and mixtures thereof. The photosensitive acid generator imparts photosensitivity to the film of the curable resin composition, and is a material capable of undergoing photocuring of the film of interest when irradiated such as light. As the photosensitive acid generator, (1) various onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts, iminium salts, arsonium salts, selenium salts and pyridinium salts; (2) sulfone compounds such as β-ketoesters, β-sulfonylsulfones and α-diazo compounds thereof; (3) sulfonic acid esters such as alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters and iminosulfonates; (4) sulfonimide compounds; (5) diazomethane compounds; And others may be mentioned, and these may be appropriately used. Among them, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferred in view of photosensitivity to photopolymerization initiation, material stability of compounds, and the like. For example, the compounds described in paragraphs [0058] to [0059] of JP-A-2002-29162 are mentioned.

The photosensitive acid generator may be used alone or in combination of two or more thereof. Moreover, the photosensitive acid generator may also be used in combination with the above-mentioned thermal acid generator. The ratio of the photosensitive acid generator to be used is preferably 0 to 20 parts by weight, more preferably 0.1 to 10 parts by weight based on 100 parts by weight of the fluorine-containing polymer in the curable resin composition. When the ratio of the photosensitive acid generator is below the above-mentioned upper limit, the resulting cured film is preferable because it has excellent strength and satisfactory transparency.

Photosensitive acid generators may also be used in layers other than the low refractive index layers mentioned above, for example in hard coat layers. The use ratio thereof is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the curable resin composition.

In addition, the contents disclosed in, for example, JP-A-2005-43876 can be used as specific compounds and methods of using the same.

1- (8) Translucent Particles:

Various translucent particles can be used to impart antiglare (surface scattering) or internal scattering properties to the films of the invention, in particular antiglare or hard coat layers.

Translucent particles may be organic particles or inorganic particles. If the particle size is not interspersed, the scattering characteristics in the scattering feature are small, making it easy to design haze values. Plastic beads are suitable as translucent particles. In particular, those having high transparency and having the above-mentioned numerical values in the difference in refractive index with the binder are preferable.

Examples of the organic particles include polymethyl methacrylate particles (refractive index: 1.49), crosslinked poly (acryl-styrene) copolymer particles (refractive index: 1.54), melamine resin particles (refractive index: 1.57), polycarbonate particles (refractive index) : 1.57), polystyrene particles (refractive index: 1.60), crosslinked polystyrene particles (refractive index: 1.61), polyvinyl chloride particles (refractive index: 1.60), and benzoguanamine-melamine formaldehyde particles (refractive index: 1.68).

Examples of inorganic particles include silica particles (refractive index: 1.44), alumina particles (refractive index: 1.63), zirconia particles, titania particles and hollow or porous inorganic particles.

Among them, crosslinked polystyrene particles, crosslinked poly ((meth) acrylate) particles and crosslinked poly (acryl-styrene) particles are preferably used. By adjusting the refractive index of the binder suitably to the refractive index of each translucent particle selected from the above particles, the internal haze, surface haze and center line mean roughness of the present invention can be obtained.

Further, as a main component, a binder consisting of a trifunctional or polyfunctional (meth) acrylate monomer (refractive index after curing: 1.50 to 1.53) is composed of a crosslinked poly (meth) acrylate polymer having an acrylic content of 50 to 100% by weight. Preference is given to using in combination with semitransparent particles. Particular preference is given to a combination of semitransparent particles (refractive index: 1.48 to 1.54) consisting of a crosslinked poly (styrene-acrylic) copolymer and a binder.

In the present invention, the refractive index of the combination of the translucent particles and the binder (translucent resin) is preferably 1.45 to 1.70, more preferably 1.48 to 1.65. In order to make refractive index fall in the said range, the kind and quantity of a binder and a semitransparent particle can be selected suitably. The method of selecting the said kind and quantity can be known easily by experiment beforehand.

Furthermore, in the present invention, the difference in the refractive index between the binder and the semi-transparent particles [(the refractive index of the semi-transparent particles)-(the refractive index of the binder)] is converted to an absolute value, preferably 0.001 to 0.030, more preferably 0.001 to 0.020, More preferably, it is 0.001 to 0.015. When the difference exceeds 0.030, problems such as blurring of film characters, a decrease in dark room contrast, and cloudiness of the surface occur.

Here, the refractive index of the binder can be measured quantitatively, for example, by direct measurement by Abbe's refractometer or by measurement of spectral reflection spectrum or spectral ellipsometry. Can be evaluated. The refractive index of the semi-transparent particles is measured by dispersing an equivalent amount of semi-transparent particles in a solvent having a changed refractive index by changing the mixing ratio of two solvents having different refractive indices, and measuring the turbidity by using Abbe's refractometer. It measures by measuring the refractive index of the solvent used.

In the case of the semi-transparent particles, since the semi-transparent particles are easy to precipitate in the binder, an inorganic filler such as silica may be added to prevent precipitation. Incidentally, increasing the amount of inorganic filler added is effective in preventing precipitation of semi-transparent particles, but adversely affects the transparency of the film. Therefore, it is preferable that the inorganic filler having a particle size of 0.5 mu m or less is contained in the binder in an amount of less than about 0.1% by weight, which does not interfere with the transparency of the film.

The semi-transparent particles preferably have an average particle size of 0.5 to 10 μm, more preferably 2.0 to 6.0 μm. If the average particle size of the translucent particles is less than 0.5 mu m, this is not preferable because the scattering angle distribution of light spreads over a wide angle, causing smearing of characters on the display. On the other hand, when the average particle size exceeds 10 mu m, the thickness of the layer to which the semi-transparent particles are added becomes thick, causing problems such as an increase in curl and cost.

In addition, two or more kinds of translucent particles having different particle sizes may be used together. Respective antiglare can be imparted by the translucent particles having a larger particle size, respectively, and the rough feeling of the surface can be reduced by the translucent particles having a smaller particle size.

The translucent particles are formulated to contain in an amount of preferably 3 to 30% by weight, more preferably 5 to 20% by weight, based on the total solids of the layer to which the translucent particles are added. When the blending amount of the translucent particles is less than 3% by weight, the addition effect is insufficient, whereas when the blending amount exceeds 30% by weight, problems such as blurring of the image, blurring of the surface, and glare occur.

In addition, the semi-transparent particles preferably have a density of 10 to 1,000 mg / m 2, more preferably 100 to 700 mg / m 2.

<Method of producing and classifying semi-transparent particles>

Examples of the preparation method of the semi-transparent particles according to the present invention include suspension polymerization method, emulsion polymerization method, soap-free emulsion polymerization method, dispersion polymerization method and seed polymerization method. This includes. Translucent particles can be produced by any of the above methods. Such preparations are described, for example, in Kobunshi Gosei no Jikkenho (Exerimental Methods of Polymer Synthesis) by Takayuki Otsu and Masayoshi Kinoshita, issued by Kagaku-dojin Publishing Company, Inc., 130 and pages 146 to 147, Gosei Kobunshi Synthetic Polymers, Vol. 1, pages 246-290 , ibid. , Vol. 3, pages 1 to 108], Japanese Patent Nos. 2543503, 3508304, 2746275, 3521560 and 3580320, JP-A-10-1561, JP-A-7-2908, JP-A- It may be carried out according to the method described in 5-297506 and JP-A-2002-145919.

For particle size distribution of translucent particles, monodisperse particles are preferred in terms of haze value and diffusivity and homogeneity of coating surface properties. For example, when defining particles having a particle size of at least 20% larger than the average particle size as coarse particles, the proportion of such coarse particles is preferably 1% or less, more preferably 0.1% or less, even more preferred. Preferably 0.01% or less. In order to obtain particles having such particle size distribution, it is an effective method to carry out sorting after the preparation or synthesis reaction. By increasing the number of fractions or enhancing their strength, particles with the desired particle size distribution can be obtained.

For classification, it is preferable to use methods such as air fractionation, centrifugal fractionation, precipitation fractionation, filtration fractionation and electrostatic fractionation.

1- (9) inorganic particles:

In the present invention, various inorganic particles may be used to improve physical characteristics such as hardness and optical characteristics such as reflectance and scattering properties.

Examples of the inorganic particles include oxides of one or more metals selected from silicon, zirconium, aluminum, indium, zinc, tin and antimony. Also included are inorganic particles released as component (E). Specific examples thereof include ZrO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O _3, and ITO. In addition, BaSO ₄ , CaCO ₃ , talc and kaolin are included.

Regarding the particle size of the inorganic particles used in the present invention, it is preferable that the inorganic particles are separated as finely as possible in the dispersion medium. The particle size of the inorganic particles is 1 to 200 nm, preferably 5 to 150 nm, more preferably 10 to 100 nm, particularly preferably 10 to 80 nm, in terms of weight average molecular weight. By finely separating the inorganic particles to 100 nm or less, the film can be formed so that the transparency of the film is not disturbed. The particle size of the inorganic particles can be measured by light scattering or from electron micrographs.

The inorganic particles preferably have a specific surface area of 10 to 400 m 2 / g, more preferably 20 to 200 m 2 / g, most preferably 30 to 150 m 2 / g.

It is preferable to add the inorganic particles used in the present invention to the coating solution for layers used as the dispersion in the dispersion medium.

It is preferable to use a liquid having a boiling point of 60 to 170 ° C as a dispersion medium of the inorganic particles. Examples of dispersion media include water, alcohols (eg methanol, ethanol, isopropanol, butanol and benzyl alcohol), ketones (eg acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone), esters ( For example methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate and butyl formate), aliphatic hydrocarbons (eg, hexane and cyclohexane), halogenated hydrocarbons (eg Methylene chloride, chloroform and carbon tetrachloride), aromatic hydrocarbons (eg benzene, toluene and xylene), amides (eg dimethylformamide, dimethylacetamide and n-methylpyrrolidone), ethers ( Diethyl ether, dioxane and tetrahydrofuran) and ether alcohols (eg 1-methoxy-2-propanol). Among them, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferred.

Most preferred dispersion medium is methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone.

Inorganic particles are dispersed using a disperser. Examples of dispersers include sand grinder mills (eg, pin-providing bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. Among these, sand grinder mill and high speed impeller mill are particularly preferable. Moreover, preliminary dispersion processing can be performed. Examples of the disperser used for the predispersion treatment include a ball mill, a triple roll mill, a kneader and an extruder.

<High refractive index particle>

Hardening material of the composition in which the inorganic particle which has high refractive index is disperse | distributed in a monomer, an initiator, and an organic substituted silicon compound for the purpose of realizing the high refractive index of the layer which comprises this invention.

In this case, ZrO ₂ and TiO ₂ are particularly preferably used as the inorganic particles in view of the refractive index. ZrO ₂ is most preferable for the purpose of realizing the high refractive index of the hard coat layer; The fine particles of TiO ₂ are most preferred as particles for the high refractive index layer or the medium refractive index layer.

Particularly preferred as the particles of TiO ₂ described above are inorganic particles containing TiO ₂ as a main component and containing at least one element selected from cobalt, aluminum and zirconium. As used herein, "major component" means a component having the highest content (% by weight) of the components constituting the particle.

In the present invention, the particles composed of TiO ₂ as the main component preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, most preferably 2.20 to 2.80.

The primary particles of the particles composed of TiO ₂ as the main component preferably have a weight average molecular weight of 1 to 200 nm, more preferably 1 to 150 nm, even more preferably 1 to 100 nm, particularly preferably 1 To 80 nm.

In the crystal structure of the particles composed of TiO ₂ as the main component, it is preferable that the main component is a rutile structure, a rutile / analyzed mixed structure, an anatase structure, or an amorphous structure. Among these, it is especially preferable that the main component has a rutile structure. As used herein, "major component" means a component having the highest content (% by weight) of the components constituting the particle.

By including at least one element selected from Co (cobalt), Al (aluminum) and Zr (zirconium) in the particles containing TiO ₂ as a main component, the photocatalytic activity of TiO ₂ is suppressed and the weather resistance of the film of the present invention It is possible to improve.

Co (cobalt) is a particularly preferred element. Moreover, it is preferable to use 2 or more types of elements.

In the present invention, the inorganic particles composed of TiO ₂ as a main component may have a core / shell structure through surface treatment as described in JP-A-2001-166104.

The amount of the monomer or inorganic particles added in the layer is preferably 10 to 90% by weight, more preferably 20 to 80% by weight of the total weight of the binder. Two or more kinds of inorganic particles can be used in the layer.

<Low refractive index particle> [A structural component (E) of the low refractive index layer of this invention]

It is preferable that the inorganic particle contained in a low refractive index layer has a low refractive index. Examples of these include fine particles of magnesium fluoride and silica. Silica fine particles are particularly preferable in view of refractive index, dispersion stability and cost.

The average particle size of the silica fine particles is preferably 30% or more and 150% or less, more preferably 35% or more and 80% or less, even more preferably 40% or more and 60% or less of the low refractive index layer thickness. That is, when the thickness of the low refractive index layer is 100 nm, the particle size of the silica fine particles is preferably 30 nm or more and 150 nm or less, more preferably 35 nm or more and 80 nm or less, even more preferably 40 nm or more and 60 nm. It is as follows.

If the particle size of the silica fine particles is too small, the effect of improving the scratch resistance is low, and if too large, fine nonuniformity is formed on the surface of the low refractive index layer, thereby deteriorating appearance such as deep black and overall reflection. Silica fine particles can be crystalline or amorphous; It may be monodisperse particles; As long as the prescribed particle size is correct, it may be coagulated particles. Although the shape of the silica fine particles is most preferably spherical, there is no problem even when it is amorphous.

Moreover, one or more silica fine particles ("small particles-") having an average particle size of 25% or less of the low refractive index layer thickness together with the silica fine particles having the above-described particle size (referred to as "large particle-size silica fine particles"). Size silica fine particles).

Since small particle-size silica fine particles may be present in the gaps between the large particle-size silica fine particles, this may serve as a holding agent for the large particle-size silica fine particles.

When the thickness of the low refractive index layer is 100 nm, the average particle size of the small particle-sized silica fine particles is preferably 1 nm or more and 20 nm or less, more preferably 5 nm or more and 15 nm or less, particularly preferably 10 nm or more and 15 nm or less. The use of such silica fine particles is preferable in view of the raw material cost and the effect of the holding agent.

The coating amount of the low refractive index particles is preferably 1 mg / m ² to 100 mg / m ² , more preferably 5 mg / m ² to 80 mg / m ² , even more preferably 10 mg / m ² to 60 mg / m ² . When the coating amount of the low refractive index particles is too small, the effect of improving the scar resistance becomes small, and when too large, fine nonuniformity is formed on the surface of the low refractive index layer, thereby deteriorating appearance such as deep black and overall reflection.

<Hollow Silica Particles>

For the purpose of making the refractive index smaller, it is preferable to use hollow silica fine particles.

The hollow silica fine particles preferably have a refractive index of 1.15 to 1.40, more preferably 1.17 to 1.35 and most preferably 1.17 to 1.30. The refractive index referred to herein refers to the refractive index as a whole particle and does not represent the refractive index of silica alone as the outermost part to form hollow silica fine particles. At this time, if the radius of the empty space in the particle is defined as "a", and the radius of the outermost part of the particle is defined as "b", the porosity x represented by the following formula VIII:

Formula VIII

x = (4πa3 / 3) / (4πb3 / 3) × 100

Is preferably 10 to 60%, more preferably 20 to 60%, most preferably 30 to 60%. In order to make the hollow silica fine particles have smaller refractive index and greater porosity, only the outermost thickness is thinned, so that the strength as the particles is weakened. Therefore, particles having a low refractive index of less than 1.15 are not preferable in terms of scar resistance.

Processes for the preparation of hollow silica are described, for example, in JP-A-2001-233611 and JP-A-2002-79616. Particular preference is given to particles having an empty space inside the outer shell, in which the pores of the outer shell are located. Often, the refractive index of such hollow silica particles can be calculated by the method described in JP-A-2002-79616.

The coating amount of the hollow silica is preferably 1 mg / m ² to 100 mg / m ² , more preferably 5 mg / m ² to 80 mg / m ² , even more preferably 10 mg / m ² to 60 mg. / m ² . If the coating amount of the hollow silica is too small, the effect of realizing low refractive index and the improvement of scar resistance are low, and if too high, fine nonuniformity is formed on the surface of the low refractive index layer, and the deep black and the overall reflection The same appearance deteriorates.

The average particle size of the hollow silica is preferably 30% or more and 150% or less, more preferably 35% or more and 80% or less, even more preferably 40% or more and 60% or less of the low refractive index layer thickness. That is, when the thickness of the low refractive index layer is 100 nm, the particle size of the hollow silica is preferably 30 nm or more and 150 nm or less, more preferably 35 nm or more and 80 nm or less, even more preferably 40 nm or more and 65 nm. It is as follows.

If the particle size of the silica fine particles is too small, the proportion of the void space is reduced, the refractive index reduction effect can not be expected, if too large, fine non-uniformity is formed on the low refractive index layer, the appearance such as deep black and overall reflection Worsens. The silica fine particles may be crystalline or amorphous and may be monodisperse particles. The shape of the silica fine particles is most preferably spherical, but there is no problem even when it is amorphous.

Moreover, for hollow silica, two or more hollow silicas with different average particle sizes can be used together. Herein, the average particle size of the hollow silica can be determined by electron micrographs.

In the present invention, the hollow silica preferably has a specific surface area of 20 to 300 m ² / g, more preferably 30 to 120 m ² / g, most preferably 40 to 90 m ² / g. Surface area can be measured by the BET method using nitrogen.

In the present invention, it is possible to use silica particles without hollow space together with hollow silica. Silicas without void spaces preferably have a particle size of 30 nm or more and 150 nm or less, more preferably 35 nm or more and 100 nm or less, most preferably 40 nm or more and 80 nm or less.

1- (10) conductive particles:

Various conductive particles can be used to impart conductivity to the film of the invention.

It is preferable that the conductive particles are formed of metal oxides or nitrides. Examples of metal oxides or nitrides include tin oxide, indium oxide, zinc oxide and titanium nitride. Of these, tin oxide and indium oxide are particularly preferred. The conductive inorganic particles include, as main components, the metal oxides or nitrides, and may further contain other elements. As used herein, "main component" means a component having the maximum content (% by weight) of the components constituting the particle. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and Halogen atoms are included. For the purpose of enhancing conductivity of tin oxide and indium oxide, it is preferable to use Sb, P, B, Nb, In, V or halogen atoms. Particular preference is given to tin oxides (ATO) comprising Sb and indium oxides (ITO) comprising Sn. The proportion of Sb in ATO is preferably from 3 to 20% by weight; The proportion of Sn in ITO is preferably 5 to 20% by weight.

The primary particles of the conductive inorganic particles used in the antistatic layer preferably have an average particle size of 1 to 150 nm, more preferably 5 to 100 nm and most preferably 5 to 70 nm. The conductive inorganic particles in the antistatic layer to be formed have an average particle size of 1 to 200 nm, preferably 5 to 150 nm, more preferably 10 to 100 nm and most preferably 10 to 80 nm. The average particle size of the conductive inorganic particles is the average particle size that predicts the weight of the particles, and can be measured by light scattering techniques or electron micrographs.

The conductive inorganic particles preferably have a specific surface area of 10 to 400 m ² / g, more preferably 20 to 200 m ² / g, most preferably 30 to 150 m ² / g.

Conductive inorganic particles can be applied to the surface treatment. Surface treatment is carried out using inorganic compounds or organic compounds. Examples of the inorganic compound used for the surface treatment include alumina and silica. Silica treatment is particularly preferred. Examples of organic compounds used for surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents and titanate coupling agents. Of these, the silane coupling agent is most preferred. Surface treatment can be performed by combining two or more surface treatments.

The shape of the conductive inorganic particles is preferably rice grain, spherical, square, spindle shaped or amorphous.

Two or more kinds of conductive particles may be used together in a specific layer or as a film.

The proportion of the conductive inorganic particles in the antistatic layer is preferably 20 to 90% by weight, more preferably 25 to 85% by weight, even more preferably 30 to 80% by weight.

The conductive inorganic particles can be used in the dispersion state for preparing the antistatic layer.

1- (11) Surface Treatment Agents:

For the purpose of inventing to enhance binding properties or compatibility of binder components or dispersions in dispersions or coating solutions or to stabilize dispersions, the inorganic particles used in the present invention are subjected to physical surface treatments such as plasma discharge treatment and corona discharge treatment. Or the chemical surface treatment using a surfactant, a coupling agent, or the like.

