TWI663225B - Manufacturing method of hard coating film, hard coating film, polarizing plate, and liquid crystal display device - Google Patents

Abstract

A method for producing a hard coat film, which is a method for producing a hard coat film having a hard coat layer on at least one side of a transparent support, which comprises at least hardening a hard coat layer forming composition containing the following a) to d) to In the step of forming the hard coat layer, when the total solid content of the hard coat layer forming composition is 100% by mass, the hard coat layer forming composition includes 10 to 40% by mass of a), and 40 to 89.8% by mass. b), 0.1 to 10% by mass, c), 0.1 to 10% by mass of d), a) having an alicyclic epoxy group and an ethylenically unsaturated double bond group in the molecule having a molecular weight of 300 or less Compounds; b) compounds having more than 3 ethylenically unsaturated double bond groups in the molecule; c) radical polymerization initiators; d) cationic polymerization initiators.

Description

Manufacturing method of hard coating film, hard coating film, polarizing plate, and liquid crystal display device

The present invention relates to a method for manufacturing a hard coating film, a hard coating film, a polarizing plate, and a liquid crystal display device.

For example, cathode ray tube display (CRT), plasma display (PDP), electroluminescence display (ELD), fluorescent display (VFD), field emission display (FED), or liquid crystal display (LCD). It prevents damage to the display surface, and is suitable for providing a hard coating film with a hard coating on a transparent support.

The hard coating film is used for the outermost surface of the display, and therefore requires high film hardness. On the other hand, image display devices are becoming thinner, and thinning of a hard coating film is strongly demanded.

In order to reduce the thickness of the hard coating film, it is necessary to reduce the thickness of the transparent support. However, if the thickness of the transparent support is reduced, the hardness of the film is reduced, or the transparent support becomes unable to resist the hardening and shrinkage of the hard coating. Wrinkling or curling deteriorates, and the operation of manufacturing and processing the hard coating film becomes difficult. The film is cracked during the operation, causing a problem of peeling after bonding. In addition, as the thickness of the transparent support is reduced, moisture permeability increases, and problems such as deterioration of the wet heat durability of the polarizing plate also occur. In order to improve this problem, an invention using an epoxy-based compound (Patent Documents 1 and 2) has been proposed.

Patent Document 3 describes a method for suppressing reverse warpage by using a compound having an alicyclic epoxy group and a (meth) acrylate group in the molecule as an overcoat for an optical disc. example.

In addition, there is a hard coating film provided with an ultraviolet blocking function (ultraviolet blocking function) for the purpose of preventing deterioration of a display device or the like due to ultraviolet rays. At present, an ultraviolet blocking function is generally imparted to a transparent support. However, as the thickness of the transparent support is reduced, the ultraviolet blocking function of the transparent support is reduced, and the ultraviolet blocking function is also required for the hard coat layer. Here, the hard-coat layer is an ultraviolet-curable resin. However, if the hard-coat layer is provided with an ultraviolet-blocking function, the ultraviolet rays required for hardening the hard-coat layer are also blocked, and the hardness is reduced. To solve this problem, Patent Document 4 uses a specific ultraviolet absorber to improve hardness and curl.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-237483

[Patent Document 2] Japanese Patent Laid-Open No. 08-073771

[Patent Document 3] Japanese Patent Laid-Open No. 04-236211

[Patent Document 4] Japanese Patent Laid-Open No. 2013-204001

However, according to the inventions described in Patent Documents 1 and 2, although the curl-improving effect is recognized, the surface hardness of the film is reduced, and it is difficult to have both surface hardness and these properties. In addition, as in the inventions described in Patent Documents 1 and 2, when an acrylic compound and an epoxy compound are mixed, In addition to the above problems, it is also newly known that the epoxy-based compound flows out and the film is whitened under high temperature and high humidity.

When the hardening composition described in Patent Document 3 is used as a hard coating film, the hardness is insufficient, and the curl suppressing effect cannot be said to be sufficient.

In addition, the invention described in Patent Document 4 has insufficient curl improvement effect when the hard coat layer is provided on a thin transparent support having a thickness of 25 μm or less.

In view of the problems of the prior art described above, an object of the present invention is to provide a hard coating that does not damage the surface hardness of the film, suppresses the occurrence of curls and wrinkles, and does not cause the problem of white turbidity caused by outflow or the like even in a hot and humid environment. membrane. Furthermore, in addition to the above-mentioned properties, another object of the present invention is to provide a hard coating film having sufficient ultraviolet absorption ability even if the thickness of the transparent support is 25 μm or less. In addition, the present invention also provides a polarizing plate and a liquid crystal image display device having the above-mentioned hard coating film, which are excellent in handleability and which do not deteriorate display quality due to curling or wrinkling, and which can reduce light leakage during a moist heat test.

The problem to be solved by the present invention can be solved by the present invention with the following means.

