JP2008088309A - Cured coating film, anti-reflection hard coating film using it, polarization plate and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-reflection hard coating film having an anti-reflection layer with a high elasticity excellent in a hardness and a film strength and excellent in a manufacturing efficiency and a manufacturing cost even when it is manufactured in the presence of oxygen. <P>SOLUTION: In the anti-reflection hard coating film 4, a hard coat layer 2 is formed on a transparent plastic film base material 1 and the anti-reflection layer 3 is formed thereon. The anti-reflection layer 3 is an anti-reflection layer 3 formed by forming a coating film of an anti-reflection layer formation material containing a multi-functional polymerizable compound having at least two polymerizable functional groups, a polysiloxane compound having a radical-polymerizable functional group and an active hydrogen group and a ketone based solvent and curing the coating film. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a cured film, an antireflection hard coat film using the same, a polarizing plate, and an image display device.

  There is a liquid crystal display (LCD) as one of the various image display devices, but with the technological innovations related to higher viewing angles, higher definition, faster response, and color reproducibility of LCDs, applications that use LCDs are also notes. It is changing from personal computers and monitors to television. In LCD, a gap is provided between a flat glass having two transparent electrodes by a spacer, and a liquid crystal material is injected and sealed there, and then a polarizing plate is placed on the front and back surfaces of the flat glass. The configuration of attaching is the basic configuration. Conventionally, a cover plate made of glass or plastic is attached to the LCD surface to prevent damage to the polarizing plate attached to the LCD surface. However, mounting a cover plate is disadvantageous in terms of cost and weight, and a hard coat film has been gradually attached to the polarizing plate surface.

  However, when the hard coat film is attached to the LCD surface, for example, the visibility of the display is lowered due to the reflection of light on the polarizing plate surface. In particular, in car navigation monitors, video camera monitors, and the like that are frequently used under bright illumination, the reduction in visibility due to surface reflection is significant. In order to solve this problem, an antireflection layer (low refractive index layer) is formed on the hard coat layer of the hard coat film to prevent reflection. In most displays that are frequently used outdoors, the hard coat film to be mounted on the surface has an antireflection layer.

  The antireflection layer is generally formed of a plurality of thin films made of materials having different refractive indexes by a dry method such as a vacuum deposition method, a sputtering method, a CVD method, or a wet method using a die or gravure roll coating. It is provided by forming a multilayer laminate or a single layer made of a low refractive index material. In general, an antireflection layer having a single layer structure is widely used industrially because it can be produced without complicating the process and the cost can be reduced. The thickness of the single-layer antireflection layer is 0.1 to 0.5 μm, but due to oxygen inhibition in the curing process, interfacial damage may occur due to insufficient adhesion with the hard coat layer. The film strength may not be sufficient. With the transition of LCD applications to home TVs, general home TV users will handle TVs using LCDs in the same way as conventional TVs using glass CRTs. Is easily assumed. Therefore, even in the antireflection hard coat film, further improvement in hardness and improvement in film strength are required.

  As a method for improving the film strength of the antireflection layer, 15 to 80 parts by weight of a polysiloxane compound having a polymerizable functional group in the molecule and compounds 20 to 85 having at least two polymerizable functional groups in the molecule. There is a prior document describing a method of forming a cured film formed of a composition containing parts by weight as a thin film (Patent Document 1). However, in this prior document, a combination of a polysiloxane compound having a cationic polymerizable functional group that is not affected by oxygen inhibition and a polyfunctional cationic polymerizable compound that is also not affected by oxygen inhibition is sufficient even if it is thin. A polysiloxane compound having a radical polymerizable functional group that is affected by oxygen inhibition, and a polyfunctional radical polymerizable compound that is similarly affected by oxygen inhibition. There is no description or suggestion of a technique for obtaining a cured film that is sufficiently cured even if it is thin.

  Further, there is an antireflection film in which a low refractive index layer located farthest from the transparent support contains hollow silica particles and a compound that reduces surface free energy (Patent Document 2). However, this antireflection film is generally composed mainly of a fluorine-containing polymer having insufficient hardness, and requires a large amount of heat and nitrogen purge during curing, which is desirable from the viewpoint of cost and productivity. Absent.

JP 2004-314468 A JP 2005-186568 A

  Accordingly, the present invention provides a cured film that has a high elastic modulus even when manufactured in the presence of oxygen, has excellent hardness and film strength, and can be manufactured efficiently at low cost, and an antireflection hardware using the same. An object is to provide a coat film, a polarizing plate, and an image display device.

  In order to achieve the above object, the cured film of the present invention comprises a polyfunctional polymerizable compound having at least two polymerizable functional groups, a polysiloxane compound having a radical polymerizable functional group and an active hydrogen group, and a ketone solvent. It is a cured film formed by forming a coating film of a cured film forming material, and curing the coating film.

  The antireflection hard coat film of the present invention is an antireflection hard coat film in which a hard coat layer and an antireflection layer are laminated in this order on at least one surface of a transparent plastic film substrate, The layer is a cured film of the present invention.

  The polarizing plate of the present invention is a polarizing plate including an antireflection hard coat film, wherein the antireflection hard coat film is the antireflection hard coat film of the present invention.

  The image display device of the present invention is an image display device equipped with at least one of an antireflection hard coat film and a polarizing plate, wherein the antireflection hard coat film is the antireflection hard coat film of the present invention, and the polarization The plate is the polarizing plate of the present invention.

  The cured film of the present invention has a high elastic modulus even when produced in the presence of oxygen, and as a result, has excellent hardness and film strength, and does not require a large amount of heat or nitrogen purge during production. The production can be carried out efficiently at a low cost. Therefore, in the antireflection hard coat film of the present invention having the cured film as an antireflection layer (low refractive index layer), the antireflection layer is firmly adhered to the hard coat layer to prevent peeling and the like. The hardness of the layer is high, and its production can be carried out efficiently at low cost. In the present invention, even if the polymerizable functional group of the polysiloxane compound is a radical polymerizable functional group, the reason why a thin cured film having high hardness and high film strength can be formed without being affected by oxygen is as follows. Although it is unclear, the present inventors presume that the ketone solvent does not suffer from the adverse effects of oxygen by preventing the diffusion of oxygen. However, this inference does not limit the present invention at all. Moreover, although the cured film of this invention is used suitably for the antireflection layer of the antireflection hard coat film of this invention, it is not limited to this, The cured film of this invention may be used for another use. .

  In the cured film of the present invention, the ketone solvent is preferably contained in a proportion of 3 parts by weight or more with respect to 100 parts by weight of the cured film forming material. Examples of the ketone solvent include acetone, diethyl ketone, dipropyl ketone, diisobutyl ketone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK). MIBK is preferable, and MIBK is used alone. It is to be.

  In the polysiloxane compound of the cured film of the present invention, the radical polymerizable functional group is at least one of an acryloyloxy group and a methacryloyloxy group, and the active hydrogen group is at least one of a hydroxyl group, an amino group, and a carboxyl group. It is preferably a group.

  In the cured film of the present invention, the polysiloxane compound is preferably at least one compound selected from the group consisting of the following compounds (A), (B) and (C).

(A) At least one siloxane unit of a dimethylsiloxane unit represented by the following general formula (1), a siloxane unit represented by the following general formula (2), and a siloxane unit represented by the following general formula (3) And a polysiloxane compound.

(B) A polysiloxane compound containing a dimethylsiloxane unit represented by the following general formula (1), a siloxane unit represented by the following general formula (4), and a siloxane unit represented by the following general formula (5).

(C) A polysiloxane compound represented by the following general formula (6).

前記一般式（４）において、ｘは１〜１０の整数である。

In the general formula (4), x is an integer of 1 to 10.

前記一般式（５）において、ｘは１〜１０の整数である。

In the general formula (5), x is an integer of 1 to 10.