Surface treatment can be performed using a surface treating agent made of an inorganic compound or an organic compound. Examples of the inorganic compound used for the surface treatment include cobalt-containing inorganic compounds (for example, CoO ₂ , Co ₂ O ₃ and Co ₃ O ₄ ), aluminum-containing inorganic compounds (for example, Al ₂ O ₃ and Al ( OH) ₃ ), zirconium-containing inorganic compounds (eg ZrO ₂ and Zr (OH) ₄ ), silicon-containing inorganic compounds (eg SiO ₂ ) and iron-containing inorganic compounds (eg Fe ₂ O ₃ ) Is included.

Of these, cobalt-containing inorganic compounds, aluminum-containing inorganic compounds and zirconium-containing inorganic compounds are particularly preferable; Most preferred are cobalt containing inorganic compounds, Al (OH) ₃ and Zr (OH) ₄ .

Examples of organic compounds used for surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents and titanate coupling agents. Of these, the silane coupling agent is most preferred. Particular preference is given to performing the surface treatment with one or more silane coupling agents (eg organosilane compounds) and partial hydrates or condensates thereof.

Examples of titanate coupling agents include metal alkoxides such as tetramethoxytitanium, tetraethoxytitanium and tetraisopropoxytitanium; And PLENACT series (eg, KR-TTS, KR-46B, KR-55 and KR-41B, all of which are manufactured by Ajinomoto Co., Inc.).

As the organic compound used for the surface treatment, polyols and alkanolamines and other organic compounds containing anionic groups are preferable; Especially preferred are organic compounds comprising a carboxyl group, sulfonic acid group or phosphoric acid group. Stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid and the like can be preferably used.

It is preferable that the organic compound used for surface treatment further contains a crosslinking or a polymerizable functional group. Examples of crosslinking or polymerizable functional groups include ethylenically unsaturated groups (eg, (meth) acrylic groups, allyl groups, stearyl groups, and vinyloxy groups), cations that can withstand addition reactions or polymerization reactions by radical species. Sexically polymerizable groups (eg, epoxy groups, oxantanyl groups and vinyloxy groups) and polycondensation reactive groups (eg, hydrolyzable silyl groups and N-methylol groups). Of these, ethylenically unsaturated group-containing groups are preferred.

Two or more kinds of the above surface treatments may be employed. Particular preference is given to combinations of aluminum containing inorganic compounds and zirconium containing inorganic compounds.

When the inorganic particles are silica, it is particularly preferable to use a coupling agent. Alkoxy metal compounds (for example, titanium coupling agents and silane coupling agents) are preferably used as coupling agents. Above all, the silane coupling process is particularly effective.

The coupling agent is a surface treatment agent for the inorganic filler of the low refractive index layer, and is used for pre-surface treatment application before the preparation of the coating solution. It is preferable to include a coupling agent in the target layer by further adding as an additive in preparing the coating solution for the layer.

For the purpose of reducing the load of the surface treatment, it is preferable to disperse the silica fine particles in the medium before the surface treatment.

Specific examples of surface treating agents and catalysts for surface treatment which can be preferably used in the present invention include organosilane compounds and catalysts described, for example, in WO 2004/017105.

1- (12) Dispersant:

Various dispersants may be used to disperse the particles used in the present invention.

It is preferred that the dispersant further comprise a crosslinking or polymerizable functional group. Examples of crosslinking or polymerizable functional groups include ethylenically unsaturated groups (e.g., (meth) acrylic groups, allyl groups, stearyl groups and vinyloxy groups) capable of withstanding addition reactions or polymerization reactions by radical species, cationic Polymerizable groups (eg, epoxy groups, oxatanyl groups and vinyloxy groups) and polycondensation reactive groups (eg, hydrolyzable silyl groups or N-methylol groups). Among these, an ethylenically unsaturated group containing group is preferable.

For the dispersion of the inorganic particles, in particular for the dispersion of the inorganic particles composed of TiO ₂ as a main component, it is preferable to use a dispersant containing an anionic group. More preferably, the dispersant comprises anionic groups and crosslinked or polymerizable functional groups. It is particularly preferable that the target crosslinking or polymerizable functional group is included in the side chain of the dispersant.

As anionic groups, acidic proton-containing groups such as carboxyl groups, sulfonic acid groups (sulfo), phosphoric acid groups (phosphono) and sulfonamide groups or salts thereof are effective. Above all, carboxyl groups, sulfonic acid groups, phosphoric acid groups and salts thereof are preferred; Carboxyl groups and phosphoric acid groups are particularly preferred. Regarding the number of anionic groups included in the dispersant per molecule, several species may be included in one molecule. The number of anionic groups is on average preferably 2 or more, more preferably 5 or more, particularly preferably 10 or more. Moreover, several species of anionic groups to be included in the dispersant may be included in one molecule.

In the dispersant comprising anionic groups in the side chain, the composition of the anionic group-containing repeating unit is 10 ^-4 to 100 mol%, preferably 1 to 50 mol%, particularly preferably 5 to 20 mol, based on the total moles of the repeating unit. %to be.

It is preferred that the dispersant further comprise a crosslinking or polymerizable functional group. Examples of crosslinking or polymerizable functional groups include ethylenically unsaturated groups (e.g., (meth) acrylic groups, allyl groups, stearyl groups and vinyloxy groups) capable of withstanding addition reactions or polymerization reactions by radical species, cationic Polymerizable groups (eg, epoxy groups, oxatanyl groups and vinyloxy groups) and polycondensation reactive groups (eg, hydrolyzable silyl groups and N-methylol groups) are included. Among these, groups containing ethylenically unsaturated groups are preferable.

The number of crosslinking or polymerizable functional groups contained in the dispersing agent per molecule is preferably 2 or more, more preferably 5 or more, particularly preferably 10 or more on average. Moreover, various kinds of crosslinking or polymerizable functional groups to be included in the dispersant may be included in one molecule.

In a preferred dispersant used in the present invention, as the repeating unit containing an ethylenically unsaturated group in the side chain, poly-1,2-butadiene or poly-1,2- bonded to a specific residue (R group in -COOR or -CONHR) Isoprene structures or repeating units of (meth) acrylic esters or amides can be used. Examples of the specific residue (R group) include-(CH ₂ ) _n -CR ²¹ = CR ²² R ²³ ,-(CH ₂ O) _n -CH ₂ CR ²¹ = CR ²² R ²³ ,-(CH ₂ CH ₂ O) _n -CH ₂ CR ²¹ = CR ²² R ²³ ,-(CH ₂ O) _n -NH-CO-O-CH ₂ CR ²¹ = CR ²² R ²³ ,-(CH ₂ ) _n -O-CO-CR ²¹ = CR ²² R ²³ and — (CH ₂ CH ₂ O) _n —X _wherein R ²¹ to R ²³ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group, or an aryloxy R ²¹ and R ²² or R ²³ may be taken together to form a ring; n represents an integer from 1 to 10; X represents a dicyclopentadienyl moiety. Specific examples of R of the ester moiety include -CH ₂ CH = CH ₂ (corresponding to the polymer of allyl (meth) acrylate described in JP-A-64-17047), -CH ₂ CH ₂ O-CH ₂ CH = CH ₂ , -CH ₂ CH ₂ OCOCH = CH ₂ , -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , -CH ₂ C (CH ₃ ) = CH ₂ , -CH ₂ CH = CH-C ₆ H ₅ , -CH ₂ CH ₂ OCOCH = CH-C ₆ H ₅ , -CH ₂ CH ₂ -NHCOO-CH ₂ CH = CH ₂ and -CH ₂ CH ₂ OX (where X represents a dicyclopentadienyl residue) Included. Specific examples of R of the amide moiety include -CH ₂ CH = CH ₂ , -CH ₂ CH ₂ -Y (wherein Y represents 1-cyclohexenyl residue), -CH ₂ CH ₂ -OCO-CH = CH ₂ and —CH ₂ CH ₂ —OCO—C (CH ₃ ) ═CH ₂ .

In the ethylenically unsaturated group-containing dispersant, free radicals (polymerization initiation radicals or growth radicals in the course of the polymerization of the polymerizable compound) are added to the unsaturated group and the addition polymerization is carried out directly between the molecules or through the polymerization chain of the polymerizable compound. Causing crosslinking between the molecules to cause curing. Alternatively, atoms in the molecule (eg, hydrogen atoms on carbon atoms adjacent to unsaturated bond groups) are removed by free radicals to form polymer radicals, which are then bonded to each other to form crosslinks between the molecules, thereby providing curing Occurs.

There is no particular limitation on the weight average molecular weight (Mw) of the dispersant containing an anionic group and a crosslinking or polymerizable functional group, and including a target crosslinking or polymerizable functional group in the side chain, but is preferably 1,000 or more. The weight average molecular weight (Mw) of the dispersant is more preferably 2,000 to 1,000,000, even more preferably 5,000 to 200,000, particularly preferably 10,000 to 100,000.

Although the monomer containing a crosslinking or polymerizable functional group may constitute all of the repeating units other than the anionic group containing repeating unit, preferably 5 to 50 mol%, particularly preferably 5 to 30 mol% of the total moles of the crosslinking or repeating unit. Occupies.

The dispersant may be a copolymer with suitable monomers other than monomers comprising crosslinked or polymerizable functional groups and anionic groups. There is no particular limitation on the copolymerization component, but it is selected from various aspects such as dispersion stability, compatibility with the remaining monomer components, and strength of the film to be formed. Preferred examples thereof include methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate and styrene.

The form of the dispersant is not particularly limited, but is preferably in the form of a block copolymer or a random copolymer. In view of ease of synthesis, the form of the random copolymer is particularly preferred.

The amount of the dispersant used for the inorganic particles is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, most preferably 5 to 20% by weight. Moreover, two or more dispersants may be used together.

1- (13) antifouling agent:

In the film of the present invention, in particular at the top layer of the film, it is preferable to appropriately add a known polysiloxane-based or fluorine-based antifouling agent and a slipping agent, etc., for the purpose of imparting properties such as antifouling property, water resistance, fire resistance and smoothness. Do.

When such an additive is added, the amount of the additive added is preferably in the range of 0.01 to 20% by weight, more preferably in the range of 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight of the total solids of the low refractive index layer. Is in the range of.

[Compound of polysiloxane structure]

[Structural Component (F) of Low Refractive Index Film of the Present Invention]

Next, the compound of polysiloxane structure will be described.

In the present invention, a compound having a polysiloxane structure is used for the purpose of improving the scratch resistance by imparting smoothness and imparting antifouling property. The structure of the compound is not particularly limited, and examples thereof include a structure including a plurality of dimethylsilyloxy units as repeating units, and a substituent including a substituent at the side chain and / or terminal of the chemical chain. In addition, structural units other than dimethylsilyloxy may be included in the chemical chain containing dimethylsilyloxy as a repeating unit.

The molecular weight of the compound of the polysiloxane structure is not particularly limited, but is preferably 100,000 or less, particularly preferably 50,000 or less, most preferably 3,000 to 30,000.

In view of preventing migration from occurring, it is preferable to contain a hydroxyl group or a functional group capable of reacting with a hydroxyl group to form a bond. The bond formation reaction proceeds rapidly under heating conditions and / or in the presence of a catalyst. Examples of such substituents include epoxy groups and carboxyl groups. Preferred examples of such compounds will be provided below, but the invention should not be construed as being limited thereto.

(Hydroxyl group-containing compound)

X-22-16OAS, KF-600l, KF-6002, KF-6003, X-22-17ODX, X-22-176DX, X-22-1 76D and X-22-176F (all of these are Shin-Etsu Chemical Co., Ltd .; FM-441l, FM-442l, FM-4425, FM-041l, FM-0421, FM-0425, FM-DA11, FM-DA21 and FM-DA25 (all of which are manufactured by Chisso Corporaiton); And CMS-626 and CMS-222 (all of which are manufactured by Gelest, Inc.).

(Compound containing functional group that can react with hydroxyl group)

X-22-162C and KF-105, all of which are manufactured by Shin-Etsu Chemical Co., Ltd .; And FM-5511, FM-5521, FM-5525, FM-6611, FM-6621, and FM-6625 (all of which are manufactured by Chisso Corporation)

In addition to the above polysiloxane based compounds, other polysiloxane based compounds may further be used together. Preferred examples thereof include compounds containing a plurality of dimethylsilyloxy units as repeating units, and containing substituents on the side chain and / or terminal of the chemical chain. In addition, structural units other than dimethylsilyloxy may be included in the chemical chain containing dimethylsilyloxy as a repeating unit. The substituents may be the same or different, and it is preferable that a plurality of substituents are contained. Preferred examples of the substituent include, for example, groups containing acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, oxetanyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group or amino group. Included. The molecular weight of the polysiloxane based compound is not particularly limited, but is preferably 100,000 or less, more preferably 50,000 or less, particularly preferably 3,000 to 30,000, most preferably 10, 000 to 20,000. The silicon atom content of the silicone based compound is not particularly limited, but is preferably at least 18.0% by weight, particularly preferably 25.0 to 37.0% by weight, most preferably 30.0 to 37.0% by weight. Preferred examples of silicone based compounds include X-22-174DX, X-22-2426, X-22-164B, X-22-164C and X-22-1821 (all of which are manufactured by Shin-Etsu Chemical Co., Ltd.). Trade name); FM-0725, FM-7725, FM-6621 and FM-1121 (all of which are trade names of Chisso Corporation); And DMS-U22, RMS-033, RMS-083, UMS-l82, DMS-H21, DMS-H31, HMS-301, FMS121, FMS123, FMS131, FMS141 and FMS221, all of which are trade names of Gelest, Inc. This includes.

As a fluorine-based compound used as an antifouling agent, a compound containing a fluoroalkyl group is preferable. The target fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Fluoroalkyl groups are linear structures (e.g., -CF ₂ CF ₃ , -CH ₂ (CF ₂ ) ₄ H, -CH ₂ (CF ₂ ) ₃ CF ₃ and -CH ₂ CH ₂ (CF ₂ ) ₄ H) Branched structures (eg, CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ and CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H), or An alicyclic structure (preferably a 5-membered ring or a 6-membered ring; for example, a perfluorocyclohexyl group, a perfluorocyclopentyl group, and an alkyl group substituted with the aforementioned group); Ether linkages (eg, CH ₂ OCH ₂ CF ₂ CF ₃ , CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ and CH ₂ CH ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H). Plural fluoroalkyl groups may be contained in the same molecule.

It is preferable that a fluorine base compound further contains the substituent which contributes to formation of the bond with respect to a low refractive index layer film, or miscibility with these. The target substituents may be the same or different and preferably contain a plurality of substituents. Preferred examples of the substituent include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group and amino group. The fluorine based compound may be an oligomer or a polymer with a fluorine atom-free compound. Its molecular weight is not particularly limited. The content of fluorine atoms in the fluorine-based compound is not particularly limited, but is preferably 20% by weight or more, particularly preferably 30 to 70% by weight, most preferably 40 to 70% by weight. Preferred examples of the fluorine-based compound include R-2020, M-2020, R-3833 and M-3833 (all of which are trade names of Daikin Industries, Ltd.); And MEGAFAC F-171, MEGAFAC F-172 and MEGAFAC F-170A and DEFENSA MCF-300 (all of which are trade names of Dainippon Ink and Chemical, Incorporated). However, the present invention should not be construed as being limited thereto.

For the purpose of imparting properties such as dust removal properties and antistatic properties, dust removers or antistatic agents such as known cationic surfactants and polyoxyalkylene based compounds may also be added as appropriate. In such dust removers or antistatic agents, structural units thereof may be included as part of the functional groups in the silicone based compound or fluorine based compound. When such a dust remover and an antistatic agent are added as an additive, preferably in the range of 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight of the total solids of the low refractive index layer Is added in amounts. Preferred examples of dust remover or antistatic agent include MEGAFAC F-150 (Dainippon Ink and Chemicals, trade name of Incorporated) and SH-3748 (trade name of Dow Corning Toray Co., Ltd.). However, the present invention should not be construed as being limited thereto.

1- (14) Surfactant:

In particular, in order to ensure uniformity in surface properties such as coating non-smoothness, dry non-smoothness and point defects, any one or both of the fluorine based surfactant and the silicon based surfactant may be added to the coating composition for forming the light diffusion layer. It is preferable to contain. In particular, fluorine-based surfactants can be preferably used because of their effect of improving the defects of surface properties such as coating non-smoothness, dry non-smoothness and point defects with smaller amounts of addition. By bringing high speed coating applicability it is possible to improve productivity and at the same time improve the uniformity of the surface properties.

Preferred examples of fluorine-based surfactants include fluoro aliphatic group-containing copolymers (also referred to as "fluorine-based polymers"). As the fluorine-based polymer, an acrylic resin or methacrylic resin, or a copolymerizable vinyl-based monomer, containing a repeating unit corresponding to the following monomer (i) or containing a repeating unit corresponding to the following monomer (ii). And copolymers thereof are useful.

(i) a fluoro aliphatic group-containing monomer represented by the following formula (a):

In formula (a), R ¹¹ represents a hydrogen atom or a methyl group; X represents an oxygen atom, a sulfur atom or -N (R ¹² )-; m represents an integer of 1 or more and 6 or less; n represents the integer of 2-4. R <^12> represents a hydrogen atom or a C1-C4 alkyl group, especially a methyl group, an ethyl group, a propyl group, or a butyl group, Among these, a hydrogen atom and a methyl group are preferable. X is preferably an oxygen atom.

(ii) a monomer represented by the following formula (b) copolymerizable with the monomer of (i):

In formula (b), R ¹³ represents a hydrogen atom or a methyl group; Y represents an oxygen atom or a sulfur atom or -N (R ¹⁵ )-; R <^15> represents a hydrogen atom or a C1-C4 alkyl group, especially a methyl group, an ethyl group, a propyl group, or a butyl group, Among these, a hydrogen atom and a methyl group are preferable. Y is preferably an oxygen atom, -N (H)-or -N (CH ₃ )-.

R ¹⁴ represents an optionally substituted linear, branched or cyclic alkyl group having 4 to 20 carbon atoms. Examples of the substituent of the alkyl group represented by R ¹⁴ include hydroxyl group, alkylcarbonyl group, arylcarbonyl group, carboxyl group, alkyl ether group, aryl ether group, halogen atom (for example, fluorine atom, chlorine atom and bromine atom), nitro group , Cyano groups and amino groups are included. However, it should not be construed that the present invention is limited thereto. As a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, Pentadecyl groups, octadale groups and eicosanyl groups (each of which may be linear or branched); Monocyclic cycloalkyl groups such as cyclohexyl group and cycloheptyl group; And polycyclic cycloalkyl groups such as bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, tetracyclododecyl group, adamantyl group, norbornyl group and tetracyclodecyl group.

The amount of the fluoro aliphatic group-containing monomer represented by the formula (a) used in the fluorine-based polymer used in the present invention is 10 mol% or more, preferably 15 to 70 mol, based on each monomer of the fluorine-based polymer. %, More preferably 20 to 60 mol%.

The fluorine-based polymer used in the present invention preferably has a weight average molecular weight of 3,000 to 100,000, more preferably 5,000 to 80,000.

In addition, the amount of the fluorine-based polymer used in the present invention is preferably in the range of 0.001 to 5% by weight, more preferably in the range of 0.005 to 3% by weight, more preferably 0.01 to 1% by weight, based on the coating solution. Range. When the added amount of the fluorine-based polymer is less than 0.001% by weight, the effect is insufficient, while when the added amount is more than 5% by weight, the drying of the film is not sufficiently performed, and the performance as a film (for example, reflectance and scar resistance) ) Is adversely affected.

1- (15) Thickener:

In the films of the invention, thickeners can be used for the purpose of controlling the viscosity of the coating solution.

In particular, for the hard coat layer containing scattering particles, it is preferable to add a thickener. By increasing the viscosity, it is possible to lower the surfacing or downwelling rate of the scattering particles.

As used herein, "thickener" means a substance that can increase the viscosity of a solution by addition thereof. The level of increase in viscosity of the coating solution by addition of thickeners is preferably 0.05 to 50 cP (mPa.s), more preferably 0.10 to 20 cP (mPa.s), most preferably 0.10 to 10 cP ( mPa · s).

Examples of such thickeners will be provided below, but the present invention should not be construed as being limited thereto.