<1>

A method for producing a hard coat film, which is a method for producing a hard coat film having a hard coat layer on at least one side of a transparent support, which comprises at least hardening a hard coat layer forming composition containing the following a) to d) to The step of forming the above-mentioned hard coat layer, When the total solid content of the hard coating layer-forming composition is 100% by mass, the hard coating layer-forming composition includes 10 to 40% by mass of the following a) and 40 to 89.8% by mass of the following b) 0.1 to 10% by mass of the following c), 0.1 to 10% by mass of the following d).

a) A compound having one alicyclic epoxy group and one ethylenically unsaturated double bond group in the molecule, and having a molecular weight of 300 or less

b) Compounds with more than 3 ethylenically unsaturated double bond groups in the molecule

c) radical polymerization initiator

d) Cationic polymerization initiator

<2>

The method for producing a hard coat film as in <1>, wherein when the total solid content of the hard coat layer forming composition is 100% by mass, the hard coat layer forming composition further contains 5 to 40% by mass of e. ) Inorganic fine particles having reactivity with an epoxy group or an ethylenically unsaturated double bond group.

<3>

The method for producing a hard coat film according to <1> or <2>, wherein the hard coat layer-forming composition further comprises f) an ultraviolet absorber.

<4>

The method for producing a hard coating film according to any one of <1> to <3>, wherein the ratio t _H / t _T of the thickness t _{T of} the transparent support to the thickness t _H of the hard coating layer is 0.2 or more and 0.7 or less. .

<5>

The method for producing a hard coating film according to any one of <1> to <4>, wherein a) is epoxy cyclohexyl methyl (meth) acrylate.

<6>

The method for producing a hard coating film according to any one of <1> to <5>, wherein the transparent support system is a cellulose film, and the thickness of the transparent support is 25 μm or less.

<7>

The method for producing a hard coating film according to any one of <1> to <6>, wherein the transparent support is an acrylic resin film, and the thickness of the transparent support is 40 μm or less.

<8>

The method for producing a hard coat film according to any one of <1> to <6>, wherein the transparent support system tritiated cellulose film contains at least a compound represented by the following general formula I.

In the general formula I, R ¹ , R ³ and R ⁵ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aromatic group. The alkyl group, cycloalkyl group, alkenyl group, and aromatic group may have a substituent. Among them, any of R ¹ , R ^3, and R ⁵ is an alkyl group or a cycloalkyl group substituted with a group having a ring structure, and the total number of ring structures existing in R ¹ , R ^3, and R ⁵ is 3 or more. .

<9>

A hard coating film is manufactured by the manufacturing method of the hard coating film as described in any one of <1> to <8>.

<10>

A polarizing plate includes at least one polarizer and a hard coat film such as <9> as a protective film of the polarizer.

<11>

A liquid crystal display device includes a liquid crystal cell and a polarizing plate such as <10> arranged on at least one side of the liquid crystal cell, and the hard coating film is disposed on the outermost surface.

According to the present invention, it is possible to provide a hard coating film that does not damage the surface hardness of the film, suppresses the occurrence of curls and wrinkles, and does not cause the problem of white turbidity due to outflow or the like even in a hot and humid environment. In addition, according to the present invention, it is possible to provide a hard coating film having sufficient ultraviolet absorption ability in addition to the above-mentioned properties, even if the thickness of the transparent support is 25 μm or less. In addition, it is also possible to provide a polarizing plate and a liquid crystal image display device having the above-mentioned hard coating film, which are excellent in handleability, and which do not deteriorate display quality due to curling or wrinkling, and which can reduce light leakage during a moist heat test.

[Form of Implementing Invention]

The description of the constituent elements described below may be completed based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In addition, the numerical range indicated using "~" in this specification means the range including the numerical value described before and after "~" as a lower limit and an upper limit. "Acrylic resin" means a resin obtained by polymerizing a methacrylic acid or a derivative of acrylic acid, and a resin containing the derivative. In addition, unless specifically limited, "(meth) acrylate" means an acrylate and a methacrylate, and "(meth) acrylic" means an acrylic acid and a methacrylic acid.

<Manufacturing Method of Hard Coating Film>

The method for producing a hard coat film of the present invention is a method for producing a hard coat film having a hard coat layer on at least one side of a transparent support. The method for producing the hard coat film includes at least a hard coat including the following a) to d). The step of hardening the layer-forming composition to form the above-mentioned hard coating layer. When the total solid content of the hard-coat-forming composition is 100% by mass, the above-mentioned hard-coat-forming composition includes: 10 to 40% by mass The following a), 40 to 89.8% by mass of the following b), 0.1 to 10% by mass of the following c), and 0.1 to 10% by mass of the following d).

a) A compound having one alicyclic epoxy group and one ethylenically unsaturated double bond group in the molecule, and having a molecular weight of 300 or less

b) Compounds with more than 3 ethylenically unsaturated double bond groups in the molecule

c) radical polymerization initiator

d) Cationic polymerization initiator

Hereinafter, details regarding each component included in the hard coat layer forming composition will be described.