前記一般式（６）において、少なくとも一つのＲが、シロキサン構造を有する置換基であり、少なくとも一つのＲが、アクリロイルオキシ基およびメタクリロイルオキシ基の少なくとも一方を有する置換基であり、少なくとも一つのＲが、活性水素基を有する置換基である。

In the general formula (6), at least one R is a substituent having a siloxane structure, at least one R is a substituent having at least one of an acryloyloxy group and a methacryloyloxy group, and at least one R Is a substituent having an active hydrogen group.

  In the cured film of the present invention, the polymerizable functional group of the polyfunctional polymerizable compound is preferably at least one of an acryloyloxy group and a methacryloyloxy group.

  In the antireflection hard coat film of the present invention, the thickness of the hard coat layer is preferably in the range of 2 to 50 μm.

  In the antireflection hard coat film of the present invention, the antireflection layer preferably contains hollow spherical silicon oxide ultrafine particles.

  In the antireflection hard coat film of the present invention, it is preferable that the surface of the hard coat layer has an uneven shape and has an antiglare property.

  The method for producing a cured film of the present invention includes, for example, a cured film containing a polyfunctional polymerizable compound having at least two polymerizable functional groups, a polysiloxane compound having a radical polymerizable functional group and an active hydrogen group, and a ketone solvent. This is a manufacturing method in which a coating film of a forming material is formed, and the coating film is cured to form a cured film. In the method for producing a cured film of the present invention, the coating film is preferably dried and then cured. In the method for producing a cured film of the present invention, preferred embodiments thereof are the same as those exemplified in the description of the cured film of the present invention described above and below.

  The method for producing an antireflection hard coat film of the present invention is a method for producing an antireflection hard coat film in which a hard coat layer and an antireflection layer are laminated in this order on at least one surface of a transparent plastic film substrate. The antireflection layer is the cured film of the present invention, and the cured film is produced by the method for producing a cured film of the present invention. In the method for producing an antireflection hard coat film of the present invention, preferred embodiments thereof are the same as those exemplified in the description of the antireflection hard coat film of the present invention described above and below.

  The cured film forming material of the present invention comprises a polyfunctional polymerizable compound having at least two polymerizable functional groups, a polysiloxane compound having a radical polymerizable functional group and an active hydrogen group, and a ketone solvent. . In the cured film forming material of the present invention, preferred embodiments thereof are the same as those exemplified in the description of the cured film of the present invention described above and below.

  The antireflection layer-forming material of the present invention comprises a polyfunctional polymerizable compound having at least two polymerizable functional groups, a polysiloxane compound having a radical polymerizable functional group and an active hydrogen group, and a ketone solvent. To do. In the antireflection layer-forming material of the present invention, preferred embodiments thereof are the same as those exemplified in the description of the cured film of the present invention described above and below.

  Next, the present invention will be described in detail with examples.

  The polyfunctional polymerizable compound having two or more polymerizable functional groups for forming the cured film or the antireflection layer of the present invention is not particularly limited as long as it is a compound that is cured by heat, ultraviolet rays, electron beams, or the like. As the polyfunctional polymerizable compound, for example, synthesized from a polyfunctional acrylate resin such as an acrylic ester or methacrylic ester of a polyhydric alcohol, a diisocyanate, a polyhydric alcohol, and a hydroxyalkyl ester of acrylic acid or methacrylic acid. Polyfunctional urethane acrylate resin, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Multifunctional acrylate or polyfunctional methacrylate such as dipentaerythritol hexaacrylate It comes out gel. Furthermore, a polyether resin having an acrylate functional group, a polyester resin, an epoxy resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiol polyene resin and the like can be suitably used as necessary. In addition, melanin resins, urethane resins, alkyd resins, silicone resins and the like are also preferably used. Among these resins, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate Tri- or higher functional acrylates or methacrylates such as dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are preferably used in order to make the resulting cured film or antireflection layer more excellent in hardness.

A reactive diluent can be used for the polyfunctional polymerizable compound. Examples of the reaction diluent include acrylate or methacrylate of ethylene oxide modified phenol, acrylate or methacrylate of propylene oxide modified phenol, acrylate or methacrylate of ethylene oxide modified nonylphenol, acrylate or methacrylate of propylene oxide modified nonylphenol,
2-ethylhexyl carbitol acrylate, 2-ethylhexyl carbitol methacrylate,
Isobornyl acrylate, isobornyl methacrylate,
Tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate,
Hydroxyethyl acrylate, hydroxyethyl methacrylate,
Hydroxypropyl acrylate, hydroxypropyl methacrylate,
Hydroxybutyl acrylate, hydroxybutyl methacrylate,
Hydroxyhexyl acrylate, hydroxyhexyl methacrylate,
Diethylene glycol monoacrylate, diethylene glycol monomethacrylate,
Dipropylene glycol monoacrylate, dipropylene glycol monomethacrylate,
Triethylene glycol monoacrylate, triethylene glycol monomethacrylate,
Monofunctional acrylate or monofunctional methacrylate such as tripropylene glycol monoacrylate, tripropylene glycol monomethacrylate,
Diethylene glycol diacrylate, diethylene glycol dimethacrylate,
Triethylene glycol diacrylate, triethylene glycol dimethacrylate,
Tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate,
Dipropylene glycol diacrylate, dipropylene glycol dimethacrylate,
Tripropylene glycol diacrylate, tripropylene glycol dimethacrylate,
Tetrapropylene glycol diacrylate, tetrapropylene glycol dimethacrylate,
Polypropylene glycol diacrylate, polypropylene glycol dimethacrylate,
1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate,
Neopentyl glycol diacrylate, neopentyl glycol dimethacrylate,
Diacrylate of ethylene oxide modified neopentyl glycol, dimethacrylate of ethylene oxide modified neopentyl glycol,
Diacrylate of ethylene oxide modified bisphenol A, dimethacrylate of ethylene oxide modified bisphenol A,
Propylene oxide modified bisphenol A diacrylate, propylene oxide modified bisphenol A dimethacrylate,
Diacrylate of ethylene oxide modified hydrogenated bisphenol A, dimethacrylate of ethylene oxide modified hydrogenated bisphenol A,
Trimethylolpropane diacrylate, trimethylolpropane dimethacrylate,
Trimethylolpropane allyl ether diacrylate, trimethylolpropane allyl ether dimethacrylate, and the like can be used.

  Next, the polysiloxane compound having a radical polymerizable functional group for forming the cured film or the antireflection layer of the present invention includes a part having a siloxane bond in one molecule, a radical polymerizable functional group and an active hydrogen group. If it is a compound which has this, it will not restrict | limit in particular. As the radical polymerizable functional group, as described above, an acryloyloxy group and a methacryloyloxy group are preferable. Examples of the active hydrogen group include a hydroxyl group (hydroxy group), a carboxyl group, and an amino group. The polysiloxane compound is preferably a linear or branched polysiloxane compound.

The siloxane structure is not particularly limited, and examples thereof include those having a repeating unit of — (Si (R ¹ ) (R ² ) —O) —. The siloxane structure usually has polysiloxane units in which they repeat. Examples of R ¹ and R ² include an alkyl group having 1 to 6 carbon atoms and a phenyl group. The siloxane structure is preferably a dimethylsiloxane unit represented by the general formula (1).

In the polysiloxane compound, the introduction of an acryloyloxy group, a methacryloyloxy group, and an active hydrogen group is performed by replacing at least one of R ¹ and R ² of the siloxane structure with at least one of an acryloyloxy group, a methacryloyloxy group, and an active hydrogen group. It can implement by setting it as the substituent which has group. In this case, since the polysiloxane compound as a whole only needs to have an active hydrogen group and at least one of an acryloyloxy group and a methacryloyloxy group, the substituent may be, for example, an acryloyloxy group and a methacryloyloxy group. It may have both groups of at least one of these and an active hydrogen group, and may have any group.

  Examples of the siloxane unit introduced with a substituent having at least one of an acryloyloxy group and a methacryloyloxy group and a hydroxy group include, for example, the siloxane unit represented by the general formula (2) and the above There is a siloxane unit represented by the general formula (3).