Poly-ε-caprolactone

Poly-ε-caprolactone diol

Poly-ε-caprolactone triol

Polyvinyl acetate

Poly (ethylene adipate)

Poly (1,4-butylene adipate)

Poly (1,4-butylene glutarate)

Poly (1,4-butylene succinate)

Poly (1,4-butylene terephthalate)

Poly (ethylene terephthalate)

Poly (2-methyl-1,3-propylene adipate)

Poly (2-methyl-1,3-propylene glutarate)

Poly (neopentyl glycol adipate)

Poly (Neopentyl Glycol Sebacate)

Poly (1,3-propylene adipate)

Poly (1,3-propylene glutarate)

Polyvinyl butyral

Polyvinyl formal

Polyvinyl acetal

Polyvinyl propanal

Polyvinyl hexanal

Polyvinylpyrrolidone

Polyacrylic acid ester

Polymethacrylic acid ester

Cellulose acetate

Cellulose propionate

Cellulose acetate butyrate

In addition, known viscosity modifiers and thixotropic agents such as smectite, fluorotetrasilicomica, bentonite, silica, montmorillonite and poly (sodium acrylate) as described in JP-A-8-325491; And ethyl cellulose, polyacrylic acid and organic clays as described in JP-A-10-219136 may also be used.

1- (16) Coating Solvent:

As the solvent used in the coating composition for forming each layer of the present invention, various solvents (each component can be dissolved or dispersed therein; it is easy to obtain uniform surface properties in the coating step and the drying step; Liquid preservation can be ensured; selected in view of having a suitable saturated vapor pressure) can be used.

Mixtures of two or more solvents may be used. In particular, from the viewpoint of the drying load, it is preferable to use a solvent having a boiling point of 100 ° C. or lower as a main component at room temperature under atmospheric pressure, but a small amount of solvent having a boiling point of 100 ° C. or higher is contained for the purpose of controlling the drying rate.

Examples of solvents having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point: 68.7 ° C.), heptane (boiling point: 98.4 ° C.), cyclohexane (boiling point: 80.7 ° C.), and benzene (boiling point: 80.1 ° C.); Halogenated hydrocarbons such as dichloromethane (boiling point: 39.8 ° C.), chloroform (boiling point: 61.2 ° C.), carbon tetrachloride (boiling point: 76.8 ° C.), 1,2-dichloroethane (boiling point: 83.5 ° C.) and trichloroethylene (boiling point: 87.2 ° C.) ); Ethers such as diethyl ether (boiling point: 34.6 ° C.), diisopropyl ether (boiling point: 68.5 ° C.), dipropyl ether (boiling point: 90.5 ° C.) and tetrahydrofuran (boiling point: 66 ° C.); Esters such as ethyl formate (boiling point: 54.2 ° C.), methyl acetate (boiling point: 57.8 ° C.), ethyl acetate (boiling point: 77.1 ° C.) and isopropyl acetate (boiling point: 89 ° C.); Ketones such as acetone (boiling point: 56.1 ° C.) and 2-butanone (same as methyl ethyl ketone, boiling point: 79.6 ° C.); Alcohols such as methanol (boiling point: 64.5 ° C.), ethanol (boiling point: 78.3 ° C.), 2-propanol (boiling point: 82.4 ° C.) and 1-propanol (boiling point: 97.2 ° C.); Cyano compounds such as acetonitrile (boiling point: 81.6 ° C.) and propionitrile (boiling point: 97.4 ° C.); And carbon disulfide (boiling point: 46.2 ° C.). Of these, ketones and esters are preferred; Ketones are particularly preferred. Of the ketones, 2-butanol is particularly preferred.

Examples of a solvent having a boiling point of 100 ° C. or more include octane (boiling point: 125.7 ° C.), toluene (boiling point: 110.6 ° C.), xylene (boiling point: 138 ° C.), tetrachloroethylene (boiling point: 121.2 ° C.), chlorobenzene (boiling point: 131.7 ° C), dioxane (boiling point: 101.3 ° C), dibutyl ether (boiling point: 142.4 ° C), isobutyl acetate (boiling point: 118 ° C), cyclohexanone (boiling point: 155.7 ° C), 2-methyl-4-pentanone (Same as MIBK, boiling point: 115.9 ° C), 1-butanol (boiling point: 117.7 ° C), N, N-dimethylformamide (boiling point: 153 ° C), N, N-dimethylacetamide (boiling point: 166 ° C) and dimethyl Sulfoxide (boiling point: 189 ° C.) is included. Among these, cyclohexanone and 2-methyl-4-pentanone are preferable.

1- (17) Other:

In addition to the above components, resins, coupling agents, colorants, colorants (eg pigments and dyes), antifoams, levelers, flame retardants, ultraviolet absorbers, infrared absorbers, tackifiers, polymerization inhibitors, antioxidants, surface modifiers, and the like This may also be added to the film of the present invention.

1- (18) support:

The support of the film of the present invention is not particularly limited, and examples thereof include a transparent resin film, a transparent resin flat plate, a transparent resin sheet, and a transparent glass. Examples of transparent resin films include cellulose acylate films (eg, cellulose triacetate films (refractive index: 1.48), cellulose diacetate films, cellulose acetate butyrate films and cellulose acetate propionate films), polyethylene terephthalate films, polyethers Contains sulfone films, polyacrylic resin films, polyurethane base films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyether ketone films, and (meth) acrylonitrile films do.

<Cellulose acylate film>

Above all, the cellulose acylate film which is high in transparency, low in optical birefringence, is easy to manufacture, and is generally used as a protective film of a polarizing plate, and a cellulose triacetate film is particularly preferable. Moreover, the thickness of the transparent support is usually 25 μm to 1,000 μm.

In the present invention, it is preferable to use cellulose acetate having an acetylation level of 59.0 to 61.5% for cellulose acylate film.

"Acetylation level" as referred to herein means the amount of acetic acid bound per unit weight of cellulose. Acetylation levels are in accordance with the measurements and calculations of ASTM D-817-91 (test methods for testing cellulose acetate and the like).

The cellulose acylate preferably has a viscosity average degree of polymerization (DP) of 250 or more, more preferably 290 or more.

Moreover, the cellulose acylate used in the present invention has a Mw / Mn value measured by gel permeation chromatography, where Mw represents a weight average molecular weight and Mn represents a number average molecular weight, that is, close to 1.0 Narrow molecular weight distribution is preferable. Specifically, the Mw / Mn value is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and most preferably 1.4 to 1.6.

In general, it can be said that the hydroxyl groups at 2-, 3- and 6-positions of cellulose acylate are not distributed equally every third of the total degree of substitution, and the degree of substitution of hydroxyl groups at the 6-position Tends to be small. In this invention, it is preferable that substitution degree of the hydroxyl group in the 6-position of a cellulose acylate is larger than the thing in 2- or 3-position.

The hydroxyl group in this position is preferably substituted with an acyl group in a proportion of at least 32%, more preferably at least 33%, particularly preferably at least 34% of the total degree of substitution. In addition, it is preferable that the substitution degree of an acyl group in the 6-position of a cellulose acylate is 0.88 or more. The hydroxyl group in the 6-position may be substituted with an acyl group having 3 or more carbon atoms in addition to the acetyl group (eg, propionyl group, butyroyl group, valeroyl group, benzoyl group and acryloyl group). Measurement of the degree of substitution at each position can be determined by NMR.

In the present invention, JP-A-11-5851, paragraphs [0043] to [0044], [Examples] [Synthesis Example 1], paragraphs [0048] to [0049], [Synthesis Example 2], and paragraph [0051] To cellulose acetate obtained by the method as described in Synthesis Example 3 can be used as the cellulose acylate.

<Polyethylene terephthalate film>

In the present invention, polyethylene terephthalate film is also preferably used because it is not only excellent in transparency, mechanical strength, flatness, chemical resistance and moisture resistance but also inexpensive.

For the purpose of further improving the adhesion of the transparent plastic film and the hard coat layer to be provided thereon, it is more preferable to apply the transparent plastic film to an easy adhesion treatment.

Commercially available optical easy-adhesion layer-providing PET films include COSMOSHINE A4100 and A4300 manufactured by Toyobo Co., Ltd.

2.Layer constituting the antireflection film:

The antireflective film of the present invention is obtained by mixing and coating the respective layer constituents on the support. Next, the layers constituting the antireflective film of the present invention will be described.

2- (1) anti-glare layer:

For the film, an anti-glare layer is formed for the purpose of imparting anti-glare properties due to surface scattering as defined in the present invention and preferably hard coat properties for improving the scar resistance of the film.

A method of forming an antiglare layer, comprising: a method of forming an antiglare layer by laminating a film of a mat-like shape having fine irregularities on a surface as described in JP-A-6-16851; A method of forming an anti-glare layer by curing and shrinking of the ionizing radiation curable resin due to the difference in the amount of ionizing radiation as described in JP-A-2000-206317; As described in JP-A-2000-338310, the solidification of the semi-transparent fine particles and the semi-transparent resin, simultaneously with the gelation by reducing the weight ratio of the good solvent to the semi-transparent resin upon drying, resulting in the formation of irregularities on the film surface Anti-glare layer forming method; And JP-A-2000-275404, a method of forming an antiglare layer by imparting surface irregularities by pressure from the outside is known. Known methods can be used.

In the anti-glare layer which can be used in the present invention, a binder capable of imparting a hard coat property, semi-transparent particles and a solvent for imparting anti-glare properties are contained as essential components, and surface irregularities protrude from the translucent particles themselves, or a plurality of them. It is preferably formed by the protrusion formed by the aggregate of particles of.

The anti-glare layer formed by the dispersion of the mat particles is made of a binder and semi-transparent particles dispersed in the binder. It is preferable that an anti-glare layer having anti-glare property has both anti-glare property and hard coat property.

Specific examples of mat particles suitably used include particles of inorganic compounds such as silica particles and TiO ₂ particles; And resin particles such as acrylic resin particles, crosslinked acrylic resin particles, polystyrene particles, crosslinked styrene resin particles, melamine resin particles and benzoguanamine particles. Among these, crosslinked styrene resin particles, crosslinked acrylic resin particles and silica particles are preferable.

The shape of the mat particles that can be used can be spherical or amorphous.

The particle size distribution of the mat particles is measured by the particle counter method, and the measured distribution is converted into the particle number distribution.

By adjusting the refractive index of the translucent resin according to the refractive index of each translucent particle selected from the particles, the internal haze and the surface haze of the present invention can be achieved. Specifically, as the main component, a translucent resin composed of a trifunctional or polyfunctional (meth) acrylate monomer (refractive index after curing: 1.55 to 1.70) and 50, which is preferably used in the anti-glare layer of the present invention as described below, and 50 Combinations of translucent particles and / or benzokuanamine particles consisting of crosslinked poly (meth) acrylate polymers having a styrene content of from 100% by weight to 100% by weight are preferred; Particular preference is given to a combination of semitransparent particles (refractive index: 1.54 to 1.59) consisting of the translucent resin and a crosslinked poly (styrene-acrylate) copolymer having a styrene content of 50 to 100% by weight.

The semi-transparent particles are preferably blended in the formed antiglare layer in an amount of 3 to 30% by weight in the total solid of the antiglare layer. The amount of semitransparent particles is more preferably 5 to 20% by weight. When the amount of the semi-transparent particles is less than 3% by weight, the anti-glare property is insufficient, while when the amount of the semi-transparent particles is more than 30% by weight, problems such as blurring of the image, blurring of the surface, and glare are caused.

Moreover, the density of the semi-transparent particles is preferably 10 to 1,000 mg / m 2, more preferably 100 to 700 mg / m 2.

Moreover, the difference in absolute values between the refractive indices of the semitransparent resin and the refractive indices of the semitransparent particles is preferably 0.04 or less. The difference in absolute value between the refractive index of the semitransparent resin and the refractive index of the semitransparent particles is more preferably 0.001 to 0.030, more preferably 0.001 to 0.020, particularly preferably 0.001 to 0.015. If this difference exceeds 0.040, problems such as bleeding of film characters, a decrease in dark room contrast and blurring of the surface are caused.

Here, the refractive index of the translucent resin can be quantitatively determined and evaluated, for example, by direct measurement with Abbe's refractometer or by spectral reflection spectrum measurement or spectroscopic ellipsometry. The refractive index of the semi-transparent particles is to change the mixing rate of the two kinds of solvents having different refractive index for measuring the turbidity, dispersing the same amount of semi-transparent particles in the solvent having various refractive index, and the turbidity is minimized by Abe's refractometer It is measured by measuring the refractive index of the solvent to be

It is also possible to use two or more kinds of mat particles having different particle sizes together. Matte particles with larger particle size can impart anti-glare properties, and matte particles with smaller particle size can impart other optical properties, respectively. For example, if an antiglare antireflective film is stuck onto a high resolution display having 133 ppi or more, there is a possibility of causing a defect in display image quality called "glare". "Glare" derives from the point that pixels lose or lose luminance uniformity by being enlarged or shrunk by irregularities present on the surface of the anti-glare antireflective film. Glare can usually be improved by using matt particles having a smaller particle size than matt particles that can impart anti-glare properties and can have different refractive indices from the binder.

The thickness of the antiglare layer is preferably 1 to 10 µm, more preferably 1.2 to 8 µm. If the anti-glare layer is too thin, the hard properties are insufficient, while if it is very thick, the curling or brittleness may deteriorate and possibly lower the process applicability. Therefore, it is preferable that the thickness of an anti-glare layer exists in the said range.

On the other hand, the range of the centerline average roughness Ra of the antiglare layer is preferably 0.10 to 0.40 m. When the centerline average roughness Ra of the anti-glare layer exceeds 0.40 μm, problems such as whitening of the surface are caused when glare or external light is reflected. Moreover, the delivered image sharpness value is preferably 5 to 60%.

The strength of the anti-glare layer is preferably at least H, more preferably at least 2H, most preferably at least 3H, by a pencil strength test.

2- (2) hard coat layer:

In order to impart physical strength to the film in addition to the anti-glare layer, a hard coat layer may be provided for the film of the present invention.

Preferably, a low refractive index layer is provided thereon; More preferably, a medium refractive index layer and a high refractive index layer are provided between the hard coat layer and the low refractive index layer to form an antireflection film.

The hard coat layer may consist of a stack of two or more layers.

In the present invention, according to the optical design for obtaining the antireflective film, the hard coat layer preferably has a refractive index of 1.48 to 2.00, preferably a refractive index of 1.52 to 1.90, more preferably a refractive index of 1.55 to 1.80. In the present invention, since at least one low refractive index layer is present on the hard coat layer, when the refractive index is very low compared with this range, the antireflection property is reduced, whereas when the refractive index is very large, the color of the reflected light is decreased. Tends to be strong.

In view of imparting sufficient durability and impact resistance to the film, the thickness of the hard coat layer is usually about 0.5 μm to 50 μm, preferably 1 μm to 20 μm, more preferably 2 μm to 10 μm. And most preferably from 3 μm to 7 μm.

Moreover, the strength of the hard coat layer is preferably at least H, more preferably at least 2H, most preferably at least 3H, by a pencil strength test.

In addition, it is preferable that the amount of wear of the specimen before and after the test is as small as possible in a taper test according to JIS K5400.

It is preferable that a hard-coat layer is formed by the crosslinking reaction or polymerization reaction of an ionizing radiation curable compound. For example, a hard coat layer can be formed by coating a coating composition containing an ionizing radiation curable polyfunctional monomer or polyfunctional oligomer on a transparent support and applying the polyfunctional monomer or polyfunctional oligomer to a crosslinking reaction or a polymerization reaction.

As a functional group of an ionizing radiation curable polyfunctional monomer or a polyfunctional oligomer, a photopolymerizable functional group, an electron beam polymerizable functional group, and a radiation polymerizable functional group are preferable, and a photopolymerizable functional group is especially preferable.

Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as (meth) acryloyl group, vinyl group, styryl group and allyl group, and a (meth) acryloyl group is preferable.

For the purpose of imparting internal scattering properties, mat particles having an average particle size of 1.0 to 10.0 μm, preferably 1.5 to 7.0 μm, for example inorganic particles or resin particles may be contained in the hard coat layer. .

In order to control the refractive index of the hard coat layer, high refractive index monomers or inorganic particles or both may be added to the binder of the hard coat layer. The inorganic particles have an effect of suppressing hardening and shrinkage due to the crosslinking reaction in addition to the effect of controlling the refractive index. In the present invention, this is referred to as a binder comprising a polymer as formed by polymerization of the above polyfunctional monomer and / or a high refractive index monomer and the like and inorganic particles as diffused therein after formation of the hard coat layer.

In order to maintain image sharpness, in addition to controlling the irregular shape of the surface, it is desirable to adjust the transmitted image sharpness. The clear antireflective film preferably has a delivered image clarity of at least 60%. The transmitted image clarity is generally an index indicating the blurring state of the image transmitted and projected through the film. The higher this value, the better the clarity of the image seen through the film. The delivered image sharpness is preferably at least 70%, more preferably at least 80%.

2- (3) high and medium refractive index layers:

In the film of the present invention, the antireflection property can be enhanced by providing a high refractive index layer and a medium refractive index layer.

In this specification, the high refractive index layer and the medium refractive index layer are often referred to collectively as the high refractive index layer. Incidentally, in the present invention, the terms "high", "medium" and "low" in the high refractive index layer, the medium refractive index layer, and the low refractive index layer express relatively large and small interrelationships between layers. Moreover, as long as the relationship with the transparent support is related, the refractive index preferably satisfies the relationship of [(transparent support)> (low refractive index layer)] and [(high refractive index layer)> (transparent support)].

Moreover, in this specification, the high refractive index layer, the medium refractive index layer and the low refractive index layer will often be referred to collectively as an antireflection layer.

In order to form a low refractive index layer on the high refractive index layer to produce an antireflection film, the high refractive index layer is preferably 1.55 to 2.40, more preferably 1.60 to 2.20, more preferably 1.65 to 2.10, most preferably 1.80 to It has a refractive index of 2.00.

In the case where the medium refractive index layer, the high refractive index layer and the low refractive index layer are coated and provided on the support in this order to prepare the antireflection film, the high refractive index layer is preferably 1.65 to 2.40, more preferably 1.70 to 2.20 Has The refractive index of the medium refractive index layer is adjusted to have a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the medium refractive index layer is preferably 1.55 to 1.80.

Inorganic particles composed of TiO ₂ as a main component, used in the high refractive index layer and the medium refractive index layer, are used in a dispersed state for formation of the high refractive index layer and the medium refractive index layer.

Upon dispersing the inorganic particles, the inorganic particles are dispersed in the dispersion medium in the presence of a dispersant.

The high refractive index layer and the medium refractive index layer used in the present invention preferably contain a binder precursor (e.g., ionizing radiation curable polyfunctional monomer or polyfunctional oligomer as described below), a photopolymerization initiator, and the like, which are essential for matrix formation, in a dispersion medium. It is formed by further addition in a dispersion having dispersed inorganic particles to prepare a coating composition for forming a high refractive index layer and a coating composition for forming a medium refractive index layer, and a coating composition for forming a high refractive index layer and a coating composition for forming a medium refractive index layer. It is preferable to coat on a transparent support and then to cure them by polymerization reaction or crosslinking reaction of an ionizing radiation curable compound (for example, polyfunctional monomer and polyfunctional oligomer).

In addition, the binder of the high refractive index layer and the binder of the medium refractive index are preferably applied to the crosslinking reaction or the polymerization reaction using a dispersant when coating the layer or after coating.

In the binder of the high refractive index layer and the binder of the medium refractive index layer thus prepared, for example, the preferred dispersant and the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer undergo a crosslinking reaction or a polymerization reaction, whereby the anionic groups of the dispersant Enter each binder. Furthermore, in each of the binder of the high refractive index layer and the binder of the medium refractive index layer, the anionic groups have a function of maintaining the dispersed state of the inorganic particles, and the crosslinked or polymerized structure imparts a film forming ability to the binder, thereby containing inorganic particles, respectively. It improves the physical strength, chemical resistance and weather resistance of the high refractive index layer and the medium refractive index layer.

The binder of the high refractive index layer is added in an amount of 5 to 80% by weight based on the solids content of the coating composition of the target layer.

The content of the inorganic particles in the high refractive index layer is preferably 10 to 90% by weight, more preferably 15 to 80% by weight, particularly preferably 15 to 75% by weight based on the weight of the high refractive index layer. Two or more kinds of inorganic particles may be used together in the high refractive index layer.

When the low refractive index layer is present on the high refractive index layer, it is preferable that the refractive index of the high refractive index layer is larger than that of the transparent support.