[a] A compound having one alicyclic epoxy group and one ethylenically unsaturated double bond group in its molecule and having a molecular weight of 300 or less]

A compound having a molecular weight of 300 or less having an alicyclic epoxy group and an ethylenically unsaturated double bond group in the a) contained in the composition for forming a hard coat layer in the present invention will be described. A) a compound having one alicyclic epoxy group and one ethylenically unsaturated double bond group in its molecule and having a molecular weight of 300 or less is also referred to as "a) component".

Examples of the ethylenically unsaturated double bond group include polymerizable functional groups such as (meth) acrylfluorenyl, vinyl, styryl, and allyl. Among them, (meth) acrylfluorenyl is preferred. And -C (O) OCH = CH ₂ , particularly preferably (meth) acrylfluorenyl. By having an ethylenically unsaturated double bond group, high hardness can be maintained, and moist heat resistance can be imparted.

In the present invention, the number of epoxy groups and ethylenically unsaturated double bond groups in the molecule is one. This is because when the number of each functional group is two or more, as the number of functional groups increases, the molecular weight increases and the hardness decreases.

a) The molecular weight of the component is 300 or less, but preferably 210 or less, and more preferably 200 or less.

When the molecular weight is more than 300, the site other than the epoxy group or the ethylenically unsaturated double bond group increases, and the hardness is deteriorated. By setting the molecular weight to 300 or less, deterioration in hardness can be prevented.

In addition, from the viewpoint of suppressing volatilization during formation of the hard coat layer, The molecular weight of a) is preferably 100 or more, and more preferably 150 or more.

The component a) is not limited as long as it has one alicyclic epoxy group and one ethylenically unsaturated double bond group in the molecule, and the molecular weight is 300 or less, but it is preferably in the following general formula (1 ).

In the general formula (1), R represents a monocyclic hydrocarbon or a crosslinked hydrocarbon, L represents a single bond or a divalent linking group, and Q represents an ethylenically unsaturated double bond group.

In the case where R in the general formula (1) is a monocyclic hydrocarbon, an alicyclic hydrocarbon is preferable, and among them, an alicyclic group having 4 to 10 carbon atoms is more preferable, and 5 to 7 carbon atoms are more preferable. The alicyclic group is particularly preferably an alicyclic group having 6 carbon atoms. Specifically, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl are preferred, and cyclohexyl is particularly preferred.

When R in the general formula (1) is a crosslinked hydrocarbon, it is preferably a bicyclic ring (bicyclo ring) or a tricyclic ring (tricyclo ring), and examples thereof include 5 to 20 carbon atoms. Crosslinked hydrocarbons, norbornyl group, norbornyl, isobornyl, tricyclodecyl, dicyclopentenyl, dicyclopentyl, tricyclopentenyl, and tricyclopentyl, adamantyl , Adamantyl substituted with lower alkyl, and the like.

When L represents a divalent linking group, a divalent aliphatic hydrocarbon group is preferred. As the divalent aliphatic hydrocarbon group, the carbon number is preferably from 1 to 6, more preferably from 1 to 3, and even more preferably from 1. The divalent aliphatic hydrocarbon group is preferably a linear, branched or cyclic alkylene group, and more preferably a linear or branched one. The alkylene group is more preferably a linear alkylene group.

Examples of Q include polymerizable functional groups such as (meth) acrylfluorenyl, vinyl, styryl, and allyl. Among these, (meth) acrylfluorenyl and -C (O) are preferred. OCH = CH ₂ , particularly preferred is (meth) acrylfluorenyl.

The specific compound as component a) is not particularly limited as long as it has one alicyclic epoxy group and one ethylenically unsaturated double bond group in its molecule, and the molecular weight is 300 or less. Japan can be used Paragraph [0015] of Japanese Patent Application Laid-Open No. 10-17614, or a compound represented by the following general formula (1A) or (1B), 1,2-epoxy-4-vinylcyclohexane, and the like.

Among these, a compound represented by the following general formula (1A) or (1B) is more preferable, and a compound represented by the following general formula (1A) having a low molecular weight is even more preferable. The compound represented by the following general formula (1A) is also preferably an isomer thereof. In the formula of the following general formula (1A), L ₂ represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 ((meth) acrylic epoxy resin). Cyclohexyl methyl ester).

By using these compounds, both high hardness and low curl can be achieved.

In the general formula (1A), R ₁ represents a hydrogen atom or a methyl group, and L ₂ represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.

In the general formula (1B), R ₁ represents a hydrogen atom or a methyl group, and L ₂ represents a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms.