  The siloxane unit represented by the general formula (2) is methyl, 3-acryloyloxy-2-hydroxypropoxypropylsiloxane.

  The siloxane unit represented by the general formula (3) is methyl, 2-acryloyloxy-3-hydroxypropoxypropylsiloxane.

Examples of the siloxane unit having an acryloyloxy group or a methacryloyloxy group include a siloxane unit represented by the general formula (4). In the siloxane structure, the siloxane unit represented by the general formula (4) is ^one in which R ¹ or R ² is a methyl group and the other is a polyethylene glycol propyl ether group having an acryloyloxy group at the terminal. In the general formula (4), x is an integer of 1 to 10.

Examples of the siloxane unit having a hydroxy group include a siloxane unit represented by the general formula (5). In the siloxane structure, the siloxane unit represented by the general formula (5) is a polyethylene glycol propyl ether group in which ^one of R ^{1 and} R ² is a methyl group and the other is a hydroxyl group at the terminal. In the general formula (5), x is an integer of 1 to 10.

  As the polysiloxane compound containing at least one of the general formula (1), the general formula (2), the general formula (3), the general formula (4), and the general formula (5), as described above, for example, The following (A) compound and (B) compound are mentioned.

(A): At least one siloxane unit of the dimethylsiloxane unit represented by the general formula (1), the siloxane unit represented by the general formula (2), and the siloxane unit represented by the general formula (3) And a polysiloxane compound.

  In the compound (A), the dimethylsiloxane unit (X1) represented by the general formula (1), the siloxane unit (X2) represented by the general formula (2), and the following general formula (3) The molar ratio (X1: X2, X3) of at least one siloxane unit (X2, X3) of the siloxane unit (X3) is, for example, in the range of 100: 1 to 50, preferably 100: 3 to 30 It is a range. In the compound (A), the molar ratio when both the siloxane unit (X2) represented by the general formula (2) and the siloxane unit (X3) represented by the general formula (3) are included ( X1: X2: X3) is, for example, in the range of 100: 1 to 50: 1 to 50, preferably in the range of 100: 5 to 40: 2 to 15, and more preferably 100: 10 to 30 : It is the range of 3-10.

(B): A polysiloxane compound containing a dimethylsiloxane unit represented by the general formula (1), a siloxane unit represented by the general formula (4), and a siloxane unit represented by the general formula (5).

  In the compound (B), the siloxane unit (X1) represented by the general formula (1), the siloxane unit (X4) represented by the general formula (4), and the siloxane represented by the general formula (5) The molar ratio (X1: X4: X5) of the unit (X5) is, for example, in the range of 100: 1 to 20: 1 to 20, and preferably in the range of 100: 3 to 10: 3 to 10.

  As the polysiloxane compound, for example, a compound having a siloxane structure introduced into isocyanuric acid obtained from a diisocyanate compound, at least one of an acryloyloxy group and a methacryloyloxy group, and an active hydrogen group is further used. Can do. Examples of such a compound include the compound (C) represented by the general formula (6) as described above.

  Examples of the skeleton unit of 6-isocyanatohexyl isocyanuric acid include a skeleton unit represented by the following general formula (7). A skeleton unit represented by the following general formula (7) is defined as a unit (b).

In R of the general formula (6), examples of the substituent having a siloxane structure include a substituent represented by the following general formula (8). In the substituent represented by the following general formula (8), it has a polydimethylsiloxane unit (d) at its terminal, and the unit (d) is bonded to the methylhydroxypropylsiloxane unit (c). In the unit (c), the hydroxy group is urethane-bonded to the terminal isocyanate group of 6-isocyanatohexyl isocyanuric acid, which is a part of the unit (b). In the polydimethylsiloxane units (d), _{x 1} is an integer of 1 to 7.

  In R of the general formula (6), examples of the substituent having an active hydrogen group include a substituent represented by the following general formula (9). In the substituent represented by the general formula (9), the terminal isocyanate group of 6-isocyanatohexyl isocyanuric acid which is a part of the unit (b) is a carboxyl group. In the substituent represented by the general formula (9), the carboxyl group may be decarboxylated to form an amino group.

  In R of the general formula (6), examples of the substituent having an acryloyloxy group include a substituent represented by the following general formula (10). In the substituent represented by the general formula (10), the terminal isocyanate group of 6-isocyanatohexylisocyanuric acid, which is a part of the unit (b), is an aliphatic polyester unit (a) and a urethane bond And the acryloyloxy group has couple | bonded with the terminal of the said unit (a). In the general formula (10), m and n may be the same or different, and are each an integer of 1 to 10, and l is an integer of 1 to 5.

  The 6-isocyanate in which the compound (C) includes the unit (b) which is the skeleton structure represented by the general formula (7) and the substituents represented by the general formulas (8) to (10). In the case of the hexyl isocyanuric acid derivative, the component ratio (molar ratio) of the unit (a): unit (b): unit (c): unit (d) is unit (b) when the unit (b) is 100. a) is, for example, in the range of 10-100, preferably in the range of 30-60, and the unit (c) is, for example, in the range of 5-80, preferably in the range of 10-60. The unit (d) is, for example, in the range of 10 to 400, and preferably in the range of 100 to 300.

In the present invention, the ratio (molar ratio) of each component of the polysiloxane compound can be determined from, for example, an integral curve of ¹ H-NMR spectrum. The weight average molecular weight of the polysiloxane compound is, for example, in the range of 500 to 150,000, and preferably in the range of 2000 to 100,000. The weight average molecular weight can be measured by GPC, for example.

  In the present invention, the cured film or the antireflection layer (low refractive index layer) is prepared by preparing the cured film forming material or the antireflection layer forming material and coating the material to form a coating film. It can be obtained by curing the film. As described above, the cured film forming material or the antireflection layer forming material contains the polyfunctional polymerizable compound, the polysiloxane compound, and a ketone solvent. In 100 parts by weight of the cured film forming material or the antireflection layer forming material, the ketone solvent is, for example, 3 parts by weight or more, preferably 4 to 50 parts by weight, and more preferably 5 to 40 parts by weight. Part. If the ketone solvent is 3 parts by weight or more, the hardness and the film strength can be further improved. In the cured film forming material or the antireflection layer forming material, it is preferable that 2 to 30 parts by weight of the polysiloxane compound (B) is contained with respect to 100 parts by weight of the polyfunctional polymerizable compound, and 5 to 20 parts by weight. Is more preferable. When the content of the polysiloxane compound is 2 parts by weight or more, surface slipperiness and antifouling performance are imparted to the formed cured film. In addition, if the content of the polysiloxane compound is 30 parts by weight or less, the content of the polyfunctional polymerizable compound tree can be relatively sufficient, and as a result, the effect film formed The elastic modulus is further improved, and the hardness and film strength can be further improved.

  The cured film forming material or the antireflection layer forming material may contain a polymerization initiator. When the polyfunctional polymerizable compound is photocurable, the polymerization initiator is a photopolymerization initiator. Examples of the photopolymerization initiator include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, benzoisopropyl ether, benzyldimethyl Ketal, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, other thioxant compounds, etc. Can be used. As other additives that can be added to the cured film forming material or the antireflection layer forming material, for example, α-hydroxyalkylphenone, acylphosphine oxide compounds, oxime esters, and the like can be used.