In the high refractive index layer, binders obtainable by crosslinking or polymerization reactions such as aromatic ring-containing ionizing radiation curable compounds, ionizing radiation curable compounds and atoms containing halogen atoms other than fluorine (eg, Br, I and Cl) For example, ionizing radiation curable compounds containing S, N and P can also be preferably used.

The thickness of the high refractive index layer can be appropriately designed depending on the application. When the high refractive index layer is used as the optical interference layer as described below, the thickness thereof is preferably 30 to 200 nm, more preferably 50 to 170 nm, particularly preferably 60 to 150 nm.

When the high refractive index layer does not contain particles capable of imparting an antiglare function, it is preferable that the haze of the high refractive index layer is as low as possible. The haze is preferably 5% or less, more preferably 3% or less, particularly preferably 1% or less.

It is preferred that a high refractive index layer is built on the transparent support directly or through another layer.

2- (4) low refractive index layer:

In order to lower the reflectance of the film of this invention, it is required to use a low refractive index layer.

The low refractive index layer preferably has a refractive index of 1.20 to 1.46, more preferably 1.25 to 1.46, particularly preferably 1.30 to 1.46.

The low refractive index layer preferably has a thickness of 50 to 200 nm, more preferably 70 to 100 nm. The low refractive index layer preferably has a haze of 3% or less, more preferably 2% or less, most preferably 1% or less. Specifically, the low refractive index layer has a strength of preferably at least H, more preferably at least 2H, most preferably at least 3H, by a pencil hardness test using a load of 500 g.

Moreover, in order to improve the antifouling performance of the optical film, the contact angle with respect to water on the surface is preferably at least 90 °, more preferably at least 95 °, particularly preferably at least 100 °.

It is preferable that the said curable composition contains (A) the said fluorine-containing polymer, (B) inorganic particle, and (C) organosilane compound.

In order to disperse and fix the fine particles of the present invention, a binder is used in the low refractive index layer. Although the binder in the hard coat layer described above can be used as the binder, it is preferable to use a fluorine-containing sol-gel raw material having a low refractive index of the fluorine-containing polymer or the binder itself. The fluorine-containing polymer or fluorine-containing sol-gel is preferably a raw material crosslinked with heat or ionizing radiation and the surface of the low refractive index layer formed here has a dynamic friction coefficient of 0.03 to 0.30 and a contact angle to water of 85 to 120 °. Have

2- (5) antistatic and conductive layers:

In the present invention, it is desirable to provide an antistatic layer in view of the static elimination on the film surface. Examples of the method of forming the antistatic layer include conventionally known methods, such as a method of coating a conductive coating solution containing conductive fine particles and a reactive curable resin, and sputtering of metal or metal oxide capable of forming a transparent film, or the like. The conductive thin film formation method by vapor deposition is included. The conductive layer can be formed on the support directly or through a primer layer that can enhance adhesion to the support. Moreover, the antistatic layer can be used as part of the antireflective film. In this case, when the antistatic layer is used for the layer closest to the outermost layer, it is possible to sufficiently obtain the antistatic property even if the film is thin.

The antistatic layer preferably has a thickness of 0.01 to 10 μm, more preferably 0.03 to 7 μm, more preferably 0.05 to 5 μm. The antistatic layer preferably has a surface resistivity of 10 ⁵ to 10 ¹² dl / sq, more preferably 10 ⁵ to 10 ⁹ dl / sq, most preferably 10 ⁵ to 10 ⁸ dl / sq. Surface resistivity can be measured by four probe methods.

It is preferable that the antistatic layer is substantially transparent. Specifically, the antistatic layer preferably has a haze of 10% or less, more preferably 5% or less, more preferably 3% or less, most preferably 1% or less. The antistatic layer preferably has a transmittance of 50% or more, more preferably 60% or more, more preferably 65% or more, and most preferably 70% or more for light having a wavelength of 550 nm.

The antistatic layer of the present invention is excellent in strength. Specifically, the antistatic layer preferably has a strength of at least H, more preferably at least 2H, more preferably at least 3H, and most preferably at least 4H, in terms of pencil strength of a load of 1 kg.

2- (6) antifouling layer:

It is possible to provide an antifouling layer on the outermost surface of the present invention. The antifouling layer reduces the surface energy of the antireflective layer so that the hydrophilic or lipophilic stain is hardly attached.

The antifouling layer can be formed by using a fluorine-containing polymer or an antifouling agent.

The antifouling layer preferably has a thickness of 2 to 100 nm, more preferably 5 to 30 nm.

2- (7) Interference Nonuniformity (Spectral Nonuniformity) Prevention Layer

When there is a substantial difference in refractive index between the transparent support and the hard coat layer or between the transparent support and the anti-glare layer (the refractive index difference is 0.3 or more), reflected light is generated on the interface between the transparent support and the hard coat layer or between the transparent support and the anti-glare layer. The reflected light may possibly be interfered by reflected light on the surface of the antireflective layer, resulting in interference unevenness caused by a slight unevenness in the thickness of the hard coat layer (or anti-glare layer). In order to prevent such interference unevenness, an interference non-uniformity prevention layer may also be provided between the transparent support and the hard coat layer (or anti-glare layer), for example having a medium refractive index n _p and whose thickness d _p satisfies the following equation:

Formula (d _p )

d _p = (2N-1) x λ / (4n _p )

Wherein λ represents the wavelength of visible light and the value is any value in the range from 450 to 650 nm; N represents a natural number.

Moreover, when the antireflective film is fixed onto an image display or the like, there may be a case where the pressure sensitive adhesive layer (or adhesive layer) is stacked on the transparent support surface on which the antireflective layer is not stacked. In such embodiments, there is a case where reflected light is generated between the transparent support and the pressure sensitive adhesion layer (or adhesion layer) when there is a substantial difference (0.3 or more) of the refractive index between the transparent support and the pressure sensitive adhesion layer (or adhesion layer). The reflected light may be interfered by the reflected light on the surface of the antireflective layer or the like to generate interference nonuniformity caused by the nonuniformity in the thickness of the support or the hard coat layer as in the above case. To prevent such interference nonuniformity, an interference nonuniformity prevention layer similar to the above layer for preventing interference nonuniformity may be provided on the side of the transparent support on which the antireflection layer is not stacked.

In addition, the interference non-uniformity preventing layer is described in detail in JP-A-2004-345333, and the interference non-uniformity preventing layer as set forth in this patent document can also be utilized in the present invention.

2- (8) easy adhesion layer:

Easy adhesion layers may be coated and provided on the films of the present invention. As used herein, the term "easy adhesion layer" means a layer that can impart a function of, for example, easily attaching a protective film for a polarizing plate and its adjacent layer or hard coat layer and a support to each other.

Examples of easy adhesion treatment include treatment of providing an easy adhesion layer on a transparent plastic film with an easy adhesive consisting of the polyester, acrylic acid ester, polyurethane, polyethyleneimine, silane coupling agent and the like. .

Examples of easy adhesion layers which are preferably used in the present technology include layers containing polymer compounds containing -COOM groups, wherein M represents a hydrogen atom or a cation. A more preferred embodiment relates to the fact that a layer containing a -COOM group-containing polymer compound is provided on the side of the film substrate and a layer containing the hydrophilic polymer compound as a main component is provided adjacent therein in the side of the polarizing film. do. Examples of the -COOM group-containing polymer compounds mentioned herein include -COOM group-containing styrene maleic acid copolymers and -COOM group-containing vinyl acetate-maleic acid copolymers or vinyl acetate-maleic acid-maleic anhydride copolymers. Included. Particular preference is given to using -COOM group-containing vinyl acetate-maleic acid copolymers. The polymer compound is used alone or in combination of two or more thereof, and its weight average molecular weight is preferably about 500 to 500,000. Particularly preferred examples of the -COOM group-containing polymer compound include those described in JP-A-6-094915 and those described in JP-A-7-333436.

Moreover, preferred examples of hydrophilic polymer compounds include hydrophilic cellulose derivatives (eg methyl cellulose, carboxymethyl cellulose and hydroxycellulose), polyvinyl alcohol derivatives (eg polyvinyl alcohol, vinyl acetate-vinyl alcohol copolymers, Polyvinyl acetal, polyvinyl formal and polyvinyl benzal), natural polymer compounds (e.g. gelatin, casein and gum arabic), hydrophilic polyester derivatives (e.g. partially sulfonated polyethylene terephthalate) and hydrophilic poly Vinyl derivatives (eg, poly-N-vinylpyrrolidone, polyacrylamide, polyvinyl indazole and polyvinyl pyrazole). The said hydrophilic polymer compound is used individually or in mixture of 2 or more types.

The easy adhesion layer preferably has a thickness of 0.05 to 1.0 μm. When the thickness of the easy adhesion layer is less than 0.05 mu m, sufficient adhesion is hardly obtained, whereas when it exceeds 1.0 mu m, the adhesion effect is saturated.

2- (9) Antiurl layer:

It is possible to perform anti-curling processing on the film of the present technology. As referred to herein, "Anti-Curling" is to impart the ability to round the surface to which the Anti-Curling is applied. By applying this processing, the application of some surface processing onto the surface of the transparent resin film serves to prevent a phenomenon in which the object surface curls in when the surface processing is applied to the two surfaces at different degrees and types.

An embodiment in which an anti-curling layer is provided on the side of the substrate opposite the side on which the anti-glare or anti-reflection layer is provided; Embodiments in which an easy adhesion layer is coated and provided on one surface of the transparent resin film; And embodiments in which anti-curling processing is applied on the opposite surface.

Specific examples of anti-curling processing include coating and providing a solvent and a transparent resin layer made of a solvent and cellulose triacetate, cellulose diacetate, cellulose acetate propionate, and the like. Specifically, the method using the solvent shown herein is carried out by coating a composition containing a solvent capable of dissolving or swelling a cellulose acetate film used as a protective film for a polarizing plate. Therefore, as the coating solution of the layer having the action of preventing curling from occurring, it is preferable to contain a ketone-based or ester-based organic solvent. Preferred examples of ketone-based organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl lactate, acetylacetone, diacetone alcohol, isophorone, ethyl n-butyl ketone, diisopropyl ketone, diethyl Ketones, di-n-propyl ketones, methyl cyclohexanone, methyl n-butyl ketones, methyl n-propyl ketones, methyl n-hexyl ketones and methyl n-heptyl ketones; Preferred examples of ester based organic solvents include methyl acetate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate. However, as the solvent used, there may be a case where a solvent which does not dissolve the cellulose acrylate film may be contained in addition to a mixture of a solvent which can dissolve the cellulose acrylate film and / or a solvent which can swell the cellulose acrylate film. have. Curling prevention processing is performed using the composition obtained by mixing the said solvent in an appropriate ratio according to the curling degree of a transparent resin film and the kind of resin in coating amount. In addition, anti-curling action is also found using transparent hard processing or antistatic processing.

2- (10) water absorbing layer:

Water absorbers can be used in the films of the present invention. The water absorbent may be selected from compounds having a water absorption action centered on alkaline earth metals. Examples thereof include BaO, SrO, CaO and MgO. In addition, the water absorbent may also be selected from metal elements such as Ti, Mg, Ba and Ca. The particle size of the absorbent particles is preferably 100 nm or less, more preferably 50 nm or less.

The layer containing the water absorbent may be prepared using the same vacuum deposition method as the barrier layer described above, or the nanoparticles may be prepared by various methods. The thickness of the layer is preferably 1 to 100 nm, more preferably 1 to 10 nm. The water absorbent-containing layer may be added between the support and the stack (a stack of barrier and organic layers), in the top layer of the stack, between the stacks, or in the organic or barrier layer in the stack. When added to the wall layer, preference is given to using a co-deposition method.

2- (11) primer layer or inorganic thin film layer:

In the film of the present invention, it is possible to enhance gas barrier properties by placing a known primer layer or inorganic thin film layer between the support and the stack.

For the primer layer, for example, acrylic resins, epoxy resins, urethane resins and silicone resins can be used. However, in the present invention, an organic / inorganic hybrid layer is preferred as the primer layer. Moreover, a fine inorganic coating thin film by the inorganic vapor deposition layer or the sol-gel method is preferable as the inorganic thin film layer. The inorganic deposition layer may be formed by a vacuum deposition method, a sputtering method, or the like.

3. Layer arrangement of film:

With regard to the film of the present invention, known layer arrangements using the layers described above can be used. Representative examples thereof will be shown below.

(a) support / hard coat layer

(b) support / hard coat layer / low refractive index layer (see FIG. 1)

(c) support / hard coat layer / high refractive index layer / low refractive index layer (see FIG. 2)

(d) support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer (see FIG. 3)

(b) As in (FIG. 1), by stacking the low refractive index layer 5 on the hard coat layer 2 coated on the support 1, a stack can be suitably used as an antireflection film. By forming the low refractive index layer 5 on the hard coat layer 2 with a thickness of about 1/4 of the light wavelength, the surface reflection due to the principle of thin film interference can be reduced.

Furthermore, as in (c) (FIG. 2), by stacking the high refractive index layer 4 and the low refractive index layer 5 on the hard coat layer 2 coated on the support 1, as an antireflection film The stack may be suitably used. Further, as in (d) (FIG. 3), the support 1, the hard coat layer 2, the medium refractive index layer 3, the high refractive index layer 4 and the low refractive index layer 5 are layered in this order. By arranging, the reflectance can be kept at 1% or less.

In the arrangement of (a) to (d), the hard coat layer 2 can be made of an antiglare layer having antiglare characteristics. The anti-glare property may be provided by dispersing the matte particles illustrated in FIG. 4, or may be provided by forming a surface by a method such as embossing illustrated in FIG. 5. The anti-glare layer formed by dispersing the mat particles consists of a binder and semi-transparent particles dispersed in the binder. Preferably, the anti-glare layer having anti-glare properties has both anti-glare properties and hard coating properties, and may be composed of, for example, a plurality of layers of 2 to 4 layers.

Moreover, examples of layers that may be provided between the layer on the outermost surface or on one side of the surface and the transparent support include requirements such as interference nonuniformity (spectroscopic nonuniformity) prevention layer, antistatic layer (reduction of surface resistance value from the display surface). If present, or if staining on the surface is a problem), other hard coat layers (if the hardness is insufficient only with a single hard coat layer or antiglare layer), gas barrier layer, water absorbing layer (waterproof layer), adhesion Enhancement layer and antifouling layer (pollution-preventing layer) are included.

In the present invention, the refractive index of each layer constituting the anti-glare antireflection film having the antireflection layer preferably satisfies the following relationship.

(Refractive index of hard coat layer)> (Refractive index of transparent support)> (Refractive index of low refractive index layer)

4. Manufacturing Method:

The film of the present invention may be formed by the following method, but the present invention should not be construed as being limited thereto.

Preparation of 4- (1) Coating Solution

<Production>

First, a coating solution containing the components forming each layer is prepared. In that case, by minimizing the volatilization amount of the solvent, it is possible to suppress the increase in the water content in the coating solution. The water content in the coating solution is preferably 5% or less, more preferably 2% or less. Inhibition of the volatilization amount of the solvent is achieved by, for example, filling each tank with a raw material and then improving the firmness upon stirring and minimizing the air contact surface of the coating solution during the liquid transfer operation. Furthermore, the drop in the water content in the coating solution during or before coating can be measured.

Physical Properties of Coating Solution

In the coating system of the present invention, it is necessary to control the physical properties of the solution, in particular the viscosity and the surface tension, during coating since the upper limit on the coating is greatly influenced by the physical properties of the solution.

The viscosity of the low refractive index layer used in the present invention is preferably 2.0 [mPa · s] or less, more preferably 1.5 [mPa · s] or less, and most preferably 1.0 [mPa · s] or less. Since the viscosity depends on the shear rate depending on the coating solution, the above values represent the viscosity at the shear rate at the time of coating. By adding thixotropic agents to the coating solution, the viscosity is lower for coatings where high shear is applied, while the viscosity is high for drying where the shear is not substantially applied to the coating solution, and there is little variation in drying. . Thus, this is desirable.

Moreover, in addition to the physical properties of the solution, the amount of coating solution to be coated on the transparent support also affects the upper limit on which coating is possible. The amount of coating solution coated on the transparent support is preferably 2.0 to 5.0 [ml / m 2]. By increasing the amount of coating solution to be coated on the transparent support, the upper limit of the amount at which coating is possible is increased, and thus such is preferable. However, if the amount of coating solution coated on the transparent support is excessively increased, the load applied to drying becomes large. Therefore, it is desirable to determine the optimal amount of coating solution to be coated on the transparent support by the solution formulation and processing conditions.

The surface tension is preferably in the range of 15 to 36 [mN / m]. Since the nonuniformity is controlled at the time of drying, it is preferable to lower the surface tension by adding a smoothing agent or by other means. On the other hand, when the surface tension is reduced too much, the upper limit of the coating ratio is lowered. Therefore, the surface tension is more preferably in the range of 17 [mN / m] to 32 [mN / m], more preferably in the range of 19 [mN / m] to 26 [mN / m].

<Filtration>

It is preferable that the coating solution used for coating be filtered before coating. As for the filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within the range in which the components in the coating solution are not removed. For filtration, a filter having an absolute filtration accuracy of 0.1 to 10 탆 is used, and a filter having an absolute filtration accuracy of 0.1 to 5 탆 is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, more preferably 0.2 to 2 mm. In that case, the filtration is carried out under a filtration pressure of 1.5 MPa or less, more preferably 1.0 MPa or less and even more preferably 0.2 MPa or less.

The filter member is not particularly limited as long as it does not affect the coating solution. Strictly speaking, the same filter source for the wet dispersion liquid of the inorganic compound as mentioned above is considered.

Moreover, it is also desirable to disperse the filtered coating solution ultrasonically just before coating, thereby helping to deflate, disperse and hold the dispersion.

4- (2) pre-coating treatment:

It is preferable to surface-treat the support used in the present invention before coating. Specific examples thereof include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment and ultraviolet irradiation treatment. Moreover, providing a bottom coating layer as described in JP-A-7-333433 is also preferably used.

In addition, examples of the dust removal method used in the dust removal process as the pre-coating process include a method of pressing a nonwoven fabric, a blade or the like onto the film surface as described in JP-A-59-150571; A method of blowing air at high speed and high cleaning to suck up the sediment separated by the adjacent suction opening to separate the sediment from the film surface as described in JP-A-10-309553; As described in JP-A-7-333613, a method of blowing vacuum compressed air and sucking the precipitate with ultrasonic waves to separate the precipitate (for example, manufactured by NEW ULTRASONIC CLEANER, Shinko Co., Ltd.) Dry dust removal methods are included.

In addition, a method of introducing the film into the cleaning tank and separating the precipitate by an ultrasonic vibrator; A method of supplying a cleaning liquid into the film, blowing high-speed air, and performing suction as described in JP-B-49-13020; And applicable wet dust removal methods, such as the method of continuously rubbing a web with a liquid-wet roll as described in JP-A-2001-38306 and then spraying and cleaning the liquid onto the rubbed surface. have. Among the dust removal methods, the ultrasonic dust removal method and the wet dust removal method are particularly preferable in terms of the dust removal effect.

In addition, removing static electricity on the film support before the dust removal process is particularly preferable in that it increases the efficiency of dust removal and suppresses adhesion of dust. In order to achieve the static elimination method, an ionizer of the corona discharge system, an ionizer of the irradiation system using light rays such as UV and soft X-rays, and the like can be used. The film support before and after dust removal and coating preferably has a charging voltage of 1,000 V or less, preferably 300 V or less, particularly preferably 100 V or less.

In view of maintaining the flatness of the film, it is preferable to adjust the temperature of the cellulose acrylate film to Tg or less, particularly 150 ° C or less, in the treatment.

When the cellulose acrylate film is made to adhere to the polarizing plate as in the case of using the film of the present invention as a protective film for the polarizing plate, it is necessary to perform acid treatment or alkali treatment, that is, saponification treatment, on the cellulose acrylate. It is especially preferable from a viewpoint.

From the standpoint of adhesion and the like, the cellulose acrylate film preferably has a surface energy of 55 mN / m or more, more preferably 60 mN / m or more and 75 mN / m or less. Surface energy can be adjusted by the surface treatment described above.

4- (3) coating:

Each layer of the film of the present invention may be formed by the following coating method, but the present invention should not be construed as being limited to the above method.

Notices such as dip coating method, air knife coating method, curtain coating method, roll coating method, wire bar coating method, gravure coating method and extrusion coating method (die coating method) (see US Patent No. 2,681,294) and microgravure coating method Use the old method. Among the above, the microgravure coating method and the die coating method are preferable.