The divalent aliphatic hydrocarbon group of L ₂ in the general formulae (1A) and (1B) has a carbon number of 1 to 6, more preferably a carbon number of 1 to 3, and even more preferably a carbon number of 1. The divalent aliphatic hydrocarbon group is preferably a linear, branched, or cyclic alkylene, more preferably a linear or branched alkylene, and even more preferably a linear alkylene. alkyl.

When the total solid content of the hard-coat layer-forming composition in the present invention is 100% by mass, the component a) is contained in an amount of 10 to 40% by mass. If the content is less than 10% by mass, the curl reduction effect or the light leakage reduction effect when applied to a liquid crystal display device is insufficient.

On the other hand, when the content is more than 40% by mass, curling deteriorates and hardness decreases.

When the total solid content of the hard-coat layer-forming composition in the present invention is 100% by mass, it is preferable to contain 12 to 35% by mass of the component a), and more preferably to contain 15 to 25% by mass.

[b] Compound having three or more ethylenically unsaturated double bond groups in the molecule]

A compound having b) having three or more ethylenically unsaturated double bond groups in the molecule contained in the composition for forming a hard coat layer in the present invention will be described. B) A compound having three or more ethylenically unsaturated double bond groups in its molecule is also referred to as a "b) component".

b) The component can exhibit high hardness by having three or more ethylenically unsaturated double bond groups in the molecule.

Examples of the component b) include esters of a polyhydric alcohol and (meth) acrylic acid, Vinylbenzene and its derivatives, vinyl fluorene, (meth) acrylamide and the like. Among them, a compound having three or more (meth) acryl fluorenyl groups is preferable from the viewpoint of hardness, and examples thereof include acrylate compounds that form a hardened product having a high hardness that are widely used in the industry. Examples of such a compound include esters of a polyhydric alcohol and (meth) acrylic acid {for example, neopentaerythritol tetra (meth) acrylate, neopentaerythritol tri (meth) acrylate, and trimethylolpropane Tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO modified phosphoric acid tri (meth) acrylic acid Ester, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dinepentaerythritol tetra (meth) acrylate, dinepentaerythritol penta ( (Meth) acrylates, dipentaerythritol hexa (meth) acrylate, neopentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexane tetramethacrylate, polyurethane Ester polyacrylate, polyester polyacrylate, caprolactone modified ginseng (propylene ethoxyethyl) isotricyanate, etc.

Specific examples of the polyfunctional acrylate compound having three or more (meth) acrylfluorenyl groups include KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., DPHA-2C, PET-30, Same as TMPTA, TPA-320, TPA-330, RP-1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, GPO-303, Osaka Organic Esters of polyhydric alcohols such as V # 400 and V # 36095D manufactured by Chemical Industry Co., Ltd. and (meth) acrylic acid. In addition, it can also be suitable for use with UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, and UV-7630B. , Same as UV-7640B, same as UV-6630B, same as UV-7000B , The same UV-7510B, the same UV-7461TE, the same UV-3000B, the same UV-3200B, the same UV-3210EA, the same UV-3310EA, the same UV-3310B, the same UV-3500BA, the same UV-3520TL, and the same UV-3700B , The same UV-6100B, the same UV-6640B, the same UV-2000B, the same UV-2010B, the same UV-2250EA, the same UV-2750B (made by Japan Synthetic Chemistry (stock)), UL-503LN (Kyoeisha Chemical (stock) ), UNIDIC 17-806, same 17-813, same V-4030, same V-4000BA (DAINIPPON INK AND CHEMICALS), EB-1290K, EB-220, EB-5129, EB-1830, EB-4358 (DAICEL UCB (share) system), Hi-coap AU-2010, same AU-2020 ((share) Tokushiki system), ARONIX M-1960 (East Asian Synthesis (share) system), ART-RESIN UN-3320HA , UN-3320HC, UN-3320HS, UN-904, HDP-4T and other tri-functional urethane acrylate compounds, ARONIX M-8100, M-8030, M-9050 (manufactured by East Asia Synthesis Co., Ltd.) ), KBM-8307 (DAICEL CYTEC), and the like.

The component b) may be composed of a single compound, or a plurality of compounds may be used in combination.

When the total solid content of the hard-coat layer-forming composition in the present invention is 100% by mass, the component b) is contained in an amount of 40 to 89.8% by mass. If the content is less than 40% by mass, sufficient hardness cannot be obtained. On the other hand, when the content is more than 89.8% by mass, since the content of the component a) is reduced, the hardening that reduces curl is insufficient.

In addition, the ratio of component a) to component b) is preferably 11 to 100%, more preferably 15 to 60%, and even more preferably 20 to 40%.

By setting a) component and b) component to the above ratio, a strong Network structure can prevent light leakage.