  The material for forming the antireflection layer preferably contains hollow spherical silicon oxide ultrafine particles. The silicon oxide ultrafine particles preferably have an average particle diameter of about 5 to 300 nm, and more preferably in the range of 10 to 200 nm. The silicon oxide ultrafine particles are hollow spheres in which cavities are formed inside the outer shell having pores, and the cavities include at least one of a solvent and a gas at the time of preparing the silicon oxide ultrafine particles. It is. Moreover, it is preferable that the precursor substance for forming the said cavity of the said silicon oxide ultrafine particle remains in the said cavity. The thickness of the outer shell is preferably in the range of about 1 to 50 nm and in the range of about 1/50 to 1/5 of the average particle diameter of the silicon oxide ultrafine particles. The outer shell is preferably formed from a plurality of coating layers. Further, in the silicon oxide ultrafine particles, it is preferable that the pores are closed and the cavity is sealed by the outer shell. This is because the porous or voids of the silicon oxide ultrafine particles are maintained in the antireflection layer, and the refractive index of the antireflection layer can be further reduced. As a method for producing such hollow and spherical silicon oxide ultrafine particles, for example, the method for producing silica-based fine particles disclosed in JP-A-2000-233611 is suitably employed.

  It is preferable to add inorganic ultrafine particles to the cured film forming material or the antireflection layer forming material for the purpose of improving the film strength of the formed film or layer. The average particle diameter of the inorganic ultrafine particles is, for example, in the range of 2 to 50 nm, and preferably in the range of 5 to 30 nm. Examples of the inorganic ultrafine particles include ultrafine particles such as silica, alumina, and magnesium fluoride. Among these, ultrafine particles of silica are particularly preferable. The addition amount of the inorganic ultrafine particles is, for example, in the range of 10 to 80 parts by weight with respect to 100 parts by weight of the total solid content of the cured film forming material or the antireflection layer forming material.

The coating method of the cured film forming material or the antireflection layer forming material is not particularly limited, and examples thereof include phanten coating, die coating, spin coating, spray coating, gravure coating, roll coating, and bar coating. In the case of the cured film, the coating film can be formed by coating the cured film forming material on the surface of a predetermined substrate. In the case of the antireflection layer, the hard coat layer can be formed. It can be carried out by coating an antireflection layer forming material on the substrate. The coating film is preferably heat-dried prior to curing. In the drying treatment, the temperature is, for example, in the range of 60 to 150 ° C., preferably 70 to 130 ° C., and the treatment time is, for example, in the range of 1 minute to 30 minutes, preferably in the range of 1 minute to 10 minutes. It is. The coating film can be heated using, for example, a hot plate, an oven, a belt furnace, or the like. The curing treatment of the coating film is appropriately selected depending on the types of the polyfunctional polymerizable compound and the polysiloxane compound, and examples thereof include a curing treatment by heat and a curing treatment by light or electron beam irradiation. As the energy beam source used for the light or electron beam irradiation, for example, an energy beam source such as a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, a nitrogen laser, an electron beam accelerator, or a radioactive element is used. The irradiation amount of the energy ray source is, for example, in the range of 50 to 5000 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm. The cured film or the antireflection layer is formed by curing the coating film. It is preferable to heat-treat the cured film or the antireflection layer in order to further improve the hardness. The conditions for the heat treatment after the curing treatment can be the same as those for the drying treatment.

  In the present invention, the thickness of the cured film or the antireflection layer is, for example, in the range of 60 to 130 nm, preferably in the range of 70 to 120 nm, and more preferably in the range of 80 to 110 nm. The thickness accuracy of the antireflection layer is preferably in the range of ± 10% with respect to the design thickness, for example. For example, when the design thickness of the antireflection layer is 95 nm, the range of 86 nm to 105 nm is preferable.

  The mechanism of the antireflection function of the antireflection layer will be described. When light strikes an object, it repeats phenomena such as reflection at the interface, absorption inside, and scattering, and passes through the back of the object. When a hard coat film is attached to an image display device, one of the factors that lower the image visibility is light reflection at the interface between air and the hard coat layer. As a method to reduce the surface reflection, an antireflection layer with strictly controlled thickness and refractive index is laminated on the surface of the hard coat layer, and the reversed phases of incident light and reflected light cancel each other using the light interference effect. The antireflection function is expressed.

In the design of the antireflection layer based on the light interference effect, the refractive index difference between the antireflection layer and the hard coat layer may be increased in order to increase the interference effect. In designing a single-layer antireflection layer, in order to maximize the antireflection function, n = (n _m ) ^{1 /} , where n is the refractive index of the antireflection layer and n _m is the refractive index of the hard coat layer. ^The refractive index n may be set to satisfy ² . This equation is referred to as an amplitude condition in a non-reflection condition. If n _m = 1.52, then n = 1.233, and the reflectance can be reduced by making the refractive index of the antireflection layer close to 1.233. Further, among the visible light wavelength range (380 nm to 780 nm), the wavelength range having particularly high visibility is in the range of 450 to 650 nm, and the reflectance that can be felt by reducing the reflectance at 550 nm, which is the central wavelength. Can be effectively reduced. For this purpose, the film thickness (layer thickness) may be set so as to satisfy nd = λ / 4, where d is the thickness of the antireflection layer and λ is the wavelength of incident light. This equation is referred to as a phase condition in a non-reflection condition. For example, when λ = 550 nm and n = 1.45, the thickness d of the antireflection layer is 95 nm.

  Next, the antireflection hard coat film of the present invention has a configuration in which a hard coat layer and an antireflection layer are laminated in this order on at least one surface of the transparent plastic film.

  In the antireflection hard coat film of the present invention, the transparent plastic film substrate is not particularly limited, but has excellent visible light transmittance (preferably light transmittance of 90% or more) and excellent transparency (preferably Those having a haze value of 1% or less are preferred. Examples of the transparent plastic film substrate include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose (TAC), acrylic polymers such as polycarbonate polymers and polymethyl methacrylate. And a film formed from a transparent polymer. Examples of the transparent plastic film substrate include styrene polymers such as polystyrene and acrylonitrile / styrene copolymers, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and olefin polymers such as ethylene / propylene copolymers. And a film formed from a transparent polymer such as vinyl chloride polymer, amide polymer such as nylon or aromatic polyamide. Further, examples of the transparent plastic film substrate include imide polymers, sulfone polymers, polyether sulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyls. Examples thereof include a film formed from a transparent polymer such as a butyral polymer, an arylate polymer, a polyoxymethylene polymer, an epoxy polymer, and a blend of the aforementioned polymers. As the transparent plastic film substrate, a transparent film with little optical birefringence is particularly preferably used. When the transparent plastic film substrate is also used as a protective film for a polarizing plate, triacetyl cellulose, polycarbonate, an acrylic polymer, polyolefin having a cyclic or norbornene structure, and the like are preferable. The thickness of the transparent plastic film substrate is not particularly limited, but is preferably in the range of 10 to 500 μm, preferably in the range of 20 to 300 μm, from the viewpoints of workability such as strength and handleability, and thin layer properties. More preferably, it is the range of 30-200 micrometers. The refractive index of the transparent plastic film base film is not particularly limited, and is, for example, in the range of 1.30 to 1.80, preferably in the range of 1.40 to 1.70.

  As described above, the surface of the hard coat layer may have a fine uneven structure to impart antiglare properties. The method for forming the fine concavo-convex structure on the hard coat layer surface is not particularly limited, and an appropriate method can be adopted. For example, the hard coat formed on the surface of the transparent plastic film base by roughening the surface in advance by an appropriate method such as sandblasting, embossing roll, chemical etching, etc. to form a fine uneven structure There is a method of making the surface of the layer a fine uneven structure. Further, a method of further laminating a hard coat layer on the hard coat layer and imparting a fine concavo-convex structure by a transfer method using a mold or the like can be mentioned. In addition, a method of imparting a fine concavo-convex structure by dispersing fine particles in the hard coat layer may be used. These fine concavo-convex structure forming methods may be formed as a layer in which two or more methods are combined to combine the fine concavo-convex structure surfaces in different states. Among the methods for forming the fine concavo-convex structure of the hard coat layer, a method of forming a fine concavo-convex structure by dispersing fine particles is preferable.