The "microgravure coating method" referred to herein is used in the present invention, wherein a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm and engraved with a gravure pattern over its entire periphery is placed under the support and At the same time, rotating the gravure roll in the reverse direction in the direction of movement of the support, peeling off the excess coating solution from the surface of the target gravure roll by the doctor blade, and fixing the coating solution in a position where the upper surface of the support is free. A coating method characterized by transferring onto a lower surface of a support and thereby coating. The transparent support in the rolled state is subsequently unwound and one or more layers of the hard coat layer and the fluorine-coated olefin based polymer-containing low refractive index layer may be coated on one side of the unwrapped support by the microgravure coating method.

For coating conditions by the microgravure method, the number of lines of the gravure pattern engraved on the gravure roll is preferably 50 to 800 lines per inch, more preferably 100 to 300 lines per inch; The depth of the gravure pattern is preferably 1 to 600 mu m, more preferably 5 to 200 mu m; The rotation speed of the gravure roll is preferably 3 to 800 rpm, more preferably 5 to 200 rpm; The moving speed of the support is preferably 0.5 to 100 m / min, more preferably 1 to 50 m / min.

In order to supply the film of this invention with high productivity, an extrusion coating method (die coating method) is used preferably. In particular, the manufacturing method disclosed in JP-A-2006-122889 can be applied to areas having a small amount of wet coating (20 cc / m 2 or less) such as a hard coat layer and an antireflective layer to improve the uniformity of the film.

4- (4) <drying>

After coating on the support, either directly or through another layer, it is preferred to transfer the film of the invention into a heated zone to dry the solvent using a web.

As a method of drying the solvent, various knowledges can be used. Specific examples of such knowledge include those described in JP-A-2001-286817, JP-A-2001-314798, JP-A-2003-126768, JP-A-2003-315505 and JP-A-2004-34002. Method is included.

The temperature of the drying zone is preferably 25 ° C. to 140 ° C .; It is preferred that the temperature of the first half of the drying zone is relatively low, while the temperature of the second half of the drying zone is relatively high. However, the temperature is preferably below the temperature at which volatilization of components other than the solvent contained in the coating composition of each layer starts. For example, among commercially available optical radical generators used in combination with ultraviolet curable resins, there are those in which several ten percent of their volatilized in a few minutes in warm air at 120 ° C. Moreover, among the monofunctional or bifunctional acrylate monomers, there are those in which volatilization proceeds in warm air at 100 ° C. In this case, the temperature of the drying zone is preferably below the temperature at which volatilization of components other than the solvent contained in the coating composition of each layer starts.

Furthermore, with respect to dry air after coating the coating composition of each layer on the support, if the solids content of the coating composition is 1-50%, the air velocity on the surface of the coating film is 0.1 to prevent the occurrence of dry unevenness. It is preferably in the range of 2 m / sec.

Furthermore, after coating the coating composition of each layer on the support, if the temperature difference between the moving rolls in contact with the opposite surface of the support with respect to the coating surface falls within the range of 0 to 20 ° C. in the drying zone, It is possible to prevent the occurrence of dry unevenness due to heat transfer unevenness, and therefore such is preferable.

4- (5) Curing:

After drying of the solvent, the coating film can be cured by passing the film of the invention through a zone where each coating film can be cured by ionizing radiation and / or heating by a web.

It is preferable that the film of the present invention is heated at a temperature of 70 ° C. or higher and 130 ° C. or lower for a period of 5 to 20 minutes, and then cured by active energy rays provided by ultraviolet rays.

The heat curing temperature is preferably 70 ° C or more and 120 ° C or less, and most preferably 80 ° C or more and 115 ° C or less.

In the present invention, the kind of ionizing radiation is not particularly limited, and may be appropriately selected from ultraviolet rays, electron beams, near ultraviolet rays, visible rays, near infrared rays, infrared rays, and X-rays depending on the type of curable composition forming the film. Above all, ultraviolet rays and electron beams are preferred; Ultraviolet light is particularly preferred in that it is simple and easy to handle and high energy is easily obtained.

As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source can be used as long as it can emit ultraviolet rays. For example, low pressure mercury vapor lamps, medium pressure mercury vapor lamps, high pressure mercury vapor lamps, ultra-high pressure mercury vapor lamps, carbon arc lamps, metal halide lamps, xenon lamps and the like can be used. In addition, ArF excimer lasers, KrF excimer lasers, excimer lamps, synchrotone irradiation and the like can also be used. Among them, ultra-high pressure mercury vapor lamps, high pressure mercury vapor lamps, low pressure mercury vapor lamps, carbon arc lamps, xenon arc lamps and metal halide lamps can be preferably used.

In addition, electron beams can be used similarly. As electron beams, electron beams having an energy of 50 to 1,000 keV, preferably 100 to 300 keV, can be enumerated, which are Cockcroft-Walton type electron beam accelerators, van de Graaff type electron beam accelerators, resonance conversion type electron beam accelerators, insulating core conversions. It emits from various electron beam accelerators such as sieve type electron beam accelerators, linear electron beam accelerators, dynamtron type electron beam accelerators and high frequency type electron beam accelerators.

Irradiation conditions vary with each lamp. The energy intensity of the irradiation dose is preferably 10 mJ / cm 2 or more, more preferably 50 mJ / cm 2 to 10,000 mJ / cm 2, particularly preferably 50 mJ / cm 2 to 2,000 mJ / cm 2. In this case, the irradiation dose distribution in the width direction of the web including both ends is preferably 50 to 100%, more preferably 80 to 100% based on the maximum irradiation dose at the center.

In the present invention, the step of irradiating the ionizing radiation in the atmosphere having an oxygen concentration of 10% by volume or less in the state of ionizing radiation, and heating for a period of 0.5 seconds or more after starting irradiation with ionizing radiation at a film surface temperature of 60 ℃ or more It is preferred to cure one or more layers adhering on the support.

It is also preferable to perform heating simultaneously or continuously with irradiation with ionizing radiation in an atmosphere having an oxygen concentration of 3% by volume or less.

In particular, it is preferable to harden the low refractive index layer which is outermost layer and a thickness is thin by the said method. The curing reaction is accelerated by heat, so that a film with good physical strength and chemical resistance can be formed.

The ionizing irradiation time is preferably 0.7 seconds or more and 60 seconds or less, and more preferably 0.7 seconds or more and 10 seconds or less. If the ionizing irradiation time is 0.5 seconds or less, the curing reaction cannot be completed and curing cannot be achieved as a whole. It is also undesirable to maintain low oxygen conditions for long periods of time because of the large size of the equipment and the large amount of inert gas required.

It is preferable to form a film by crosslinking reaction or polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 6 vol% or less. The oxygen concentration in the atmosphere is more preferably at most 4% by volume, particularly preferably at most 2% by volume and most preferably at most 1% by volume. In order to reduce the oxygen concentration above what is necessary, a large amount of inert gas such as nitrogen is required, and such is not preferable in view of the manufacturing cost.

As a measure of adjusting the oxygen concentration to 10% by volume or less, it is preferable to replace air (nitrogen concentration: about 79% by volume, oxygen concentration: about 21% by volume) with another gas. Particular preference is given to substituting (purging) air with nitrogen.

By supplying an inert gas into the ionizing radiation chamber and setting a condition to slightly blow the inert gas into the web injection surface of the irradiation chamber, it is possible to exclude the entrained air after the movement and to effectively reduce the oxygen concentration in the reactor chamber. In addition, it is also possible to effectively reduce the substantial oxygen concentration on polar surfaces with large curing disturbances due to oxygen. The direction of inert gas flow at the web injection side of the irradiation chamber can be adjusted by adjusting the balance between the air supply and the discharge of the irradiation chamber.

As for the method of discharging entrained air, it is preferable to blow inert gas directly onto the web surface.

In addition, by providing a front chamber in front of the reaction chamber to remove oxygen from the web surface in advance, the curing process can be made more effective. In addition, the gap between the side and the web surface of the web inlet side of the ionizing radiation reaction chamber or front chamber for the purpose of effectively using the inert gas is preferably 0.2 to 15 mm, more preferably 0.2 to 10 mm, most preferably 0.2 to 5 mm. However, in order to produce the web continuously, it is necessary to join and connect the webs. For joining, a method of pasting with a joining tape or the like is widely used. For this reason, too narrow a gap between the web inlet side and the web of the ionizing radiation reaction chamber or front chamber causes a problem such as a sticking of a bonding member such as a bonding tape. For this reason, in order to narrow the gap, it is preferable to make at least one portion of the web inlet side of the ionizing radiation reaction chamber or the front chamber movable, so that the gap is widened at a rate corresponding to the thickness of the joint when the joint portion comes in. . Methods that can be used to realize this include a method of making the inlet side of the ionizing radiation reaction chamber or the front chamber move back and forth in the direction of movement, and moving back and forth as the junction passes therethrough to widen the gap; And making the inlet side of the ionizing radiation reaction chamber or the front chamber moveable in the vertical direction of the web surface, and moving up and down to widen the gap as the joining portion passes therethrough.

In hardening, it is preferable to heat a film surface to 60 degreeC or more and 170 degrees C or less. When the heating temperature is lower than 60 ° C., the heating effect is low, whereas when it is higher than 170 ° C., problems such as deformation of the substrate are caused. The heating temperature is more preferably 60 ° C to 100 ° C. The temperature of "film surface" as referred to herein means the temperature at which the film surface of the layer cures. Thus, the time required to reach the temperature is at least 0.1 seconds and at most 300 seconds, more preferably at most 10, after the start of UV irradiation. If the time for keeping the temperature of the film surface within the above temperature range is too short, the reaction of the curable composition capable of forming a film cannot be accelerated. On the other hand, if it is too long, problems in production, such as deterioration in optical performance of the film and increase in equipment, are caused.

The heating method is not particularly limited, but preferred examples thereof include a method of heating a roll and contacting it with a film; A method of blowing heated nitrogen; And a method of irradiating near infrared rays and infrared rays. A method of performing heating while flowing a medium such as hot water, steam and oil into a rotating metal roll, described in Japanese Patent No. 2523574, can also be used. As the heating means, a dielectric heating roll or the like can be used.

Ultraviolet irradiation can be performed each time when providing one layer for each of the plurality of structural layers, or after lamination. Alternatively, the investigation can be performed by combining this. It is preferable to irradiate an ultraviolet-ray after laminating | stacking multiple layers from a productivity viewpoint.

In the present invention, one or more layers laminated to the support can be cured by irradiating the ionizing radiation several times. In this case, the ionizing radiation is preferably carried out two or more times in a continuous reaction chamber in which the oxygen concentration does not exceed 3% by volume. By carrying out the ionizing radiation irradiation several times in the reaction chamber having the same low oxygen concentration, it is possible to effectively secure the reaction time required for curing.

In particular, when increasing the production rate for high productivity, it is necessary to perform ionizing irradiation several times in order to secure the energy of the ionizing radiation required for the curing reaction.

Furthermore, if the cure rate [100- (remaining functional group content)] value is less than 100%, in providing a layer thereon and curing through ionizing radiation and / or heat, the cure rate of the lower layer is higher than before providing the top layer. When high, the adhesion between the bottom layer and the top layer is improved, which is desirable.

4- (6) Handling:

Continuous delivery of a roll of support film for continuous production of the film of the invention; Coating and drying of the coating solution; Curing of the coating film; And winding the support film having the cured layer.

The film support is continuously transferred from the rolled film support into the clean chamber; Static electricity charged in the film support is removed by a destaticization device in the clean chamber; Subsequently, the foreign matter adhering to the film support is removed by the dust removal unit. The coating solution is then coated on the film support of the coating portion while located in the clean chamber, and the coated film support is sent to a drying chamber and dried.

The film support having the dried coating layer is transferred from the drying chamber to the curing chamber, and the monomers contained in the coating layer are polymerized and cured. In addition, the film support having the cured layer is sent to a curing portion, where curing is completed; The film support having the fully cured layer is wound to a roll state.

The foregoing steps can be performed for each layer formation. By providing a plurality of coating portions / drying chambers / curing portions, it is possible to carry out the formation of each layer.

In order to produce the film of the present invention, at the same time as the microfiltration process of the coating solution, the coating step of the coating portion and the drying step in the drying chamber are performed in a high clean air atmosphere, and before the coating is carried out, contaminants on the film And dust thoroughly. The air cleanliness in the coating step and in the drying step is preferably based on air cleanliness in accordance with Federal Standard No. 209E, preferably of grade 10 (number of particles having a diameter of 0.5 μm or more, 353 / m ³ or less), more preferably of class 1 (0.5) The number of particles having a thickness of not less than 35.5 / m ³ ). It is also desirable to have high air cleanliness in steps other than the coating and drying steps, such as transfer and winding up.

4- (7) Saponification Treatment:

In manufacturing a polarizing plate using the film of this invention as one of the two surface protection films of a polarizing film, it is preferable to hydrophilize the surface of the surface to which a polarizing film adheres, and to improve the adhesive force of an adhesion surface.

(a) Method of Dipping in Alkaline Solution

This method is a means by which the film is immersed in an alkaline solution to saponify all surfaces that are reactive with alkali over the entire film surface. This method does not require special equipment and is therefore preferable in terms of cost. An aqueous sodium hydroxide solution is preferred as the alkaline solution. The concentration of the alkaline solution is preferably 0.5 to 3 mol / L, more preferably 1 to 2 mol / L; And the liquid temperature of the alkaline solution is preferably 30 to 75 ° C, more preferably 40 to 60 ° C.

Although the combination of the saponification conditions is a combination of relatively moderate conditions, it can be set according to the arrangement of the raw material and the film and the contact angle required.

After being immersed in the alkaline solution, it is preferable to neutralize the alkali component by thoroughly washing the film with water or immersing the film in dilute acid so that the alkali component does not remain on the film.

By the saponification treatment, the opposite surface of the surface on which the coating layer is present is hydrophilized. The protective film for polarizing plates is provided for use after attaching the hydrophilized surface of a transparent support body to a polarizing film.

Hydrophilized surfaces are effective in improving adhesion to adhesion surfaces made of polyvinyl alcohol as a main component.

In the saponification process, from the viewpoint of adhesion to the polarizing film, it is preferable that the contact angle to water of the transparent support surface on the opposite side to the side where the coating layer is present is as low as possible. On the other hand, in the immersion method, since the film is simultaneously damaged by alkali from the surface where the coating layer exists to the inside of the film, it is important to apply the minimum conditions necessary. When the contact angle of the transparent support on the surface on the opposite side to water is used as an index of damage received by each layer by alkali, especially when the transparent support is triacetyl cellulose, the contact angle is preferably 10 ° to 50 °, more preferably. 30 ° to 50 °, more preferably 40 ° to 50 °. If the contact angle exceeds 50 °, problems arise in adhesion to the polarizing film, and therefore this is not preferable. On the other hand, if it is less than 10 °, the damage to the film becomes excessively large and the physical strength is hindered, which is not preferable.

(b) Alkaline solution coating method:

As a means for avoiding damage to each film in the immersion method, it is preferable to use the method of coating the alkali solution only by coating the alkali solution only on the surface opposite to the surface on which the coating layer is present, followed by heating, washing with water and drying. desirable. In this case, however, "coating" as used herein means contacting an alkaline solution or the like only with the surface on which saponification has been performed. In addition to coatings, spraying, contact with liquid-containing belts or other means are also included. With this method, since the apparatus and steps for coating the alkaline solution are separately required, this method is inferior in cost compared to the dipping method (a). On the other hand, since the alkaline solution contacts only the surface to which the saponification treatment has been applied, a layer using a raw material vulnerable to the alkaline solution can be provided on the opposite surface. For example, in vapor deposition films or sol-gel films, various effects such as corrosion, decomposition and delamination are caused due to the alkaline solution. Therefore, it is not desirable to provide such vapor deposition film or sol-gel film by dipping, but in this coating method, since the film is not in contact with the solution, such vapor deposition film or sol-gel film can be used without any problem. Can be.

In all the saponification methods (a) and (b) above, the film can be unrolled from the support in a rolled state, and after forming each layer, saponification can be carried out, so that it can be added after the film production step, and a series of Can be achieved in the process. Further, by continuously performing the step of attaching to a polarizing plate made of a support body which is similarly unwound in general, a polarizing plate can be produced with good efficiency as compared with the case of performing the same process for each sheet.

(c) How to protect with laminate film to achieve saponification:

Similar to the above method (b), when the coating layer lacks resistance to the alkaline solution, after forming the final layer, the laminate film is applied to the surface on which the final layer is formed, and then immersed in the alkaline solution to form the surface on which the final layer is formed. Only the triacetyl cellulose surface on the opposite side can be hydrophilized and the laminate film can be peeled off. According to this method, sufficient hydrophilicity treatment as a protective film for polarizing plates can be applied only to the surface of the triacetyl cellulose film on the side opposite to the surface on which the final layer is formed, without damaging the coating layer. Compared with the above method (b), this method has the advantage that the laminate film is produced as waste, but no special apparatus for coating the alkaline solution is required.

(d) After forming the intermediate layer, the method is immersed in alkaline solution:

If the lower layer has resistance to the alkaline solution, but the resistance of the upper layer to the alkaline solution is insufficient, after forming the lower layer, the film is immersed in the alkaline solution to hydrophilize both surfaces, and then the upper layer Can be formed. The production process is complicated. However, for example, in a film composed of a low refractive index layer and an antiglare layer made of a fluorine-containing sol-gel film, the advantage that the interlayer adhesion between the antiglare layer and the low refractive index layer is improved when a hydrophilic layer is present have.

(e) A method of forming a coating layer on a previously saponified triacetyl cellulose film:

The coating layer may be formed directly or through another layer on one surface of the triacetyl cellulose film which has been immersed in alkaline solution or previously saponified by other means. When saponification of the triacetyl cellulose film by dipping in an alkaline solution, the interlayer adhesion to the hydrophilized triacetyl cellulose surface through saponification may be deteriorated. In this case, this problem can be solved by removing only the surface on which the coating layer is formed after saponification, by treating with corona discharge or glow discharge or by other means to remove the hydrophilized surface. In addition, when the coating layer includes hydrophilic groups, the interlayer adhesion may be good.

Preparation of 4- (8) Polarizing Film:

The film of this invention can be used as a polarizing film using it as a polarizing film and a protective film arrange | positioned at one side or both sides thereof.

The film of the present invention can be used as one protective film, while a conventional cellulose acetate film can be used as another protective film. However, it is preferable to use the cellulose acetate film produced by the solution film forming method and stretched in the width direction in the roll state, so that the stretching ratio is 10 to 100%.

In addition, it is preferable that the polarizing plate of the present invention is an antireflection film while one surface thereof is an optical correction film made of a liquid crystalline compound.

Examples of the polarizing film include an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, and a polyene-based polarizing film. Iodine based polarizing films and dye based polarizing films are generally produced using polyvinyl alcohol based films.

The slow axis of the transparent support of the antireflective film or cellulose acetate film and the transmission axis of the polarizing film are arranged substantially parallel to each other.

For the production of polarizing plates, the moisture permeability of the protective film is important. The polarizing film and the protective film are attached to each other through the aqueous adhesive, and the solvent of the adhesive is diffused into the protective film, so that drying is achieved. When the moisture permeability of the protective film is high, drying is faster and productivity is improved. However, when the moisture permeability is too high, moisture enters the polarizing film in the use environment of the liquid crystal display device (under high humidity), and thus the polarizing ability is lowered.

The moisture permeability of the protective film is determined by the thickness, free volume, hydrophilicity or hydrophobicity, etc. of the transparent support or the polymer film (and the polymerizable liquid crystal compound).

When the film of the present invention is used as a protective film for a polarizing plate, the moisture permeability is preferably 100 to 1,000 g / m ² · 24 hours, more preferably 300 to 700 g / m ² · 24 hours.

In the case of forming a film, the thickness of the transparent support can be adjusted by lip flow rate and linear velocity or stretching or compression. Since moisture permeability changes with the main raw material used, moisture permeability of a preferable range can be set by adjusting thickness.

When forming the film, the free volume of the transparent support can be adjusted by drying temperature and time.

In this case, the moisture permeability also varies depending on the main raw materials used, so that the free volume can be adjusted to determine the desired range.

Hydrophilicity or hydrophobicity of the transparent support can be adjusted with additives. By adding hydrophilic additives to the free volume, the moisture permeability is increased, while the addition of hydrophobic additives can lower the moisture permeability.