[c) Free radical polymerization initiator]

The c) radical polymerization initiator contained in the composition for hard-coat layer formation of this invention is demonstrated. C) The radical polymerization initiator is also referred to as "c) component".

Polymerization of a compound having an ethylenically unsaturated group can be performed by irradiation or heating with ionizing radiation in the presence of a photo radical polymerization initiator or a thermal radical polymerization initiator. Commercially available compounds can be used as photo- and thermal polymerization initiators, which are described in "Latest UV Hardening Technology" (p.159, Issuer: Takahiro Ichihiro, Issuing Agency: Technical Information Association (Shares), 1991 (Issued), or a catalog of CIBA SPECIALTY CHEMICALS (shares).

As component c), specifically, an alkyl phenone-based photopolymerization initiator (Irgacure651, Irgacure184, DAROCURE1173, Irgacure2959, Irgacure127, DAROCURE MBF, Irgacure907, Irgacure369, Irgacure379EG), fluorenylphosphine oxide-based photopolymerization can be used. Initiator (Irgacure819, LUCIRIN TPO), others (Irgacure784, Irgacure OXE01, Irgacure OXE02, Irgacure754) and the like.

When the total solid content of the hard coat layer-forming composition in the present invention is 100% by mass, the amount of the component c) is in the range of 0.1 to 10% by mass, preferably 1 to 5% by mass. More preferably, it is 2 to 4% by mass. When the addition amount is less than 0.1% by mass, the polymerization does not proceed sufficiently and the hardness of the hard coat layer is insufficient. On the other hand, in the case of more than 10% by mass, the UV light does not reach the inside of the film and the hardness of the hard coat layer is insufficient. These free radicals The initiator may be used alone or in combination of plural kinds.

[d) Cationic polymerization initiator]

The d) cationic polymerization initiator contained in the composition for forming a hard coat layer in the present invention will be described. D) cationic polymerization initiator is also referred to as "d) component".

Examples of the component d) include well-known compounds such as a photocationic polymerization photoinitiator, a pigment-based photochromic agent, a photochromic agent, or a well-known acid generator used in microphotoresist, and the like. The mixture and so on.

For example, an onium compound, an organic halogen compound, and a difluorene compound are mentioned. Specific examples of these organic halogen compounds and difluorene compounds are the same as those described for the compounds that generate the above-mentioned radicals.

Examples of onium compounds include diazonium salts, ammonium salts, iminium salts, sulfonium salts, sulfonium salts, sulfonium salts, sulfonium salts, selenium salts, and the like, and for example, Japanese Patent Application Laid-Open No. 2002-29162 The compounds described in paragraph numbers [0058] to [0059] in the gazette.

In the present invention, as a particularly suitable cationic polymerization initiator, an onium salt is mentioned. From the viewpoint of the photosensitivity of starting photopolymerization and the stability of the material of the compound, diazonium salts, sulfonium salts, Among sulfonium salts and imine salts, sulfonium salts are most preferred from the viewpoint of light resistance.

Specific examples of the onium salt that can be suitably used in the present invention include, for example, the ammonium sulfonium salt described in paragraph number [0035] of Japanese Patent Application Laid-Open No. 9-268205 and Japanese Patent Application Laid-Open No. 2000 -71366 diary sulfonium salt or triaryl sulfonium salt described in paragraph numbers [0010] to [0011], and thiobenzoic acid S-benzene described in paragraph number [0017] of Japanese Patent Laid-Open No. 2001-288205 Phosphonium salt 2. Onium salts and the like described in paragraph numbers [0030] to [0033] of Japanese Patent Laid-Open No. 2001-133696.

As another example, the organometallic / organohalide described in paragraph numbers [0059] to [0062] of Japanese Patent Application Laid-Open No. 2002-29162, a photoacid generator having an ortho-nitrobenzyl type protecting group, A compound such as a sulfonic acid compound (iminosulfonate, etc.) is generated by photodecomposition.

As the specific compound of the sulfonium-based cationic polymerization initiator, B2380 (manufactured by Tokyo Chemical Industry), BBI-102 (manufactured by Green Chemical), WPI-113 (manufactured by Wako Pure Chemical Industries), WPI-124 (Wako Pure Chemical Industries, Ltd.) Industrial), WPI-169 (Wako Pure Chemical Industries), WPI-170 (Wako Pure Chemical Industries), DTBPI-PFBS (Toyo Synthetic Chemicals).

As component d), only one kind may be used, or two or more kinds may be used in combination.

When the total solid content of the hard-coat layer-forming composition in the present invention is 100% by mass, the component d) is added in a range of 0.1 to 10% by mass, preferably 0.5 to 3.0% by mass. Add to. In consideration of the stability, the polymerization reactivity, and the like of the curable composition, the addition amount is preferably within the above range.