  Examples of the fine particles for making the surface structure of the hard coat layer have an uneven structure include inorganic fine particles and organic fine particles. The inorganic fine particles are not particularly limited, and examples thereof include silicon oxide fine particles, titanium oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles, tin oxide fine particles, calcium carbonate fine particles, barium sulfate fine particles, talc fine particles, kaolin fine particles, calcium sulfate fine particles and the like. Can be given. The organic fine particles are not particularly limited, and examples thereof include polymethyl methacrylate acrylate resin powder (PMMA fine particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder, Examples thereof include polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, polyfluorinated ethylene resin powder, and organic fine particles made of a copolymer. These inorganic fine particles and organic fine particles may be used alone or in combination of two or more.

  The shape of the fine particles is not particularly limited, and may be, for example, a bead-like substantially spherical shape or an irregular shape such as a powder. The weight average particle diameter of the fine particles is, for example, in the range of 1 to 30 μm, and preferably in the range of 2 to 20 μm. The fine particles are preferably substantially spherical, more preferably substantially spherical fine particles having an aspect ratio of 1.5 or less.

  The mixing ratio of the fine particles is not particularly limited and can be set as appropriate. The blending ratio of the fine particles is, for example, in the range of 2 to 60 parts by weight, and preferably in the range of 5 to 50 parts by weight with respect to 100 parts by weight of the hard coat layer forming material.

  The thickness of the hard coat layer is preferably in the range of 2 to 50 μm, for example. When the thickness is in the predetermined range, the hardness of the hard coat layer is sufficient (for example, pencil hardness of 4H or more), and curling and cracking can be more effectively prevented. The thickness of the hard coat layer is preferably in the range of 5 to 30 μm, more preferably in the range of 15 to 25 μm.

  The hard coat layer is prepared, for example, by preparing a hard coat layer forming material in which a hard coat layer forming resin is dissolved or dispersed in a solvent, and the hard coat layer forming material is provided on at least one surface of the transparent plastic film substrate. It can be formed by coating to form a coating film and curing the coating film.

  As the hard coat layer forming resin, for example, a resin curable by heat, light, or electron beam can be used. The hard coat layer forming resin is not particularly limited, and examples thereof include an ionizing radiation curable resin, a thermosetting resin, and a thermoplastic resin. Among these, it is particularly preferable to use an ionizing radiation curable resin because of its high processing speed and low heat damage to the transparent plastic film substrate. Examples of the ionizing radiation curable resin are synthesized from polyfunctional acrylate resins such as polyhydric alcohol acrylic acid or methacrylic acid ester, diisocyanate, polyhydric alcohol, and hydroxyalkyl ester of acrylic acid or methacrylic acid. Examples of such polyfunctional urethane acrylate resins. Furthermore, polyether resins having an acrylate functional group, polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins and the like can be suitably used as necessary. In addition, melanin resins, urethane resins, alkyd resins, silicone resins and the like are also preferably used.

  The solvent is not particularly limited, and various solvents can be used. For example, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1, 3,5-trioxane, tetrahydrofuran, acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, propionic acid Methyl, ethyl propionate, n-pentyl acetate, acetylacetone, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, -Butanol, 1-pentanol, 2-methyl-2-butanol, cyclohexanol, isobutyl acetate, methyl isobutyl ketone (MIBK), 2-octanone, 2-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, ethylene Examples include glycol monoethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. These may be used alone or in combination of two or more. The solvent preferably contains ethyl acetate in a proportion of 20% by weight or more of the whole, more preferably from the viewpoint of improving the adhesion between the transparent plastic film substrate and the hard coat layer. It is to contain ethyl acetate in a proportion of 25% by weight or more, and optimally to contain ethyl acetate in a proportion of 30 to 70% by weight of the whole. If it is 70% by weight or less, the volatilization rate of the solvent can be made appropriate, and coating unevenness and drying unevenness can be effectively prevented. The type of solvent used in combination with ethyl acetate is not particularly limited, and examples thereof include butyl acetate, methyl ethyl ketone, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether.

  In the hard coat layer forming material, when the hard coat layer forming resin is a photocurable resin, a conventionally known photopolymerization initiator can be used. Examples of the photopolymerization initiator include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, benzoinpropyl ether, benzyl Dimethyl ketal, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, etc. In addition, thioxant compounds can be used.

  Metal oxide ultrafine particles having a particle size of 100 nm or less can be added to the hard coat layer forming material. Examples of ultrafine particles of metal oxide having a particle size of 100 nm or less include titanium oxide, silicon oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, oxidative power lucium, indium oxide, and antimony oxide. Things can also be used. As the ultrafine particles of the metal oxide, those having a particle size exceeding 100 nm are used because light scattering occurs, the transmittance is reduced and the hard coat layer is colored, and the transparency is lowered. Absent.

  The ultrafine particles of metal oxide having a particle size of 100 nm or less have a function of adjusting the apparent refractive index of the hard coat layer in accordance with the amount of the metal oxide. The refractive index of the transparent plastic film substrate and the refractive index of the hard coat layer are preferably approximated. When the refractive index difference between the transparent plastic film substrate and the hard coat layer is large, a phenomenon called interference fringes in which reflected light of external light incident on the antireflection hard coat film exhibits a rainbow hue occurs. The display quality is degraded. In particular, interference fringes appear conspicuously under a three-wavelength fluorescent lamp that is widely used in general offices and the like.

  When the difference in refractive index between the transparent plastic film substrate and the hard coat layer is d, d is preferably 0.04 or less. More preferably, it is 0.02 or less. When a polyethylene terephthalate film is used as the transparent plastic film substrate, titanium oxide is used as ultrafine particles of metal oxide having a particle size of 100 nm or less, for example, 30 to 40 with respect to all resin components of the hard coat layer forming material. By blending about%, d can be controlled to 0.02 or less with respect to the refractive index of about 1.64 of the polyethylene terephthalate film, and the generation of interference fringes can be suppressed. Further, when a triacetyl cellulose film is used as the transparent plastic film substrate, silicon oxide is used as ultrafine particles of a metal oxide having a particle size of 100 nm or less, for all resin components of the hard coat layer forming material, for example, By blending about 35% to 45%, d can be controlled to 0.02 or less with respect to the refractive index of about 1.48 of the triacetyl cellulose film, and the occurrence of interference fringes can be suppressed. .

  Various leveling agents can be added to the hard coat layer forming material. As the leveling agent, a fluorine-based or silicone-based leveling agent can be used as appropriate, but a fluorine-based leveling agent is more preferable. When a fluorine-based one is selected as the leveling agent, there is little influence of repelling the antireflection layer formed on the hard coat layer. Examples of the fluorine leveling agent include perfluoroalkyl group-containing sulfonates such as perfluorobutyl sulfonate, perfluoroalkyl group-containing oligomers, perfluoroalkyl group-containing carboxylates, and perfluoroalkyl group-containing phosphoric acid. Examples thereof include esters and perfluoroalkylethylene oxide adducts. If a fluorine-based or silicone-based leveling agent is added to the hard coat layer forming material, the fluorine-based or silicone-based leveling agent bleeds to the air interface during preliminary drying and solvent drying in the formation of the hard coat layer. Therefore, it is possible to prevent the hard coat layer forming resin from being inhibited from curing by oxygen, and as a result, the outermost surface of the hard coat layer can have sufficient hardness. The compounding amount of the fluorine-based or silicone-based leveling agent is, for example, 5 parts by weight or less, preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the total resin components of the hard coat layer forming material.

  In the hard coat layer forming material, pigments, fillers, dispersants, plasticizers, UV absorbers, surfactants, antioxidants, thixotropic agents, etc. are added as necessary, as long as the performance is not impaired. May be. These additives may be used alone or in combination of two or more.

  Examples of the method for coating the hard coat layer forming material on a transparent plastic film substrate include, for example, a phanten coating method, a die coating method, a spin coating method, a spray coating method, a gravure coating method, a roll coating method, and a bar coating method. Etc. can be used.

  The hard coat layer forming material is applied to form a coating film on the transparent plastic film substrate, and the coating film is cured. Prior to the curing, the coating film is preferably dried. The drying may be, for example, natural drying, air drying by blowing air, heat drying, or a combination of these.