By independently controlling the moisture permeability, it is possible to produce a polarizing plate having optical correction capability at low cost and high productivity.

As the polarizing film, it is possible to use a polarizing film and a known polarizing film in which the absorption axis is cut from the terminal polarizing film which is not parallel or perpendicular to the longitudinal direction. The terminal polarizing film whose absorption axis is not parallel or perpendicular to the longitudinal direction is produced by the following method.

That is, this polarizing film is a polarizing film manufactured by extending | stretching the polymer continuously supplied by giving tension, fixing both ends in a holding unit. The polarizing film extends the film at a ratio of 1.1 to 20.0 times at least in the film width direction; The difference in the speed of movement between the fixing units at both film ends in the longitudinal direction is within 3%; And a stretching method of bending the moving direction of the film in a state where both ends of the film are fixed so that an angle between the moving direction of the film and the substantially stretching direction of the film is inclined at 20 ° to 70 ° at the exit of the step of fixing the both ends of the film. Can be produced by In particular, a polarizing film in which the object angle is inclined at 45 ° is preferably used in view of productivity.

The stretching method of the polymer film is described in detail in paragraphs [0020] to [0030] of JP-A-2002-86554.

Among the two protective films of the polarizer, it is also preferable that the film which is not an antireflection film is an optical correction film having an optical correction layer including an optically anisotropic layer. Optical correction films (delay films) can improve viewing angle characteristics of liquid crystal display screens.

Known optical correction films can be used as the optical correction films. The optical correction film of JP-A-2001-100042 is preferable from a viewpoint of extending a viewing angle.

5. Uses of the Invention Embodiments:

The film of the present invention is used in an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescent display device (ELD) and a cathode ray tube display device (CRT). The optical filter according to the present invention can be used for a known display device such as a plasma display panel (PDP) or the like.

5- (1) liquid crystal display device:

The film of the present invention can advantageously be used in an image display device such as a liquid crystal display device. It is preferable to use the film of the present invention for the outermost layer of the display.

In the liquid crystal display device, a liquid crystal cell and two polarizing plates are disposed on both sides thereof, and the liquid crystal cell supports the liquid crystal between the two electrode substrates. In addition, one optically anisotropic layer may be disposed between the liquid crystal cell and one polarizing plate, or two optically anisotropic layers may be disposed between the liquid crystal cell and two respective polarizing plates.

It is preferable that a liquid crystal cell is TN mode, VA mode, OCB mode, IPS mode, or ECB mode.

<TN mode>

In the liquid crystal cell of the TN mode, the liquid crystalline molecules are sometimes arranged substantially horizontally, and further aligned in a twisted state at 60 ° to 120 ° when no voltage is applied.

Liquid crystal cells in TN mode are most frequently used as color TFT liquid crystal display devices and are described in many references.

<VA mode>

In the liquid crystal cell of VA mode, the liquid crystalline molecules are aligned substantially vertically at the time when no voltage is applied.

The liquid crystal cell in VA mode is (1) the liquid crystal cell in narrow VA mode in which the liquid crystalline molecules are substantially vertically aligned at the time when no voltage is applied, while the liquid crystal cells are substantially horizontally aligned at the time when voltage is applied. In addition to (described in JP-A-2-176625), (2) a liquid crystal cell of multi-domain VA mode (MVA mode) for viewing angle extension (described in SID 97, Digest of Tech. Papers , 28 (1997), p 845). search), (3) rods liquid crystalline molecules are liquid crystal cells (n-ASM mode of the mode in which the twisted multi-domain alignment at the time that is aligned substantially perpendicular to the timing at which the voltage is not applied, the voltage is applied) (Preprints of Forum on Liquid Crystal, p 58-59 (1998)), and (4) liquid crystal cells in SURVIVAL mode (presented in LCD International 98 ).

<OCB Mode>

Liquid crystal cells in OCB mode are liquid crystal cells in a bent alignment mode in which liquid crystalline molecules are sometimes aligned substantially in opposite directions (symmetrically) at the top and bottom of the liquid crystal cell, US Pat. Nos. 4,583,825 and 5,410,422 It is described in the issue. Since liquid crystalline molecules are symmetrically aligned at the top and bottom of the liquid crystal cell, the bent alignment mode liquid crystal cell has a self optical compensation capability. For this reason, this liquid crystal mode was named OCB (optical supplementary bend) liquid crystal mode. The bent alignment mode liquid crystal display device has advantages such as fast reaction speed.

<IPS Mode>

The liquid crystal cell of the IPS mode is to open and close the system by applying a transverse electric field to the nematic liquid crystal. For details, see Proc. IDRC (Asia Display `95), p 577-580 and p 707-710.

<ECB mode>

In the liquid crystal cell of the ECB mode, the liquid crystalline molecules are aligned substantially horizontally at the time when no voltage is applied. The ECB mode is one of the liquid crystal display modes having the simplest structure, and details are described, for example, in JP-A-5-203946.

Display other than 5- (2) liquid crystal display device

<PDP>

Plasma display panels (PDPs) generally consist of substrates, glass substrates, electrodes, electrode lead materials, thick film printing materials and fluorescent materials. The glass substrate consists of two sheets, a front glass substrate and a back glass substrate. In each of the two organic substrates, an electrode and an insulating layer are formed. In the back glass substrate, a layer of fluorescent material is additionally formed. Two glass substrates are assembled and the gas is sealed therebetween.

Plasma display panels (PDPs) are already commercially available. Plasma display panels are described in JP-A-5-205643 and JP-A-9-306366.

In some cases, the front plate may be arranged in front of the plasma display panel. It is desirable that the front plate is strong enough to protect the plasma display panel. The front plate may be used at regular intervals from the plasma display panel, or may be directly attached to the body of the plasma display panel.

In an image display device such as a plasma display panel, an optical filter may be directly attached to the display surface. In addition, when the front plate is provided in front of the display, the optical filter may be attached to the front side (outside side) or the rear side (display side) of the front plate.

<Touch panel>

The film of the present invention can be applied to a touch panel as described in JP-A-5-l27822 and JP-A-2002-48913 and the like.

<Organic EL element>

The film of this invention can be used as a board | substrate (substrate film), a protective film, etc. of organic electroluminescent element.

When the film of this invention is used for organic electroluminescent element etc., JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP-A-2001 -192653, JP-A-2001-335776, JP-A-2001-247859, JP-A-2001-1816l6, JP-A-2001-1816l7, JP-A-2002-181816, JP-A-2002-l8l617 And JP-A-2002-056976 can be applied. Moreover, it is preferable to use combining the content of JP-A-2001-148291, JP-A-2001-221916, and JP-A-2001-231443.

6. Various characteristic values:

Various measurement methods and preferred property values will be presented below in connection with the present invention.

6- (1) Reflectance:

Regarding the measurement of mirror reflectance and color taste, using a spectrophotometer "V-550" (manufactured by JASCO Corporation) equipped with adapter "ARV-474", the angle of incidence 5 ° and the angle of reflection -5 ° In each case, the mirror reflectance is measured in the wavelength region of 380 to 780 nm, and the average reflectance at 450 to 650 nm is calculated, thereby evaluating antireflective properties.

Regarding the anti-glare antireflection film of the present invention, a mirror reflectance of 2.0% or less and a transmittance of 90% or more are preferable because reflection of external light can be suppressed and visibility can be improved. The mirror reflectance is particularly preferably 1.5% or less. Most preferably, the reflectance is adjusted to 1.0% or less using the layer arrangement as described in 3- (d).

6- (2) color:

With respect to the polarizing plate of the present invention provided with antireflection capability, the color of light specularly reflected against the angle of incidence at the angle of incidence 5 ° in the region of the CIE standard light source D ₆₅ , having a wavelength of 380 nm to 780 nm, namely CIE1976 L *, It is possible to evaluate color by setting the L *, a * and b * values of the a * and b * color spaces.

The L *, a * and b * values preferably satisfy the relationship of (3≤L * ≤20), (-7≤a * ≤7) and (-10≤b * ≤10), respectively. By allowing this value to fall within this range, the color of the reflected light from red purple to blue purple, an aspect that has been considered problematic until now, is reduced. Further, when the L *, a * and b * values satisfy the relationship of (3≤L * ≤10), (0≤a * ≤5) and (-7≤b * ≤0), respectively, The phosphorus problem is greatly reduced, and when the polarizing plate is applied to the liquid crystal display device, even when external light having high luminescence such as light emitted from a fluorescent lamp in the room is weakly reflected, the color is neutral and inconspicuous. In detail, in the case of (a * ≦ 7), the red color is not excessively strong, whereas in the case of (a * ≧ 7), the cyan color is not excessively strong, so this is preferable. In addition, in the case of (b * ≧ 7), the blue color does not become excessively strong, whereas in the case of (b * ≦ 0), the yellow color does not become excessively strong, so this is preferable.

In addition, the color uniformity of the reflected light is a * and b * on the L * a * b * chromaticity diagram as determined from the reflection spectrum of the reflected light at 380 nm to 680 nm by the conversion of color according to the following formula (21). Can be obtained from.

Formula (21)

[Conversion of color in (a *)] = [(a * _max -a * _min ) / a * _average ] × 100

[Conversion of color in (b *)] = [(b * _max -b * _min ) / b * _average ] × 100

Where a * _max and a * _min represent the maximum and minimum values of the a * values, respectively; b * _max and b * _min represent the maximum and minimum values of the b * values, respectively; a * _mean and b * _mean represent the mean value of a * value and the mean value of b * value, respectively. Each of the color conversions is preferably 30% or less, more preferably 20% or less, and most preferably 8% or less.

Furthermore, the film of this invention, Preferably, (DELTA) EW which is a change of the color feeling before _and behind a weather resistance test is 15 or less, More preferably, it is 10 or less, Most preferably, it is 5 or less. When ΔE _W lies within this range, it is possible to achieve both low reflectance and a reduction in the color of the reflected light. Thus, for example, when the film of the present invention is applied to the outermost layer of an image display device, even when external light having high luminescence such as light emitted from a fluorescent lamp in the room is weakly reflected, the color is neutral and the display image is Since the quality becomes good, such a thing is preferable.

ΔE _{W, which} is a change in color, may be determined according to the following equation (22).

Formula (22)

△ E _W = [(△ L _W ) ² + (△ a _W ) ² + (△ b _W ) ² ] ^1/2

Here, ΔL _W , Δa _W and Δb _W represent the amount of change in L * value, the amount of change in a * value and the amount of change in b * value before and after the weathering test, respectively.

6- (3) transmitted image clarity:

The transmitted image clarity is Suga Test Instruments Co., Ltd. It can be measured using an optical comb having a slit width of 0.5 mm according to JIS K7105 by an image sharpness meter (MICM-2D Model) as manufactured by.

The film of the invention preferably has a transmitted image clarity of 15 to 100%. The transmitted image clarity is generally an indicator for indicating the bleeding state of the image transmitted and projected through the film. The larger the value, the better the sharpness of the image seen through the film. When the film of the present invention is an anti-glare film, it is preferable that the transmitted image clarity of the film is 15% to 40%, since sufficient anti-glare property and improvement of image blur and reduction of dark room contrast can be achieved. .

6- (4) Surface Roughness:

The measurement of the center line average roughness Ra can be performed according to JIS B0601.

The antireflective film of the present invention has a centerline average roughness Ra of 0.08 to 0.30 mu m in relation to the surface irregularity shape; 10-point average roughness Rz is 10 times or less of Ra; The average crest / root distance Sm is 1 to 100 μm; The standard deviation of the height of the convex portion from the deepest portion of the irregularity is 0.5 μm or less; The standard deviation of the mean crest / root distance Sm relative to the centerline is 20 μm or less; It is devised in this way to occupy 10% or more of the surfaces having an incidence angle of 0 to 5 ° to achieve both sufficient anti-glare properties and visually uniform mat feel. If Ra is less than 0.08 μm, sufficient anti-glare properties are not obtained, whereas if it is more than 0.30 μm, problems such as glare and whitening of the surface are caused when external light is reflected.

6- (5) haze:

The haze of the film of the present invention is a haze value as defined in JIS K7105 and is based on Nippon Denshoku Industries Co., Ltd. based on the measurement method as described in JIS K7361-1. The haze turbidimeter " NDH-1001DP " manufactured automatically by " haze = [(scattered light) / (total transmitted light)] × 100 (%) ") is automatically measured.

In addition, surface haze and internal haze can be measured by the following procedure.

(1) The total haze value (H) of the film is measured according to JIS K7136.

(2) adding a few drops of silicone oil to the front of the film and the back of the film on the side of the low refractive index layer; Sandwiching the film from front to back by two sheets of glass plate 1 mm thick (manufactured by MICRO SLIDE GLASS Product No. S9111, Matsunami Glass Ind., Ltd.) to bring the film into full contact with the two glass plates; The haze is measured with the surface haze removed; The value obtained by subtracting the individually measured haze by putting only silicone oil between two glass plates therefrom is calculated as the internal haze (Hi) of the film.

(3) The value obtained by subtracting the internal haze (Hi) calculated in the above (2) from the total haze (H) measured in the above (1) is calculated as the surface haze (Hs).

6- (7) Scars:

<Evaluation of scar resistance by steel wool>

It is possible to provide an index for scar resistance by performing a rubbing test under the following conditions using a rubbing tester.

Evaluation environmental conditions: 25 ℃, 60% RH

Rub material: Steel Wool (manufactured by Nippon Steel Wool Co., Ltd., Grade No. 0000). Damage and fasten the band around the tip of the tester (1 cm × 1 cm) where the steel wool is in contact with the specimen.

Travel distance (one way): 13 cm

Rub Speed: 13 cm / sec

Load: 500 g / cm ² and 200 g / cm ²

Tip area of contact: 1 cm × 1 cm

Number of rubs: 10 round trips

Oily black ink is applied to the back side of the rubbed specimen, and the wound on the rubbed portion is evaluated by visual observation by reflected light or by the difference in the amount of reflected light from portions other than the rubbed portion.

<Evaluation of scar resistance by eraser rub>

It is possible to provide an index for scar resistance by performing a rubbing test under the following conditions using a rubbing tester.

Evaluation environmental conditions: 25 ℃, 60% RH

Rub material: Plastic eraser (manufactured by MONO, Tombow Pencil Co., Ltd.). Secure the plastic eraser to the tip of the tester (1 cm x 1 cm) in contact with the specimen.

Travel distance (one way): 4 cm

Rub Speed: 2 cm / sec

Load: 500 g / cm ²

Tip area of contact: 1 cm × 1 cm

Number of rubs: 100 round trips

Oily black ink is applied to the back side of the rubbed specimen, and the wound on the rubbed portion is evaluated by visual observation by reflected light or by the difference in the amount of reflected light from portions other than the rubbed portion.

<Tester test>

By the taper test according to JIS K5400, the scar resistance can be evaluated from the amount of wear of the specimen before and after the test.

It is desirable that the amount of wear is as small as possible.

6- (8) Hardness:

<Pencil hardness>

The hardness of the film of this invention can be evaluated by the pencil hardness test according to JISK5400.

Pencil hardness is preferably at least H, more preferably at least 2H, most preferably at least 3H.

Surface modulus of elasticity

In the present invention, the surface elastic modulus is a value measured using a micro-surface hardness tester (manufactured by Fischer Scope H100VP-HCU, Fischer Instruments K.K.). Specifically, the surface modulus of elasticity is measured by using a diamond-shaped pyramid indenter (tip face angle: 136 °) and measuring the indentation depth under an appropriate test load within a range where the indentation depth does not exceed 1 μm. Elastic modulus measured from the change between displacements during removal.

In addition, surface hardness can also be measured by using the micro-surface hardness tester as general hardness. General hardness is a value obtained by measuring the indentation depth under test load of a square pyramidal indenter, and dividing the test load by the surface area of the mark generated under the test load calculated from the geometry of the mark. It is known that there is a positive correlation between the surface elastic modulus and the general hardness.

The general hardness of the crosslinked polymer as defined in the present invention is determined in relation to the crosslinked polymer film having a thickness of about 20 to 30 μm, which is cured and formed on the glass plate using the micro hardness tester H100 according to the following measuring procedure. It is expressed as general hardness (N / mm ² ).

In addition to the crosslinked polymer, a coating solution containing an essential catalyst, a crosslinking agent and a polymerization initiator, and having a solid content of about 25%, is manufactured by Toshinriko Co., Ltd. On a glossy slide glass plate (26 mm x 76 mm x 1.2 mm) as prepared by the above, an appropriate bar coater was selected and coated so as to have a thickness of about 20 to 30 m after curing. If the crosslinked polymer is thermally curable, the thermal curing conditions (eg, at 125 ° C. for 10 minutes) at which the film is fully cured are predetermined; If the crosslinked polymer is ionizing radiation curable, the curing conditions (eg oxygen concentration: 12 ppm, UV irradiation dose: 750 mJ / cm ² ) at which the film is fully cured are predetermined. For each film, the load is continuously increased from 0 to 4 mN; Conical diamond indenter is indented while maximizing the 1/10 thickness that the hardness of the substrate glass plate does not affect; The general hardness is calculated from the average measured value of N = 6 of F / A measured from the indentation area A (mm ² ) against each load F.

In addition, surface hardness can be measured by nano indentation as described in JP-A-2004-354828. In this case, the hardness is preferably 2 GPa to 4 GPa, and the nano-indentation modulus is 10 GPa to 30 GPa.

6- (9) antifouling test:

<Marker ink wiping characteristics>

The film is fixed to the glass surface with an adhesive; A circle 5 mm in diameter under conditions of 25 ° C. and 60 RH% 3 times with a pen tip of the black marking pen “McKee Ultra-fine (trade name of Zebra Co., Ltd.)”; After 5 seconds, 20 reciprocating movements are carried out under a load up to the range in which the BEMCOT bundle is press-fitted by a bundle of 10-folded BEMCOT (trade name of Asahi Kasei Corporation). By repeating the drawing and wiping until the marker ink marks do not disappear by wiping under the above conditions, it is possible to evaluate the antifouling properties converted into the number of wipings that can be wiped.

The number of wipings is preferably 5 or more times, more preferably 10 or more times until the marker ink marks do not disappear.

Regarding the black marker ink, MAGIC INK No. Draw a circle 1 cm in diameter using 700 (M700-T1 Black) Ultra-fine, leave for 24 hours, then rub with BEMCOT (manufactured by Asahi Kasei Corporation). The wiping properties can then be evaluated by whether the marker ink is wiped off.

6- (10) Contact Angle:

Needle tip in dry condition (at 20 ° C and 65% RH) using pure water as liquid, using a contact angle meter ("CA-X" type contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.) Droplets having a diameter of 1.0 mm were prepared and then contacted with the surface of the film to produce droplets on the film. At the point where the film and the liquid contact each other, the angle formed between the liquid surface and the tangent to the film surface and the surface containing the liquid is defined as the contact angle.

The contact angle of the film of the present invention is preferably 94 ° or more, more preferably 97 ° or more, most preferably 101 ° or more.

6- (11) surface free energy:

Surface energy can be measured by contact angle methods, wet heat measurements, or absorption methods as described in Foundation and Application of Wetting , published by Realize Advanced Technology Limited, December 10, 1989. In the case of the film of the present invention, it is preferable to use a contact angle method.

Specifically, two kinds of solvents having a known surface energy are dropped on the cellulose acylate film; The angle of the droplet-containing face is defined by the angle formed between the droplet and the tangent drawn against the film surface at the intersection of the droplet surface and the film surface; The surface energy of a film can be calculated by calculation.

As mentioned herein, the surface free energy (γ s ^v : unit, mN / m) of the film of the present invention is described in DK Owens, J. Appl. Polym. Sci. , 13 , 1974 (1969)] from the contact angles θ _H2O and θ _CH2I2 of pure water H ₂ O and methylene iodide CH ₂ I _2, respectively, on the antireflective film as measured experimentally with reference to And the surface tension of the antireflective film as defined by the value γs ^v (= γs ^d + γs ^h ) expressed by the sum of γs ^d and γs ^h measured by (b). When the γs ^v is small and the surface free energy is low, the film has a high surface repulsive force and generally has excellent antifouling properties.