[e) Inorganic fine particles having reactivity with an epoxy group or an ethylenically unsaturated double bond group]

In the hard coat layer forming composition of the present invention, it is preferable to add e) inorganic fine particles having reactivity with an epoxy group or an ethylenically unsaturated double bond group. E) The inorganic fine particles having reactivity with an epoxy group or an ethylenically unsaturated double bond group are also referred to as e) components.

The addition of inorganic fine particles can reduce the hardening shrinkage of the hardened layer The amount can therefore reduce film curl. Furthermore, by using inorganic fine particles having reactivity with an epoxy group or an ethylenically unsaturated double bond group, pencil hardness can be improved. Examples of the inorganic fine particles include silica particles, titania particles, zirconia particles, and alumina particles. Among these, silicon oxide particles are preferred.

In general, inorganic microparticles have low affinity with organic components such as polyfunctional vinyl monomers. Therefore, only a simple mixing may form aggregates, and the cured layer after being cured may be easily broken. Therefore, in order to increase the affinity between the inorganic fine particles and the organic component, the component e) in the present invention treats the surface of the inorganic fine particles with a surface modifier containing an organic segment.

The surface modifier preferably has a functional group that forms a bond with or can be adsorbed on the inorganic fine particles and a functional group that has a high affinity for an organic component in the same molecule. As the surface modifier having a functional group capable of binding or adsorbing to inorganic fine particles, a metal alcoholate surface modifier such as silane, aluminum, titanium, zirconium, or the like, or a phosphate group, a sulfuric acid group, a sulfonic acid group, or a carboxylic acid group is preferred. Surface modifiers for anionic groups such as acid groups. In addition, the functional group having high affinity with the organic component may be a combination of only the organic component and the hydrophobicity, but a functional group capable of chemically bonding with the organic component is preferred, and an ethylenically unsaturated double bond is particularly preferred. Or a ring-opening polymerizable group.

In the present invention, a preferred inorganic fine particle surface modifier is a hardening resin having a metal alcoholate or an anionic group and an ethylenically unsaturated double bond group or a ring-opening polymerizable group in the same molecule. By chemically bonding with organic components, the crosslinking density of the hard coating layer is increased, which can improve the pencil hardness.

Representative examples of these surface modifiers include the following coupling agents containing unsaturated double bonds, organic curable resins containing a phosphate group, organic curable resins containing a sulfuric acid group, and organic curable resins containing a carboxylic acid group. Resin, etc.

S-1 H ₂ C = C (X) COOC ₃ H ₆ Si (OCH ₃ ) ₃

S-2 H ₂ C = C (X) COOC ₂ H ₄ OTi (OC ₂ H ₅ ) ₃

S-3 H ₂ C = C (X) COOC ₂ H ₄ OCOC ₅ H ₁₀ OPO (OH) ₂

S-4 (H ₂ C = C (X) COOC ₂ H ₄ OCOC ₅ H ₁₀ O) ₂ POOH

S-5 H ₂ C = C (X) COOC ₂ H ₄ OSO ₃ H

S-6 H ₂ C = C (X) COO (C ₅ H ₁₀ COO) ₂ H

S-7 H ₂ C = C (X) COOC ₅ H ₁₀ COOH

S-8 CH ₂ CH (O) CH ₂ OC ₃ H ₆ Si (OCH ₃ ) ₃

(X represents a hydrogen atom or CH ₃ )

The surface modification of these inorganic fine particles is preferably performed in a solution. The method may be as follows: when the inorganic fine particles are mechanically finely dispersed, the surface modifier is present together, or the inorganic fine particles are finely dispersed, and the surface modifier is added and stirred, or the surface is dispersed before the inorganic fine particles are finely dispersed Modification (if necessary, heating after heating, drying, or changing the pH) is followed by fine dispersion. As the solution for dissolving the surface modifier, an organic solvent having a large polarity is preferred. Specific examples include well-known solvents such as alcohols, ketones, and esters.

When the total solid content of the hard coat layer-forming composition in the present invention is 100% by mass, considering the balance between hardness and brittleness of the coating film, e) the amount of the component is preferably 5 to 40% by mass, More preferably, it is 10 to 30% by mass.

The size (average primary particle size) of the inorganic fine particles is preferably 10 nm to 100 nm, and more preferably 10 to 60 nm. The average particle size of microparticles can be determined by The submicron photo is obtained. If the particle size of the inorganic fine particles is too small, the effect of improving the hardness cannot be obtained, and if it is too large, the haze will increase.

The shape of the inorganic fine particles may be either spherical or non-spherical, but is preferably a non-spherical shape in which 2 to 10 inorganic fine particles are connected in terms of imparting hardness. It is estimated that by using a plurality of inorganic fine particles connected in a chain shape, a strong particle network structure is formed, and the hardness is improved.