The means for curing the coating film of the hard coat layer forming material is not particularly limited, but ionizing radiation curing is preferable. Various active energy rays can be used as the means, but ultraviolet rays are preferable. As the energy ray source, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, a nitrogen laser, an electron beam accelerator, a radioactive element, or the like is preferable. The irradiation amount of the energy ray source is preferably 50 to 5000 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm. When the irradiation amount is 50 mJ / cm ² or more, the curing becomes more sufficient and the hardness of the formed hard coat layer becomes more sufficient. Moreover, if it is 5000 mJ / cm < ² > or less, coloring of the hard-coat layer formed can be prevented and transparency can be improved.

  And if the antireflection layer is formed on the hard coat layer by the above-mentioned method, the antireflection hard coat film of the present invention can be produced.

  An example of the configuration of the antireflection hard coat fill of the present invention is shown in the configuration diagram of FIG. As shown in the figure, the antireflection hard coat film 4 of this example has a hard coat layer 2 and an antireflection layer (low refractive index layer) 3 laminated in this order on one side of a transparent plastic film substrate 1. It is a configuration. In this example, the hard coat layer 2 and the antireflection layer 3 are formed on one side of the transparent plastic film substrate 1, but the present invention is not limited to this, and on both sides of the transparent plastic film substrate 1. The hard coat layer 2 and the antireflection layer 3 may be formed. The hard coat layer 2 and the antireflection layer 3 may be a single layer or a multilayer structure in which a plurality of layers are laminated.

  Another example of the antireflection hard coat film of the present invention is shown in FIG. In FIG. 2, the same parts as those in FIG. As shown in the figure, the antireflection hard coat film of this example includes fine particles 5 in the hard coat layer 2, whereby the hard coat layer 2 surface and the antireflection layer 3 surface have an uneven structure. ing. Thus, if the surface of the hard coat layer 2 and the antireflection layer 3 is an uneven structure, the antiglare property can be exhibited.

  In the antireflection hard coat film of the present invention, various surface treatments are preferably performed on each surface of the transparent plastic film substrate or the hard coat layer. Thereby, the adhesiveness in each interface of the said transparent plastic film base material and the said hard-coat layer, the said transparent plastic film base material and a polarizer, or the said hard-coat layer and an antireflection layer can be improved. As the surface treatment, for example, low-pressure plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. Moreover, as a surface treatment when a TAC film is used as the transparent plastic film substrate, an alkali saponification treatment is preferable. The alkali saponification treatment is preferably performed by repeating a series of operations of immersing the TAC film surface in an alkali solution, washing with water and drying, several times. Examples of the alkaline solution include potassium hydroxide solution and sodium hydroxide solution, and the prescribed concentration of hydroxide ions is preferably 0.1 to 3.0N, and preferably 0.5 to 2.0N. Is more preferable. The alkaline solution temperature is preferably in the range of 25 to 90 ° C, more preferably 40 to 70 ° C. After the saponification treatment, a TAC film subjected to a surface treatment can be obtained by performing a water washing treatment and a drying treatment.

  Below, the polarizing plate which laminated | stacked the antireflection hard coat film of this invention is demonstrated. A polarizing plate having the function of the present invention can be obtained by laminating the antireflection hard coat film of the present invention with a polarizer or a polarizing plate using an adhesive or a pressure-sensitive adhesive. The polarizing plate is usually disposed on both sides of the liquid crystal cell. Usually, two said polarizing plates are arrange | positioned so that an absorption axis may mutually cross substantially orthogonally. The polarizer usually has a transparent protective film on one side or both sides of the polarizer. When providing a transparent protective film on both surfaces of a polarizer, the same material may be sufficient as the transparent protective film of front and back, and a different material may be sufficient as it.

  The polarizer is not particularly limited, and examples thereof include hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, ethylene / vinyl acetate copolymer partially saponified films, iodine and dichromatic Examples include polarizers produced by adsorbing a dichroic substance such as a neutral dye and uniaxially stretching, polarizers of polyene-based oriented films such as dehydrated polyvinyl alcohol and dehydrochlorinated polyvinyl chloride. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is particularly preferable because of its high polarization dichroic ratio. The thickness of these polarizers is not particularly limited, but is, for example, about 5 to 80 μm.

  A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol by immersing it in an iodine aqueous solution and stretching it 3 to 7 times the original length. The iodine aqueous solution may contain boric acid, zinc sulfate, zinc chloride and the like as necessary. The immersion may use an aqueous solution such as potassium iodide. Further, if necessary, before the dyeing, the polyvinyl alcohol film is preferably immersed in water and washed with water. By washing the polyvinyl alcohol film with water, it is possible to clean the surface of the polyvinyl alcohol film and the anti-blocking agent, and by swelling the polyvinyl alcohol film, unevenness such as uneven dyeing can be obtained. There is also an effect to prevent. Stretching may be performed after dyeing with iodine, or may be performed while dyeing, or may be performed with dyeing after iodine. The film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.

  As the transparent protective film provided on one side or both sides of the polarizer, those having excellent transparency, mechanical strength, thermal stability, moisture shielding property, retardation value stability and the like are preferable. Examples of the material for forming the transparent protective film include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, cellulose resins such as diacetyl cellulose and triacetyl cellulose (TAC), acrylic resins such as polymethyl methacrylate, and polystyrene. Styrene resins such as acrylonitrile / styrene copolymer, styrene resin, acrylonitrile / styrene resin, acrylonitrile / butadiene / styrene resin, acrylonitrile / ethylene / styrene resin, styrene / maleimide copolymer, styrene / maleic anhydride copolymer, etc. And polycarbonate resins. Also, cycloolefin resins, norbornene resins, polyolefin resins such as polyethylene, polypropylene, ethylene / propylene copolymers, vinyl chloride resins, amide resins such as nylon and aromatic polyamide, aromatic polyimides, polyimide amides, etc. Imide resins, sulfone resins, polyether sulfone resins, polyether ether ketone resins, polyphenylene sulfide resins, vinyl alcohol resins, vinylidene chloride resins, vinyl propylar resins, arylate resins, polyoxymethylenes Examples of the transparent protective film include a polymer film made of a resin, an epoxy resin, or a blend of the resins. Further, the transparent protective film may be a cured film of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylic urethane, epoxy, or silicone.

  Examples of the transparent protective film include a polymer film described in JP-A-2001-343529 (WO01 / 37007), for example, (A) a thermoplastic resin having a substituted and / or unsubstituted imide group in the side chain; (B) A film formed from a resin composition containing a thermoplastic resin having a substituted and / or unsubstituted phenyl and nitrile group in the side chain. Specific examples thereof include a polymer film of a resin composition containing an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile / styrene copolymer.

  As the transparent protective film, cellulose-based resins such as TAC and norbornene-based resins are preferable from the viewpoints of polarization characteristics and durability. Specific examples of preferable transparent protective films include the product name “Fujitac” manufactured by Fuji Photo Film Co., Ltd., the product name “Zeonoa” manufactured by Nippon Zeon Co., Ltd., and the product name “Arton” manufactured by JSR. Can be given.

  Although the thickness of the said transparent protective film can be determined suitably, generally it is about 1-500 micrometers from points, such as workability | operativity, such as intensity | strength and a handleability, and thin layer property. Within this range, the polarizer is mechanically protected, and the polarizer does not contract even when exposed to high temperature and high humidity, and stable optical characteristics can be maintained. The thickness of the transparent protective film is preferably in the range of 5 to 200 μm, and more preferably in the range of 10 to 150 μm.

  As the transparent protective film, since the retardation value in the film plane and the retardation value in the thickness direction may affect the viewing angle characteristics of the liquid crystal display device, the one having the optimized retardation value should be used. Is preferred. However, the transparent protective film for which optimization of the retardation value is desired is a transparent protective film laminated on the surface of the polarizer on the side close to the liquid crystal cell, and is laminated on the surface of the polarizer on the side far from the liquid crystal cell. This is not the case because the transparent protective film does not change the optical characteristics of the liquid crystal display device.