Formula (a)

1 + cosθ _H2O = 2√γs ^d (√γ _H2O ^d / γ _H2O ^v ) + 2√γs ^h (√γ _H2O ^h / γ _H2O ^v )

Equation (b)

1 + cosθ _CH2I2 = 2√γs ^d (√γ _CH2I2 ^d / γ _CH2I2 ^v ) + 2√γs ^h (√γ _CH2I2 ^h / γ _CH2I2 ^v )

γ _H2O ^d = 21.8, γ _H2O ^h = 51.0, γ _H2O ^v = 72.8

γ _CH2I2 ^d = 49.5, γ _CH2I2 ^h = 1.3, γ _CH2I2 ^v = 50.8

Kyowa Interface Science Co., Ltd., which controls the film under humidity of 25 ° C. and 60% for at least 1 hour, is an automatic contact angle meter. A contact angle measurement was performed by dropping 2 μL of droplets onto the film using a CA-V150 Model prepared by the present invention and after 30 seconds, measuring the contact angle.

The surface free energy of the film of the present invention is preferably 25 mN / m or less, particularly preferably 20 mN / m or less.

6- (12) Curl:

The curl is measured using the template for curl measurement of method A in "Determination of the curl of photographic film" of JIS K7619-1988.

The measurement is carried out for a humidity control time of 10 hours under conditions at 25 ° C. and 60% relative humidity.

In the film of the present invention, the curl is preferably a value represented by the following formula, in the range from -15 to +15, more preferably in the range from -12 to +12, even more preferably from -10 to +10 It has a value represented by a range. At this time, in the case of the coating of a web state, the measurement direction of the curl in a sample is a conveyance direction of a board | substrate.

Equation

Curl = I / R (R: radius of curvature (m))

This is an important property for preventing cracking or film separation that occurs in manufacturing, processing and handling in the film market. It is preferable that the curl value is within this range and small.

Here, a curl with a positive value means that the coating side of the film is curled inwards, whereas a curl with a negative value means that the coating side of the film is curled outwards.

In addition, in the film of the present invention, when only the relative humidity changes to 80% and 10%, respectively, based on the curl measuring method, respectively, the absolute value of the difference in curl values therebetween is preferably 24 to 0, more Preferably it is 15-0, most preferably 8-0. This is a property related to handling properties, separation and cracking when the film sticks under various humidity.

Evaluation of 6- (13) Adhesion:

The adhesion between the layers of the film or between the support and the coating layer can be evaluated by the following method.

The surface of the film in terms of where the coating layer is present is cross-cutted 11 lines in the longitudinal direction and 11 lines in the width direction using a cutter knife to provide a total of 100 squares; Press-contacting a polyester pressure-sensitive adhesive tape (No. 31B) manufactured by Nitto Denko Corporation; After holding for 24 hours, the peel test was repeated three times at the same place to visually confirm the presence or absence of peeling.

It is preferable that peeling is observed within 10 out of 100 squares; More preferably, peeling is observed in two out of 100 squares.

6- (14) Brittleness Test (Crack Resistance):

Crack resistance is an important property for preventing cracking defects in coatings such as coating, processing and cutting of films, coating of adhesives and sticking to various materials.

The surface crack cuts the film specimen into a size of 35 mm × 140 mm, which was maintained for 2 hours under a temperature of 25 ° C. and a relative humidity of 60%, rolled up into a columnar shape, and the curvature at which the crack began to occur. The radius can be measured and evaluated.

With regard to the crack resistance of the film of the present invention, when the film is rolled up in such a manner that the coating layer surface is located outward, the radius of curvature in which the crack occurs is preferably 50 mm or less, more preferably 40 mm or less, most Preferably it is 30 mm or less. With regard to cracks at the edges, it is preferred that no cracks occur or that the length of the cracks is on average less than 1 mm.

6- (15) Dust Removal Characteristics:

The dust removal characteristics can be evaluated by attaching the film of the present invention to a monitor, spraying dust (for example, blankets or bundles of fibers) onto the monitor surface, and wiping off the dust with a cleaning cloth.

It is preferable that the dust can be completely removed by six wiping cycles; More preferably, the dust can be completely removed by wiping within three times.

6- (16) Liquid Crystal Display Device Performance:

The evaluation method of the characteristic and the preferred state when using the film of the present invention on the display device will be described below.

 Peel off the polarizing plate on the viewing surface provided in the liquid crystal display device using the TN type liquid crystal cell (TH-15TA2, manufactured by Matsushita Electric Industrial Co., Ltd.), and instead, the film or polarizing plate of the present invention The adhesive was attached so that the coating surface was present on the viewing surface and the transmission axis of the polarizing plate coincided with the polarizing plate adhered to the product. Various display characteristics can be visually evaluated from various viewing angles in a bright space while displaying a liquid crystal display device in black.

<Evaluation of Image Unevenness and Color>

By using the manufactured liquid crystal display device, the nonuniformity and the change of a color feeling at the time of using a black display L1 are visually evaluated by many observers.

When ten observers evaluate, it is preferable that three or fewer observers can recognize the nonuniformity, the change of color left and right, the change of color by temperature and humidity, and white bleeding; It is more desirable that no one can recognize these.

In addition, with respect to reflection of external light, fluorescent light can be used to evaluate the change in reflection relatively visually.

<Light leak on black display>

The light leakage rate of the black display is measured in the azimuth direction of 45 ° and the polar angle direction of 70 ° from the front of the liquid crystal display device. The light leakage rate is preferably 0.4% or less, more preferably 0.1% or less.

<Contrast and viewing angle>

Regarding contrast and viewing angle, check contrast ratio and viewing angle (degree of angular range with contrast ratio of 10 or more) in the left and right direction (perpendicular to the rubbing direction of the cell) using an analyzer (EZ-Contrast 160D, manufactured by ELDIM) can do.

Example

The invention will be described in detail with reference to the following examples, but the invention should not be construed as being limited thereto. In the following examples and synthesis examples, the term "%" is% by weight unless otherwise indicated.

Example 1

<Production of Antireflection Film>

[Synthesis of fluorine-containing polymer]

Synthesis Example 1 Synthesis of Fluorine-Containing Polymer P1

An autoclave equipped with a stirrer made of stainless steel, having an internal volume of 100 mL, was charged with 40 mL of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether (HEVE) and 0.55 g of dilauroyl peroxide, The interior was deaerated and purged with nitrogen gas. Additionally, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. When the temperature of the autoclave reached 65 degreeC, the pressure was 5.4 kg / cm <2>. The reaction lasted for 8 hours while maintaining the temperature in the autoclave at 65 ° C., and the heating was stopped when the pressure reached 3.2 kg / cm 2, and then left to cool.

When the internal temperature reached room temperature, the unreacted monomer was released, the autoclave was opened and the reaction solution was taken out. The obtained reaction solution was taken into excess hexane, the solvent was removed by decantation and the precipitated polymer was taken out. Additionally, the polymer was completely removed by dissolving the polymer in a small amount of ethyl acetate and reprecipitating twice from hexane. After drying, 28 g of copolymer PI with an HFP to HEVE molar ratio of 1/1 were obtained. The polymer obtained had a number average molecular weight of 15,000.

Synthesis Examples 2 to 5

Fluorine-containing polymers P18, P37, P39 and P45 were synthesized in substantially the same manner as in the synthesis of P1 of Synthesis Example 1 above, except that the raw materials were changed to those shown in Tables 1 to 5. The number average molecular weights of the respective fluorine-containing polymers obtained are shown in Tables 1 and 2 above.

Synthesis Example 6 Synthesis of Fluorine-Containing Polymer P49

In an autoclave equipped with a stainless steel stirrer and having an internal volume of 2 dm3, 133.0 g of 2-butanone, 33.0 g of 2-propanol, 52.9 g of hydroxyethyl vinyl ether (HEVE), 28.8 g of ethyl vinyl ether (EVE), After charging 15.0 g of Syraplane FM-0721 and 3.9 g of V-65 (polymerization initiator made by Wako Pure Chemical Co., Ltd.), the interior of the system was replaced with nitrogen gas. After additionally introducing 184.1 g of hexafluoropropylene (HFP) into the autoclave, the temperature was raised to 60 ° C. The pressure was 0.93 MPa when the temperature in the autoclave reached 60 ° C. The temperature in the autoclave was maintained at 60 ° C. and the reaction was continued for 8 hours. Thereafter, the temperature of the autoclave was raised to 80 ° C. and the reaction was continued for an additional 1 hour. When the pressure reached 0.44 MPa, heating was stopped and the system was left to cool. After the internal temperature was lowered to room temperature, unreacted monomer was purged. Thereafter, the autoclave was opened to take out the reaction solution. The yield of the polymer thus obtained was 217 g. The number average molecular weight of the polymer was 11,000.

Synthesis Example 7

Fluorine-containing polymer P54 was synthesized in substantially the same manner as the synthesis of P49 in the above synthesis example. The number average molecular weight of the resulting polymer is shown in Table 5.

Synthesis Example 8: Synthesis of p-toluenesulfonate

3.0 g of diethylmethylamine was dissolved in 30 cm 3 of 2-butanone, and 5.7 g of p-toluenesulfonic acid monohydrate was slowly added thereto with stirring. After stirring was continued for an additional hour, the solvent was distilled off under vacuum. The obtained solid was recrystallized from acetone to give the diethylmethylamine salt of p-toluenesulfonic acid.

(Preparation of sol solution (a))

In a reactor equipped with a stirrer and a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyl trimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) and diisopropoxyaluminum ethyl Three parts of acetoacetate were added and mixed. After addition of 30 parts of ion-exchanged water, the mixture was reacted at 60 DEG C for 4 hours, and then cooled to room temperature. The reaction product had a weight average molecular weight of 1,600 and among the components containing the oligomer or polymer component, the component having a molecular weight of 1,000 to 20,000 accounted for 100%. In addition, gas chromatographic analysis revealed no starting acryloyloxypropyl trimethoxysilane left. The sol solution (a) was prepared by adjusting the reaction solution with methyl ethyl ketone to have a solids content of 29%.

(Preparation of sol solution (b))

In a reactor equipped with a stirrer and a reflux condenser, 80 parts of acryloyloxypropyl trimethoxysilane, 20 parts of methyl trimethoxysilane (KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.) and diisopropoxy Three parts of aluminum ethyl acetoacetate were added and mixed. After adding 30 parts of ion-exchanged water, the mixture was reacted at 40 ° C for 60 minutes. The reaction product had a weight average molecular weight of 800, and among the components containing the oligomer or polymer component, the component having a molecular weight of 1,000 to 20,000 accounted for 30%. Additionally, gas chromatography analysis showed that the starting acryloyloxypropyl trimethoxysilane and methyl trimethoxysilane had a residual rate of 10% or less.

(Preparation of Hollow Silica Dispersion A)

Isopropyl alcohol silica sol, prepared by varying the size according to Preparation Example 4 of JP-A-2002-79616, average particle size: 40 nm, shell thickness: 6 nm, silica concentration: 20 wt%, refractive index of the silica particles: 1.30) to 500 parts, 30 parts of acryloyloxypropyl trimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) and 2 parts of trimethyl methoxysilane; and 1.5 parts of diisopropoxyaluminum ethyl acetoacetate was added and mixed. After adding 9 parts of ion-exchanged water, the mixture was reacted at 60 ° C for 8 hours. After cooling to room temperature, 1.8 parts of acetyl acetone were added.

While solvent substitution was carried out by distillation under vacuum at a pressure of 20 kPa, cyclohexanone was added to 500 g of this dispersion to keep the silica content constant. This dispersion was free from the creation of foreign matter. When the solids content was adjusted to 26 wt% with cyclohexanone, the viscosity was found to be 10 mPa · s at 25 ° C. The residual amount of isopropyl alcohol in the obtained dispersion A was analyzed by gas chromatography. As a result, it was found to be 1.0%.

[Production of Antireflection Film]

[Preparation of Coating Solutions for Low Refractive Index Layers (LLL-1 to LLL-53)]

The corresponding components shown in Table 7 were mixed and dissolved in MEK to prepare a coating solution for the low refractive index layer, each having a solids content of 8%. The numerical values in parentheses of Table 7 represent the weight parts of solids of each component.

(* 1) Mixture of sol solution (a) and DPHA (1/1) (weight ratio)

(* 2) Mixture of MEK-ST-L and MEK-ST (3/7) (weight ratio)

(* 3) A mixture of hollow silica and MEK-ST-L (39/9) (weight ratio)

In addition, the material names and product names in the table are as follows.

MEK-ST: Nissan Chemical Industries, Ltd. Colloidal silica prepared by, average particle size: 10 to 15 nm

MEK-ST-L: Nissan Chemical Industries, Ltd. Colloidal silica prepared by, average particle size: about 50 nm

Hollow Silica: Hollow Silica Dispersion A. The solids content of the table represents the total sum of silica and surface treatment agent.

CYMEL 303: Nihon Cytec Industries Inc. Methylated Melamine Prepared by

TAKENATE D110: isocyanate based curing agent manufactured by Takeda Pharmaceutical Industries Limited

DPHA: Nippon Kayaku Co., Ltd. UV curable resin produced by

PTS: p-toluenesulfonic acid monohydrate

H-a and H-b are compounds having the following structure.

Fluorine-containing polymer PR1 in Table 7 is a compound having the following structure and synthesized under the same conditions as described in the following patent document.

PR1: The copolymer of Example 2 described in Japanese Patent No. 3498481.

The numbers indicate the mole fraction of each monomer.

[Preparation of Coating Solution for Anti-Glare Layer (HCL-1)]

PET-30: 50.0 g

IRGACURE 184: 2.0 g

SX-350 (30%): 1.5 g

Cross-linked acrylic-styrene particles (30%): 13.9 g

Sol solution (b): 10.0 g

Toluene: 38.5 g

The mixed solution was filtered through a filter made of polypropylene having a pore diameter of 30 μm to prepare a coating solution for hard coat layer (HCL-1).

The compound used here is as follows.

PET-30: A mixture of pentaerythritol acrylate and pentaerythritol tetraacrylate (manufactured by Nippon Kayaku Co., Ltd.)

IRGACURE 184: polymerization initiator (manufactured by Ciba Specialty Chemicals)

SX-350: crosslinked polystyrene particles having an average particle size of 3.5 μm (refractive index: 1.60, manufactured by Soken Chemical & Engineering Co., Ltd .; 30, as used after dispersion for 20 minutes at 10,000 rpm with a Polytron dispersion machine % Toluene dispersion)

[Preparation of Antireflection Film Sample 101]

The 80-micrometer-thick triacetyl cellulose film "TAC-TD80U" (manufactured by Fuji Photo Film Co., Ltd.) was unwound in a curled state; Resolution number and transfer of 30 m / min of gravure roll at 30 rpm using a doctor blade and a microgravure roll having a diameter of 50 mm and a gravure pattern having a depth of 40 μm and 180 lines per inch. Under conditions of speed, coating the coating solution for hard coat layer (HCL-1) directly thereon; 400 mW / cm 2 using an air-cooled metal halide lamp of 160 W / cm (manufactured by Eyegraphics Co., Ltd.) under a purge with nitrogen at an oxygen concentration of 0.1 vol. The coating layer was cured by irradiation with ultraviolet light having an irradiance of and an irradiation dose of 100 mJ / cm 2, thereby forming a layer having a thickness of 6 μm, which was then wound. The antiglare layer (HC-1) thus prepared and obtained had a surface roughness of Ra = 0.18 mu m and Rz = 1.40 mu m, a surface haze of 12% and an internal haze of 29%.

On the thus obtained anti-glare layer, the coating solution for low refractive index layer (LLL-1) was coated so that the low refractive index layer had a thickness of 95 nm to prepare an antireflection film sample 101. For the coating solution, each component was mixed for 2 hours and then applied; For the drying conditions, the low refractive index layer was dried at 110 ° C. for 10 minutes; For ultraviolet curing conditions, ultraviolet light was absorbed using an air-cooled metal halide lamp of 240 W / cm (manufactured by Eyegraphics Co., Ltd.) under purge with atmospheric nitrogen with an oxygen concentration of 0.01% by volume or less. Irradiation with 120 mW / cm 2 irradiation intensity and 240 mJ / cm 2 irradiation energy intensity was carried out.

[Preparation of antireflection films 102 to 153]

In the preparation of the antireflective film 101 in the same manner as in the antireflection film 101, except that the coating solution for low refractive index layer (LLL-1) was replaced with each of the coating solutions (LLL-2) to (LLL-53). Antireflective films 102 to 153 were prepared.

[Saponification treatment of antireflection film]

Each antireflective film obtained was treated and dried under the following saponification standard conditions.

Alkaline bath: 1.5 mol / dm ³ aqueous sodium hydroxide solution at 55 ° C. for 120 seconds

1st water wash tank: tap water for 60 seconds

Neutralization bath: 0.05 mol / dm ³ sulfuric acid at 30 ° C. for 20 seconds

Second wash cycle: tap water for 60 seconds

Drying: 120 ℃, 60 seconds

[Evaluation of Antireflection Film]

Each of the saponified antireflective films thus obtained was evaluated in the following manner.

(Evaluation 1) Measurement of average reflectance:

Average reflectances between 450 and 650 nm were used in the methods described herein. For the specimen processed with the polarizer, the specimen in the polarizer state was used as it is; In the case of the display device or the film itself without a polarizing plate, after the roughing treatment on the back surface of the antireflective film, light absorption treatment with black ink (transmittance at 380 to 780 nm: 10% Below), and then provided for measurement on the black table.

(Evaluation 2) scar resistance evaluation by steel wool

This experiment was performed by the method as described herein, applying oily black ink to the back side of the rubbed specimen, visually observing the scratches on the rubbed portions with reflected light and evaluating according to the following criteria. The load was set to 500 g / cm 2.

A: A flaw is not observed at all even by the very close observation.

AB: With close observation, a few minor flaws are observed.

B: A weak flaw is observed.

BC: The blemish is observed moderately.

C: blemish is observed at first sight.

(Evaluation 3) evaluation of scar resistance by eraser rub

This experiment was performed by the method as described herein, applying oily black ink to the back side of the rubbed specimen, visually observing the scratches on the rubbed portions with reflected light and evaluating according to the following criteria.

A: A flaw is not observed at all even by the very close observation.

AB: With close observation, a few minor flaws are observed.

B: A weak flaw is observed.

BC: The blemish is observed moderately.

C: blemish is observed at first sight.

CC: blemishes on the entire surface of the film.

(Evaluation 4) Marker Ink Wiping Properties:

This experiment was performed by the method as described herein and the number of wipings until the marker ink disappeared was measured. It is preferable that the number of wiping until the marker ink disappears is five or more times; More preferably, the wiping number until the marker ink disappears is 10 or more.

(Evaluation 5) Dust Removal Characteristics:

This experiment was performed in the manner as described herein and the number of wipings until the dust was completely removed. It is desirable that the dust can be completely removed by six wipings; More preferably, the dust can be completely removed by wiping up to three times.

The evaluation results are shown in Table 8.

As is apparent from this example, an antireflective film using a polymer copolymer having a hydroxyl group content of more than 20% according to the present invention and containing the constituents of the present invention has excellent SW rub resistance and eraser rub resistance and excellent You can see that it is antifouling.

Several improvements in performance due to the hydroxyl group content in the fluorine-containing polymers result from a comparison between antireflective films 101-112 and antireflective films 139-144.

Additionally, it can be seen that marker ink wiping properties are significantly improved by having a polysiloxane structure as the polymer graft chain (compare antireflective films 107 to 112 and 113 to 119).

It can also be seen that by using hollow silica the reflectance is significantly reduced (compare antireflective films 134, 135, 137, 138 and 149).

Example 2

[Production of Antireflection Film]

[Production of Coating Solution for Low Refractive Index Layer (LLL-54 to LLL-63)]

Preparation of Coating Solutions for Low Refractive Index Layers (LLL-17 and LLL-38), except that Coating Solutions LLL-54 to LLL-58 and LLL-59 to LLL-63 were changed in the type of curing catalyst shown in Table 8. Prepared in the same manner as in. In changing the curing catalyst, the change was made such that the acid was used in equimolar amounts. Base was used as acid and equivalent (1/1).

(Preparation of Coating Solution for Hard Coat Layer (HCL-2))

90 parts by weight of MEK, 10 parts by weight of cyclohexanone, 85 parts by weight of polyfunctional acrylate partially modified with caprolactone (manufactured by Nippon Kayaku Co., Ltd.), KBM-5103 (Shin-Etsu Chemical) 10 parts by weight of a silane coupling agent manufactured by Co., Ltd. and 5 parts by weight of a photopolymerization initiator (IRGACURE 184, manufactured by Ciba Specialty Chemicals) were added and stirred. This mixture was filtered through a filter made of polypropylene having a pore size of 0.4 mu m to prepare a coating solution for hard coat layer (HCL-2).