Specific examples of the inorganic fine particles include ELECOM V-8802 (spherical silica fine particles having an average particle diameter of 12 nm manufactured by Nippon Kogyo Co., Ltd.) or ELECOM V-8803 (heteromorphic silica fine particles made by Nippon Kogyo Co., Ltd.), MiBK-SD (spherical silica particles with an average particle size of 10 to 20 nm manufactured by Nissan Chemical Industry Co., Ltd.), MEK-AC-2140Z (spherical silica particles with an average particle size of 10 to 20 nm manufactured by Nissan Chemical Industry Co., Ltd.) ), MEK-AC-4130 (spherical silica particles with an average particle size of 40-50 nm manufactured by Nissan Chemical Industry Co., Ltd.), MiBK-SD-L (with an average particle size of 40-50 nm manufactured by Nissan Chemical Industry Co., Ltd.) Spherical silica particles), MEK-AC-5140Z (spherical silica particles with an average particle diameter of 70 to 100 nm, manufactured by Nissan Chemical Industries, Ltd.), etc. Among them, in view of imparting hardness, ELECOM V-8803 having a special shape is preferable.

[f) Ultraviolet absorbent]

The hard coat layer forming composition in the present invention preferably contains f) an ultraviolet absorber. f) Ultraviolet absorbent is also called f) component.

The ultraviolet absorber contributes to the improvement of the durability of the film. In particular, in a case where the hard coat film of the present invention is used as a surface protective film of an image display device, the addition of an ultraviolet absorber is effective. Ultraviolet absorption ability, can only make transparent support have this function, but When the support is made into a thin film, it is preferred that the hard coat layer is also provided with ultraviolet absorbing ability due to its reduced function. The ultraviolet absorber that can be used in the present invention is not particularly limited, and examples thereof include compounds described in paragraphs [0107] to [0185] of Japanese Patent Application Laid-Open No. 2006-184874. A polymer ultraviolet absorbent can also be preferably used, and a polymer ultraviolet absorbent described in Japanese Patent Application Laid-Open No. 6-148430 is particularly preferably used.

f) The amount of the component varies with the type of compound, the use conditions, etc., but when the total solid content of the hard coat layer-forming composition in the present invention is 100% by mass, it is preferably 0.1. The proportion of ~ 10% by mass contains the f) component.

Examples of the f) component include, but are not limited to, UV-1 to 4.

When using an ultraviolet absorber, c) the type of the radical polymerization initiator is preferably combined in such a manner that the absorption wavelengths of the ultraviolet absorber and the radical initiator do not overlap, and specifically, there is absorption in a long wave Phosphine oxide-based compounds: For example, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide (e.g., IRGACURE 819 manufactured by BASF), bis (2,6-di (Methoxybenzyl))-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide (for example, manufactured by BASF) , LUCIRIN TPO). By using the above-mentioned radical initiator, it is possible to suppress the hindrance to curing caused by the ultraviolet absorber. d) The type of the cationic polymerization initiator is preferably combined with IRGACURE PAG 103, IRGACURE PAG 121, and CGI725 having absorption in a long wave.

In addition to the above-mentioned combined long wave having an absorption initiator and a UV absorber, a hardening accelerator (sensitizer) is preferably used in combination. By combining sensitizers, the amount of polymerization initiator can be reduced, and the range of choice of materials can be increased. Specific examples of the photosensitizer that can be used in combination include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone, and oxygen sulfur. , Anthracene, diphenylbutadiene, distyrylbenzene, acridinone ring, and the like.

(Solvent)

The hard-coat layer forming composition in the present invention may contain a solvent. As the solvent, various solvents selected from the following points can be used: each component can be dissolved or dispersed; a uniform surface shape is easily obtained in the coating step and the drying step; liquid storage stability can be ensured; and a moderate saturated vapor pressure can be obtained.

The solvent can be used by mixing two or more kinds. In particular, from the viewpoint of a drying load, a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature is preferably used as a main component, and a solvent having a boiling point exceeding 100 ° C. is contained in a small amount in order to adjust the drying rate.

In the hard coat layer forming composition of the present invention, in order to prevent particles It is preferable to contain 30 to 80% by mass of the solvent having a boiling point of 80 ° C. or lower, and more preferably 50 to 70% by mass of the total composition of the coating composition. By setting the solvent ratio having a boiling point of 80 ° C. or lower to the above ratio, it is possible to moderately suppress the penetration of the resin component into the transparent support, and to increase the rate of viscosity increase due to drying, thereby suppressing particle sedimentation.

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

Examples of solvents having a boiling point exceeding 100 ° C include octane (125.7 ° C), toluene (110.6 ° C), xylene (138 ° C), tetrachloroethylene (121.2 ° C), chlorobenzene (131.7 ° C), and Alkane (101.3 ℃), dibutyl ether (142.4 ℃), isobutyl acetate (118 ℃), cyclohexanone (155.7 ℃), 2-methyl-4-pentanone (same as MIBK, 115.9 ℃), 1-butanol (117.7 ° C), N, N-dimethylformamide (153 ° C), N, N-dimethylacetamide (166 ° C), dimethylsulfine (189 ° C), and the like. Cyclohexanone and 2-methyl-4-pentanone are preferred.