  In the transparent protective film laminated on the surface of the polarizer close to the liquid crystal cell, the in-plane retardation value (Re) is, for example, in the range of 0 to 5 nm, preferably in the range of 0 to 3 nm. More preferably, it is in the range of 0 to 1 nm, and the thickness direction retardation value (Rth) is, for example, in the range of 0 to 15 nm, preferably in the range of 0 to 12 nm, and more preferably, It is in the range of 0 to 10 nm, more preferably in the range of 0 to 5 nm, and most preferably in the range of 0 to 3 nm.

  The antireflection hard coat film and the polarizing plate of the present invention can be preferably used for various image display devices such as a liquid crystal display device. The antireflection hard coat film and the polarizing plate of the present invention can be produced by sequentially laminating them sequentially in the production process of the liquid crystal display device. It is preferable because it is excellent in laminating workability and the like and can improve the manufacturing efficiency of a liquid crystal display device or the like. The liquid crystal display device can be formed according to a conventionally known method. In other words, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, an optical element, and an illumination system as necessary, and incorporating a drive circuit. There is no particular limitation except that an antireflection hard coat film or the like according to the invention is used, and it can be formed according to the conventional art. As the liquid crystal cell, any type such as a TN type, an STN type, and a TC type can be used.

  Next, examples of the present invention will be described together with comparative examples.

(Example 1)
80 parts by weight of dipentaerythritol hexaacrylate (DPHA), 20 parts by weight of 1,6-hexanediol diacrylate and 5 parts by weight of a photopolymerization initiator (trade name Irgacure 184, manufactured by Ciba Specialty Chemicals) were dissolved in ethyl acetate. The hard coat layer forming material was prepared by adjusting the nonvolatile component to 50%. The hard coat layer forming material is applied to one side of the TAC film with an 8th wire bar to form a coating film, dried at 80 ° C. for 1 minute, and then cured by irradiating with an ultraviolet ray of 300 mJ / cm ^2. And a hard coat layer having a thickness of 6 μm was formed to obtain a hard coat film. Next, 100 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of the following polysiloxane compound (compound A), 5 parts by weight of a photopolymerization initiator (trade name Irgacure 184, manufactured by Ciba Specialty Chemicals) and 3512 parts by weight of MIBK are mixed. Thus, an antireflection layer forming material was prepared. The antireflection layer forming material is coated on the hard coat layer with a third wire bar to form a coating film, dried at 80 ° C. for 3 minutes, and then irradiated with ultraviolet rays having an irradiation amount of 900 mJ / cm ^2. Then, an antireflection layer (low refractive index layer) having a thickness of 0.1 μm was formed to produce a desired antireflection hard coat film.

The polysiloxane compound (A compound) includes a dimethylsiloxane unit (X1) of the general formula (1), a methyl, 3-acryloyloxy-2-hydroxypropoxypropylsiloxane unit (X2) of the general formula (2), and , A compound having a molar ratio (X1: X2: X3) = 100: 20: 5 with the methyl, 2-acryloyloxy-3-hydroxypropoxypropylsiloxane unit (X3) of the general formula (3) It is. The weight average molecular weight of this A compound by GPC was 14800.

(Example 2)
In the antireflection layer forming material, except that 100 parts by weight of the dipentaerythritol hexaacrylate, 10 parts by weight of the polysiloxane compound (A compound), 5 parts by weight of the photopolymerization initiator, and 3630 parts by weight of MIBK, An antireflection hard coat film was produced in the same manner as in Example 1.

(Example 3)
In the antireflection layer forming material, except that 100 parts by weight of the dipentaerythritol hexaacrylate, 20 parts by weight of the polysiloxane compound (A compound), 5 parts by weight of the photopolymerization initiator, and 3862 parts by weight of MIBK are mixed. An antireflection hard coat film was produced in the same manner as in Example 1.

Example 4
An antireflection hard coat film was produced in the same manner as in Example 1 except that the polysiloxane compound (A compound) was changed to the following polysiloxane compound (C compound).

  The polysiloxane compound (C compound) includes a dimethylsiloxane unit (X7) of the general formula (7), a substituent (X8) of the general formula (8), and a substituent (X9) of the general formula (9). ) And the substituent (X10) of the general formula (10) in a molar ratio (X7: X8: X9: X10) = 286: 45: 100: 45.

(Example 5)
An antireflection hard coat film was produced in the same manner as in Example 2 except that the polysiloxane compound (A compound) was changed to the polysiloxane compound (C compound).

(Example 6)
An antireflection hard coat film was produced in the same manner as in Example 3 except that the polysiloxane compound (A compound) was changed to the polysiloxane compound (C compound).

(Example 7)
An antireflection hard coat film was produced in the same manner as in Example 1 except that the polysiloxane compound (A compound) was changed to the following polysiloxane compound (B compound).

  The polysiloxane compound (B compound) includes a dimethylsiloxane unit (X1) of the general formula (1), a siloxane unit (X4) of the general formula (4), and a siloxane unit (X5) of the general formula (5). ) In a molar ratio (X1: X4: X5) = 100: 8: 6. The weight average molecular weight of this B compound by GPC was 4320.

(Example 8)
An antireflection hard coat film was produced in the same manner as in Example 2 except that the polysiloxane compound (A compound) was changed to the polysiloxane compound (B compound).

Example 9
An antireflection hard coat film was produced in the same manner as in Example 3 except that the polysiloxane compound (A compound) was changed to the polysiloxane compound (B compound).

(Comparative Example 1)
Example 1 except that the antireflection layer forming material was prepared by mixing 100 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of the photopolymerization initiator, and 3396 parts by weight of MIBK. An antireflection hard coat film was produced in the same manner.

(Comparative Example 2)
Other than the use of a material prepared by mixing 100 parts by weight of the dipentaerythritol hexaacrylate, 5 parts by weight of the photopolymerization initiator, IPA3056.4 parts by weight, and 339.6 parts by weight of BuOH as the antireflection layer forming material. Produced an antireflection hard coat film in the same manner as in Example 1.

(Comparative Example 3)
As the antireflection layer forming material, 100 parts by weight of the dipentaerythritol hexaacrylate, 5 parts by weight of the polysiloxane compound (A compound), 5 parts by weight of the photopolymerization initiator, 3160.8 parts by weight of IPA, 351.2 parts by weight of BuOH An antireflective hard coat film was produced in the same manner as in Example 1 except that a mixture prepared by mixing was used.

(Comparative Example 4)
As the antireflection layer forming material, 100 parts by weight of the dipentaerythritol hexaacrylate, 10 parts by weight of the polysiloxane compound (A compound), 5 parts by weight of the photopolymerization initiator, 3267 parts by weight of IPA, and 363 parts by weight of BuOH are mixed. An antireflection hard coat film was produced in the same manner as in Example 1 except that the prepared one was used.

(Comparative Example 5)
As the antireflection layer forming material, 100 parts by weight of the dipentaerythritol hexaacrylate, 20 parts by weight of the polysiloxane compound (A compound), 5 parts by weight of the photopolymerization initiator, 3475.8 parts by weight of IPA, 386.2 parts by weight of BuOH An antireflective hard coat film was produced in the same manner as in Example 1 except that a mixture prepared by mixing was used.

(Comparative Example 6)
As the antireflection layer forming material, 100 parts by weight of the dipentaerythritol hexaacrylate, 5 parts by weight of the polysiloxane compound (C compound), 5 parts by weight of the photopolymerization initiator, 3160.8 parts by weight of IPA, 351.2 parts by weight of BuOH An antireflective hard coat film was produced in the same manner as in Example 1 except that a mixture prepared by mixing was used.

(Comparative Example 7)
As the antireflection layer forming material, 100 parts by weight of the dipentaerythritol hexaacrylate, 10 parts by weight of the polysiloxane compound (C compound), 5 parts by weight of the photopolymerization initiator, 3267 parts by weight of IPA and 363 parts by weight of BuOH are mixed. An antireflection hard coat film was produced in the same manner as in Example 1 except that the prepared one was used.