[Preparation and Evaluation of Antireflection Film Samples 201 to 212]

The 80-micrometer-thick triacetyl cellulose film "TAC-TD80U" (manufactured by Fuji Photo Film Co., Ltd.) was unwound in a curled state; Using a doctor blade and a microgravure roll having a diameter of 50 mm and a gravure pattern having a depth of 40 μm and 180 lines per inch, under conditions of decomposition water of a gravure roll at 30 rpm and a delivery speed of 30 m / min. Coating the coating solution for hard coat layer (HCL-2) directly thereon; 400 mW / cm 2 using an air-cooled metal halide lamp of 160 W / cm (manufactured by Eyegraphics Co., Ltd.) under a purge with nitrogen at an oxygen concentration of 0.1 vol. The coating layer was cured by irradiation with ultraviolet light having an irradiance of and an irradiation energy intensity of 100 mJ / cm 2, thereby forming a layer having a thickness of 7 μm, which was then wound. The antiglare layer (HC-2) thus prepared and obtained had a surface roughness of Ra = 0.005 mu m and Rz = 0.01 mu m.

The low refractive index layer was coated and provided on the hard coat layer HC-2 in the same manner as in Example 1 to prepare antireflective films 201 to 212. For the time from the preparation of the low refractive index layer to the coating, the standard conditions were set to 2 hours. In addition, samples of which the heat curing time was shortened to 110 minutes at 110 ° C. were simultaneously prepared, saponified under the same conditions as in Example 1, and evaluated for eraser rub resistance.

Additionally, the coating solution for the low refractive index layer was stored for 1 month and 3 months, respectively, under light-shielding and closed conditions at 30 ° C., and then coated. Oily black ink was applied to the back surface of the coating film and the surface properties on the A4-size area were evaluated according to the following criteria.

A: A flaw is not observed at all even by the very close observation.

AB: With close observation, a few flaws were observed (1-3 / A4).

B: Weak spots were observed (4-10 pieces / A4).

C: blemishes were observed at first sight (more than 11 / A4).

The evaluation results are shown in Table 9.

As is evident in this example, it can be seen that by using an acid together with the base of the present invention as a curing catalyst, an antireflection film having excellent storage stability of the coating solution and excellent scar resistance can be obtained.

Example 3

A multilayer antireflective film was prepared as described below.

The following composition was put into a mixing vessel and stirred to prepare a coating solution for a hard coat layer.

750.0 parts by weight of trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd.), 270.0 parts by weight of poly (glycidyl methacrylate) having a weight average molecular weight of 15,000, 730.0 parts by weight of methyl ethyl ketone, and cyclo 500.0 parts by weight of hexanone, 25.0 parts by weight of photo cationic polymerization initiator (RHODORSIL 2074) and 50.0 parts by weight of photopolymerization initiator (IRGACURE 184, manufactured by Ciba Specialty Chemicals) were added and stirred.

The mixture was filtered with a polypropylene-based filter having a pore size of 0.4 mu m to prepare a coating solution for hard coat layer (HCL-3).

(Preparation of titanium dioxide fine particle dispersion)

Cobalt-containing titanium dioxide fine particles surface-treated with aluminum hydroxide and zirconium hydroxide (MPT-129C, manufactured by Ishihara Sangyo Kaisha, Ltd., TiO ₂ / Co ₃ O ₄ / Al ₂ O ₃ / ZrO ₃ = 90.5 / 3.0 / 4.0 /0.5 (weight ratio)) was used as titanium dioxide fine particles.

To 257.1 parts of this particle, 41.1 parts by weight of the following dispersant and 701.8 parts by weight of cyclohexanone were added, and the mixture was dispersed with Dyno-Mill to prepare a titanium dioxide dispersion having a weight average particle size of 70 nm.

(Production of Coating Solution for Medium Refractive Index Layer)

99.1 parts by weight of the titanium dioxide dispersion described above, 68.0 parts by weight of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 3.6 parts by weight of a photopolymerization initiator (IRGACURE 907), and a photosensitizer (KAYACURE DETX, 1.2 parts by weight of Nippon Kayaku Co., Ltd.), 279.6 parts by weight of methyl ethyl ketone and 1,049.0 parts by weight of cyclohexanone were added and stirred. After complete stirring, the mixture was filtered through a polypropylene-based filter having a pore size of 0.4 mu m to prepare a coating solution for the medium refractive index layer.

(Preparation of coating solution for high refractive index layer)

469.8 parts by weight of the titanium dioxide dispersion described above, 40.0 parts by weight of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture (DPHA), 3.3 parts by weight of a photopolymerization initiator (IRGACURE 907, manufactured by Ciba Specialty Chemicals), a photosensitive agent (KAYACURE DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.1 parts by weight, 526.2 parts by weight of methyl ethyl ketone and 459.6 parts by weight of cyclohexanone were added and stirred. The mixture was filtered with a polypropylene-based filter having a pore size of 0.4 μm to prepare a coating solution for the high refractive index layer.

(Preparation of antireflection film 301)

The coating solution for the hard coat layer was coated on a triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a gravure coater. After drying at 100 ° C., the irradiance was 400 mW / cm 2 using a 160 W / cm air-cooled metal halide lamp (manufactured by Eyegraphics Co., Ltd.) while purging with nitrogen at an oxygen concentration of 1.0 vol%. UV light having a radiation energy intensity of 300 mJ / cm 2 was cured to form a hard coat layer having a thickness of 8 μm.

On the hard coat layer, a gravure coater having three coating chambers was used to continuously coat the coating solution for the medium refractive index layer, the coating solution for the high refractive index layer, and the coating solution for the low refractive index layer (LLL-1).

With respect to drying conditions, the medium refractive index layer was dried at 90 ° C. for 30 seconds; Regarding the UV curing conditions, a radiation intensity of 400 mW / cm 2 and a 180 W / cm air-cooled metal halide lamp (manufactured by Eyegraphics Co., Ltd.) while purging with nitrogen in an atmosphere having an oxygen concentration of 0.1% by volume or less and Ultraviolet rays were irradiated at a radiation energy intensity of 400 mJ / cm 2. The refractive index of the medium refractive index layer after curing was 1.630, and the thickness was 67 nm.

As to the drying conditions, the high refractive index layer was dried at 90 ° C. for 30 seconds; Regarding the UV curing conditions, using a 240 W / cm air-cooled metal halide lamp (manufactured by Eyegraphics Co., Ltd.) while purging with nitrogen in an atmosphere having an oxygen concentration of 0.1% by volume or less, a radiation intensity of 600 mW / cm 2 and Ultraviolet rays were irradiated at a radiation energy intensity of 400 mJ / cm 2.

The refractive index of the high refractive index layer after curing was 1.905, and the thickness was 107 nm.

As to the drying conditions, the low refractive index layer was dried at 110 ° C. for 10 minutes; Regarding the UV curing conditions, using a 240 W / cm air-cooled metal halide lamp (manufactured by Eyegraphics Co., Ltd.) while purging with nitrogen in an atmosphere having an oxygen concentration of 0.01% by volume or less, Ultraviolet rays were irradiated with a radiant energy intensity of 480 mJ / cm 2.

The refractive index of the low refractive index layer after curing was 1.45, and the thickness was 85 nm.

Samples 302 to 353 were prepared in the same manner as in the preparation of Sample 301 obtained above, except that the coating solution for low refractive index layer was replaced with (LLL-2) to (LLL-53), respectively. As a result of the saponification treatment and evaluation according to Example 1, the reflection was greatly reduced in all samples by providing the medium refractive index layer and the high refractive index layer. According to the present invention, it was evident that an antireflection film having low reflection and excellent marker ink wiping characteristics and scar resistance was obtained.

In addition, samples were prepared and evaluated by adding KBM-5103 (a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.) in an amount of 5% by weight based on the total solids in the high refractive index layer. As a result, especially when the fluorine-containing polymer in which the amount of hydroxyl groups exceeds 20 mol% is used, the steel wall friction resistance is particularly improved.

Example 4

(Production of Coating Solution for Hard Coat Layer (HCL-4))

100 parts by weight of DeSolite Z7404 (hard coating composition solution containing zirconia fine particles manufactured by JSR Corporation), 31 parts by weight of DPHA (UV curable resin manufactured by Nippon Kayaku Co., Ltd.), KBM-5103 (Shin-Etsu Chemical 10 parts by weight of a silane coupling agent manufactured by Co., Ltd., 8.9 parts by weight of KE-P150 (1.5 μm of silica particles manufactured by Nippon Shokubai Co., Ltd.), MXS-300 (Soken Chemical & Engineering Co. 3 parts by weight of 3 μm-crosslinked PMMA particles), Ltd., 29 parts by weight of MEK and 13 parts by weight of MIBK were put into a mixing vessel and stirred to prepare a coating solution for a hard coat layer.

(Preparation of antireflection film)

As a support, a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) was unwound in a wound state; Directly above it is used a microgravure roll and doctor blade with a gravure pattern of 135 lines per inch, depth of 60 μm and diameter of 50 mm under conditions of transport speed 10 m / min. Coating the coating solution for the hard coat layer; After drying at 60 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp (manufactured by Eyegraphics Co., Ltd.) while purging with nitrogen, the irradiance is 400 mW / cm 2 and the radiation energy intensity is 250 mJ / cm 2 The coating layer was further cured by irradiation with ultraviolet rays to form a hard coat layer, which was then wound. The hard coat 401 was manufactured by adjusting the rotation speed of the gravure roll so that the thickness of the hard-coat layer after hardening might be set to 4.0 micrometers. The surface roughness of the hard coat 401 thus obtained was Ra = 0.02 mu m, PMS = 0.03 mu m and Rz = 0.25 mu m. (Ra (center line average roughness), RMS (square average surface roughness) and Rz (n-point average roughness) were measured by the scanning probe microscope system SPI3800 manufactured by Seiko Instruments Inc.)

On the hard coat 401, a low refractive index layer of Example 1 was coated and provided, and the resulting antireflective film was saponified, and this was evaluated according to Example 1. As a result, it was evident that according to the present invention, an antireflective film having low reflection and excellent in scratch resistance and marker ink wiping characteristics was obtained.

Example 5

(Production of Coating Solution for Hard Coat Layer (HCL-5))

28 parts by mass of cyclohexanone, 15 parts by mass of cyclohexanone, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PET-30, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol 12 parts by mass of a mixture of pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) and agglomerated silica (secondary aggregate diameter: 1.5 μm, primary particle diameter: tens of nm, Nihon Silica Co., Ltd.) 5 parts by mass, photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) 1 part by mass, photopolymerization initiator (Irgacure 907, Ciba Specialty Chemicals) 0.2 parts by mass and fluorine-based surface modifier (SP-13) 0.08 mass part was added under stirring to prepare a coating solution for hard coat layer (HCL-5).

불소-기재 표면 개질제 SP-13:

Fluorine-Based Surface Modifiers SP-13:

(Coating of Hard Coating 501)

The 80 μm-thick triacetyl cellulose film “TAC-TD80U” (manufactured by Fuji Photo Film Co., Ltd.) was unwound in a wound state; Directly thereon, the coating solution for hard coat layer (HCL-5) was coated by extrusion using a coater equipped with a throttle die under conditions of a conveying speed of 30 m / min. After drying at 30 ° C. for 15 seconds, and then drying at 90 ° C. for 20 seconds, the irradiation dose is 90 mJ / cm 2 using a 160 W / cm air-cooled metal halide lamp (manufactured by Eyegraphics Co., Ltd.) while purging with nitrogen. Irradiation with phosphorus ultraviolet rays cured the coating layer, thereby forming an antiglare layer having a thickness of 2.5 μm to which antiglare characteristics were given. The film was wound up to obtain a hard coat 501. The surface haze of the hard coat 501 was 6 and the internal haze was 1.

0.5 parts by mass of PM980M (photopolymerization initiator, manufactured by Wako Pure Chemical) was added to the coating solutions LLL-51 and LLL-53 for the low refractive index layer in Example 1 to prepare a coating solution for the low refractive index layer. On the hard coating 501, coating solutions for these low refractive index layers were coated. The coated product was saponified and evaluated according to the method of Example 1. As a result, the production of an antireflection film showing low reflection and excellent in scratch resistance and marker ink wiping characteristics was reproduced.

Example 6

<Production of Polarizing Plate Provided with Antireflection Film>

Iodine was adsorbed onto the stretched polyvinyl alcohol film to prepare a polarizing film. Using an adhesive based on polyvinyl alcohol, the antireflective film of Example 1 subjected to saponification was attached to one side of the polarizing film such that the support (triacetyl cellulose) side of the antireflective film faced the polarizing film side. . "WIDE VIEW FILM SA12B" (manufactured by Fuji Photo Film Co., Ltd.), a viewing angle magnifying film with an optical correction layer, was saponified and adhered to the other side of the polarizing film using an adhesive based on polyvinyl alcohol. . In this way, a polarizing plate was produced. This polarizing plate was evaluated in accordance with Example 1. As a result, the same effect was obtained by using the low refractive index layer of this invention.

Example 7

The TN-type transmissive liquid crystal display device having the polarizing plate of the present invention manufactured as described above was excellent in visibility, scar resistance and antifouling property.

Example 8

The antireflective film sample of Example 2 was attached to the glass substrate on the surface of the organic EL display via an adhesive. As a result, reflection on the glass surface was suppressed to obtain a display device having high visibility.

This application is based on Japanese Patent Application JP 2005-225478, filed August 3, 2005 and Japanese Patent Application JP 2006-112368, filed April 14, 2006, which are incorporated by reference in their entirety as if fully disclosed. It is incorporated herein by reference.

Although the antireflection film of the present invention has sufficient antireflection properties, it is excellent in both scar resistance and antifouling property. In addition, the antireflective film of the present invention has high production adaptability since it is produced using a coating solution in which storage properties and curing activities are compatible with each other. Furthermore, the image display device provided with the antireflective film of the present invention and the image display device provided with the polarizing plate using the antireflective film of the present invention have less visibility and background reflection by external light and have excellent visibility.

Claims (27)

An antireflection film comprising a low refractive index layer and a support prepared by coating a coating composition containing the following components: (A) the main chain consists only of carbon atoms, contains at least one fluorine-containing vinyl monomer polymerized unit and at least one hydroxyl group-containing vinyl monomer polymerized unit, and has a content of 20 moles of hydroxyl group-containing vinyl monomer polymerized unit Fluorine-containing polymers having a percentage exceeding%, but having no polysiloxane structure in the main chain; (B) a crosslinking agent capable of reacting with hydroxyl groups; And (C) A compound containing two or more (meth) acryloyl groups in one molecule. An antireflection film comprising a low refractive index layer and a support prepared by coating a coating composition containing the following components: (A) the main chain consists only of carbon atoms, contains at least one fluorine-containing vinyl monomer polymerized unit and at least one hydroxyl group-containing vinyl monomer polymerized unit, and has a content of 20 moles of hydroxyl group-containing vinyl monomer polymerized unit Fluorine-containing polymers having a percentage exceeding%, but having no polysiloxane structure in the main chain; (B) a crosslinking agent capable of reacting with hydroxyl groups; And (D) A composition containing at least one of an organosilane compound or a hydrolyzate of the organosilane compound and a partial condensate of the organosilane compound. An antireflection film comprising a low refractive index layer and a support prepared by coating a coating composition containing the following components: (A) the main chain consists only of carbon atoms, contains at least one fluorine-containing vinyl monomer polymerized unit and at least one hydroxyl group-containing vinyl monomer polymerized unit, and has a content of 20 moles of hydroxyl group-containing vinyl monomer polymerized unit Fluorine-containing polymers having a percentage exceeding%, but having no polysiloxane structure in the main chain; (B) a crosslinking agent capable of reacting with hydroxyl groups; And (E) Inorganic particles having a particle size of 1 nm or more and 100 nm or less. The antireflective film of claim 1, wherein the coating composition further comprises: (E) Inorganic particles having a particle size of 1 nm or more and 100 nm or less. The antireflective film of claim 2 wherein the coating composition further comprises: (E) Inorganic particles having a particle size of 1 nm or more and 100 nm or less. The antireflection film according to claim 1, wherein the fluorine-containing polymer comprises at least one polymerized unit having a graft site in the side chain containing a polysiloxane repeating unit represented by the following general formula (1):

Wherein R ¹ and R ² may be the same or different and each represents an alkyl group or an aryl group; p represents an integer of 10 to 500}. The antireflection film according to claim 2, wherein the fluorine-containing polymer comprises at least one polymerized unit having a graft moiety containing in the side chain a polysiloxane repeating unit represented by the following general formula (1):

Wherein R ¹ and R ² may be the same or different and each represents an alkyl group or an aryl group; p represents an integer of 10 to 500}. The antireflection film according to claim 1, wherein the fluorine-containing polymer comprises at least one polymerized unit having a graft moiety containing a polysiloxane repeating unit represented by the following general formula (3) in a side chain:

Wherein R ¹ and R ² may be the same or different and each represents an alkyl group or an aryl group; p represents an integer of 10 to 500}. The antireflective film of claim 1, wherein the coating composition further comprises: (F) A polysiloxane compound having a functional group capable of reacting with a hydroxyl group or a hydroxyl group to form a bond. The antireflective film of claim 2 wherein the coating composition further comprises: (F) A polysiloxane compound having a functional group capable of reacting with a hydroxyl group or a hydroxyl group to form a bond. The antireflective film of claim 3, wherein the coating composition further comprises: (F) A polysiloxane compound having a functional group capable of reacting with a hydroxyl group or a hydroxyl group to form a bond. The antireflective film of claim 1, wherein the coating composition further comprises at least one salt comprising an acid and an organic base having a pKa of 5.0 to 10.5 of the conjugate acid. The antireflective film of claim 2, wherein the coating composition further comprises one or more salts comprising an acid and an organic base having a pKa of 5.0 to 10.5 of the conjugate acid. 4. The antireflective film of claim 3, wherein the coating composition further comprises at least one salt comprising an acid and an organic base having a pKa of 5.0 to 10.5 of the conjugate acid. The antireflective film of claim 1, wherein the coating composition further comprises at least one salt comprising a nitrogen-containing organic base and an acid having a boiling point of at least 35 ° C and at most 85 ° C. 3. The antireflective film of claim 2, wherein the coating composition further comprises at least one salt comprising a nitrogen-containing organic base and an acid having a boiling point of at least 35 ° C and at most 85 ° C. The antireflective film of claim 3, wherein the coating composition further comprises at least one salt comprising a nitrogen-containing organic base and an acid having a boiling point of at least 35 ° C and at most 85 ° C. 4. The antireflective film of claim 3, wherein the inorganic particles are hollow silica particles. The method according to claim 1, further comprising at least one layer having a refractive index greater than that of the low refractive index layer between the support and the low refractive index layer, wherein the at least one layer is an organosilane compound, or a hydrolyzate of the organosilane compound and the organosilane compound. An antireflective film containing a composition containing at least one of two partial condensates. The method according to claim 2, further comprising at least one layer having a refractive index greater than the low refractive index layer between the support and the low refractive index layer, wherein the at least one layer is an organosilane compound, or a hydrolyzate of the organosilane compound and the organosilane compound. An antireflective film containing a composition containing at least one of two partial condensates. 4. The organic silane compound according to claim 3, further comprising at least one layer having a refractive index greater than that of the low refractive index layer between the support and the low refractive index layer, wherein the at least one layer is an organosilane compound or a hydrolyzate of the organosilane compound and the organosilane compound. An antireflective film containing a composition containing at least one of two partial condensates. A polarizing plate comprising an antireflective film and a polarizing film as claimed in claim 1, wherein the antireflective film is provided in the polarizing plate as one of two protective films for the polarizing film. A polarizing plate comprising an antireflective film and a polarizing film as claimed in claim 2, wherein the antireflective film is provided in the polarizing plate as one of two protective films for the polarizing film. A polarizing plate comprising an antireflective film and a polarizing film as claimed in claim 3, wherein the antireflective film is provided in the polarizing plate as one of two protective films for the polarizing film. An image display device comprising an antireflection film as claimed in claim 1, wherein the antireflection film is provided on the outermost surface of the display. An image display device comprising an antireflection film as claimed in claim 2, wherein the antireflection film is provided on the outermost surface of the display. An image display device comprising an antireflection film as claimed in claim 3, wherein the antireflection film is provided on the outermost surface of the display.

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