(Comparative Example 8)
As the antireflection layer forming material, 100 parts by weight of the dipentaerythritol hexaacrylate, 20 parts by weight of the polysiloxane compound (C compound), 5 parts by weight of the photopolymerization initiator, 3475.8 parts by weight of IPA, and 386.2 parts by weight of BuOH An antireflective hard coat film was produced in the same manner as in Example 1 except that a mixture prepared by mixing was used.

(Comparative Example 9)
As the antireflection layer forming material, 100 parts by weight of the dipentaerythritol hexaacrylate, 5 parts by weight of the polysiloxane compound (B compound), 5 parts by weight of the photopolymerization initiator, 3160.8 parts by weight of IPA and 351.2 parts by weight of BuOH An antireflective hard coat film was produced in the same manner as in Example 1 except that a mixture prepared by mixing was used.

(Comparative Example 10)
As the antireflection layer forming material, 100 parts by weight of the dipentaerythritol hexaacrylate, 10 parts by weight of the polysiloxane compound (B compound), 5 parts by weight of the photopolymerization initiator, 3267 parts by weight of IPA and 363 parts by weight of BuOH are mixed. An antireflection hard coat film was produced in the same manner as in Example 1 except that the prepared one was used.

(Comparative Example 11)
As the antireflection layer forming material, 100 parts by weight of the pentaerythritol hexaacrylate, 20 parts by weight of the polysiloxane compound (B compound), 5 parts by weight of the photopolymerization initiator, 3475.8 parts by weight of IPA, and 386.2 parts by weight of BuOH An antireflection hard coat film was produced in the same manner as in Example 1 except that a mixture prepared was used.

  Various characteristics of the antireflection hard coat films of Examples 1 to 9 and Comparative Examples 1 to 11 obtained as described above were measured by the following methods. These results are shown in Table 1 below together with the composition of the antireflection layer forming material.

(Thickness of the hard coat layer)
The thickness of the hard coat layer was measured with a micro gauge thickness gauge manufactured by Mitutoyo Corporation. That is, first, the thickness of the entire laminate in which a hard coat layer was provided on a transparent plastic film substrate was measured, and the thickness of the hard coat layer was calculated by subtracting the thickness of the substrate.

(Thickness of antireflection layer)
The thickness of the antireflection layer was calculated from the waveform of the interference spectrum using an instantaneous multi-photometry system (trade name: MCPD2000) manufactured by Otsuka Electronics Co., Ltd.

(Elastic modulus)
The elastic modulus of the antireflection layer was evaluated by using a nano indenter (model: DCM-SA2) manufactured by MTS Systems, under the following conditions, and at a strain rate of 0.05 s ⁻¹ and an indentation depth of 8 nm. Was measured.
Indenter: Barco pitch type Ψ = 65.3 °, s / h = 7.5315, A (h) = 24.56h ^ 2, V (h) = 8.1873h ^ 3, V (A) = 0.0673A ^ 3/2, A / Af = 0.908, conversion angle = 70.32 ° (Ψ: angle formed between the perpendicular line drawn from the top of the indenter and the surface, s / h: ratio of side line to depth, A (h): Projected cross-sectional area, V (h): relationship between volume and indentation depth, V (A): relationship between volume and projected cross-sectional area, A / Af: ratio of projected cross-sectional area to contact area, conversion angle: equivalent cone Angle)

(Weight average molecular weight)
The weight-average molecular weight is as follows: Measuring instrument: trade name HLC-8120GPC manufactured by Tosoh Corporation, column: G4000H _XL + G2000H _XL + G1000H _XL (7.8 mmφ × 30 cm each, 90 cm in total) manufactured by Tosoh Corporation, column temperature: 40 ° C., eluent: Measured by GPC under conditions of tetrahydrofuran, flow rate: 0.8 ml / min, inlet pressure: 6.6 MPa, standard sample: polystyrene.

  As shown in Table 1, the elastic modulus of the antireflection layer of the hard coat film of all the examples showed a high value and was excellent in hardness and film strength. On the other hand, the antireflection layers of the hard coat films of all comparative examples in which no ketone solvent was used had a low elastic modulus and insufficient hardness and film strength.

  As described above, even when the cured film of the present invention is produced in the presence of oxygen, the elastic modulus is high, the hardness and the film strength are excellent, the production efficiency is excellent, and the production cost is low. The cured film of the present invention can be applied to, for example, an antireflection layer of an antireflection hard coat film. The antireflection hard coat film of the present invention is suitably used for various image display devices such as a polarizing plate, a CRT, a liquid crystal display (LCD), a plasma display (PDP), and an EL display (ELD).

FIG. 1 is a block diagram showing an example of the antireflection hard coat film of the present invention. FIG. 2 is a block diagram showing another example of the antireflection hard coat film of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent plastic film base material 2 Hard coat layer 3 Antireflection layer 4, 6 Antireflection hard coat film 5 Fine particle

Claims (12)

Forming a coating film of a cured film forming material comprising a polyfunctional polymerizable compound having at least two polymerizable functional groups, a polysiloxane compound having a radical polymerizable functional group and an active hydrogen group, and a ketone solvent; A cured film formed by curing a film. The cured film according to claim 1, wherein the ketone solvent is contained in a proportion of 3 parts by weight or more with respect to 100 parts by weight of the cured film forming material. The cured film according to claim 1 or 2, wherein the ketone solvent is methyl isobutyl ketone (MIBK). 2. The polysiloxane compound, wherein the radical polymerizable functional group is at least one of an acryloyloxy group and a methacryloyloxy group, and the active hydrogen group is at least one group of a hydroxyl group, an amino group, and a carboxyl group. The cured film as described in any one of 3 to 3. The cured film according to any one of claims 1 to 4, wherein the polysiloxane compound is at least one compound selected from the group consisting of the following compounds (A), (B), and (C). .
(A) a dimethylsiloxane unit represented by the following general formula (1), a siloxane unit represented by the following general formula (2) and at least one siloxane unit represented by the following general formula (3): A polysiloxane compound containing
(B) A polysiloxane compound containing a dimethylsiloxane unit represented by the following general formula (1), a siloxane unit represented by the following general formula (4), and a siloxane unit represented by the following general formula (5).
(C) A polysiloxane compound represented by the following general formula (6).

In the general formula (4), x is an integer of 1 to 10.

In the general formula (5), x is an integer of 1 to 10.

In the general formula (6), at least one R is a substituent having a siloxane structure, at least one R is a substituent having at least one of an acryloyloxy group and a methacryloyloxy group, and at least one R Is a substituent having an active hydrogen group.
The cured film according to any one of claims 1 to 5, wherein the polymerizable functional group of the polyfunctional polymerizable compound is at least one of an acryloyloxy group and a methacryloyloxy group. 7. An antireflection hard coat film in which a hard coat layer and an antireflection layer are laminated in this order on at least one surface of a transparent plastic film substrate, wherein the antireflection layer is any one of claims 1 to 6. An antireflection hard coat film, which is the cured film according to claim 1. The antireflection hard coat film according to claim 7, wherein the hard coat layer has a thickness in the range of 2 to 50 μm. The antireflection hard coat film according to claim 7 or 8, wherein the antireflection layer contains hollow and spherical silicon oxide ultrafine particles. The antireflection hard coat film according to any one of claims 7 to 9, wherein the surface of the hard coat layer has an uneven shape and has an antiglare property. A polarizing plate comprising an antireflection hard coat film, wherein the antireflection hard coat film is the antireflection hard coat film according to any one of claims 7 to 10. An image display device equipped with at least one of an antireflection hard coat film and a polarizing plate, wherein the antireflection hard coat film is the antireflection hard coat film according to any one of claims 7 to 10, An image display device, wherein the polarizing plate is the polarizing plate according to claim 11.

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