(Surfactant)

The hard coat layer-forming composition in the present invention is also suitable for using various surfactants. In general, a surfactant can suppress uneven film thickness due to uneven drying due to local distribution of drying wind.

As the surfactant, specifically, a fluorine-based surfactant, or a silicone-based surfactant, or both of them are preferable. In addition, the surfactant is preferably an oligomer or a polymer rather than a low-molecular compound.

As a preferable example of the fluorine-based surfactant, a copolymer containing a fluoroaliphatic group (hereinafter, may be abbreviated as "fluorine-based polymer") may be mentioned. The above-mentioned fluorine-based polymer includes the following ( Acrylic resins, methacrylic resins, and repeating units of monomers i) or repeating units containing monomers corresponding to (i) Copolymers of vinyl-based monomers copolymerized with them are useful.

(i) Fluoroaliphatic group-containing monomer represented by the following Formula One

Formula One

In Formula 1, R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom, or -N (R12)-, m represents an integer of 1 to 6 and n represents an integer of 2 to 4. R12 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is specifically a methyl group, an ethyl group, a propyl group, or a butyl group, and preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.

(ii) A monomer represented by the following general formula 可以 which can be copolymerized with the above (i)

Formula 贰

In the general formula 贰, R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom, or -N (R15)-, and R15 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group. A group, an ethyl group, a propyl group, or a butyl group is preferably a hydrogen atom or a methyl group. Y is preferably an oxygen atom, -N (H) -, and -N (CH ₃₎ -.

R ¹⁴ represents a linear, branched, or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. Examples of the substituent of the alkyl group of R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxylic acid, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, A nitro group, a cyano group, an amine group, and the like are not limited thereto. Suitable as a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms: straight and branched butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl , Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl, eicosyl, etc., and monocyclic rings such as cyclohexyl, cycloheptyl, etc. Alkyl and polycyclic cycloalkyl such as bicycloheptyl, bicyclodecyl, tricycloundecyl, tetracyclododecyl, adamantyl, norbornyl, tetracyclododecyl and the like.

Based on the monomers of the above-mentioned fluorine-based polymer, the amount of these fluorine-containing aliphatic group-containing monomers represented by the general formula I used in the fluorine-based polymer is 10 mol% or more, preferably 15 to 70. In the range of Molar%, it is more preferably in the range of 20 to 60 Molar%.

The preferable mass average molecular weight of the fluorine-based polymer is preferably 3000 to 100,000, and more preferably 5,000 to 80,000. In addition, with respect to 100 parts by mass of the coating liquid, the preferable addition amount of the fluorine-based polymer is in the range of 0.001 to 5 parts by mass, more preferably in the range of 0.005 to 3 parts by mass, and still more preferably in the range of 0.01 to Within 1 part by mass. If the addition amount of the fluorine-based polymer is 0.001 parts by mass or more, the effect of adding the fluorine-based polymer can be sufficiently obtained. In addition, if the amount of the fluorine-based polymer is 5 parts by mass or less, drying of the coating film does not occur and it cannot be sufficiently performed. The problem of adversely affecting the performance as a coating film.

Examples of preferred silicone compounds include: "X-22-174DX", "X-22-2426", "X22-164C", "X-22-" manufactured by Shin-Etsu Chemical Industry Co., Ltd. 176D "(above are the trade names);" FM-7725 "," FM-5521 "," FM-6621 "(above are the trade names) made by Chisso;" DMS-U22 "," RMS "made by Gelest -033 "(the above is the trade name);" SH200 "," DC11PA "," ST80PA "," L7604 "," FZ-2105 "," L-7604 "," Y-7006 "manufactured by Dow Corning Toray "," SS-2801 "(the above are the trade names); Momentive Performance "TSF400" (trade name) and the like manufactured by Materials Japan are not limited thereto.

When the total solid content of the hard-coat layer-forming composition in the present invention is 100% by mass, it is preferably 0.01 to 0.5% by mass, and more preferably 0.01 to 0.3% by mass. .

(Matting particles)

For the purpose of imparting internal scattering properties or providing unevenness on the surface, the hard coat layer may contain matting particles having an average particle diameter of 1.0 to 10.0 μm, preferably 1.5 to 5.0 μm. In addition, when the total solid content of the hard-coat layer-forming composition is 100% by mass, the preferred addition amount of the matting particles is preferably from 1.0 to 30% by mass, and more preferably from 5 to 20% by mass. In addition, in order to adjust the viscosity of the coating liquid, a polymer compound, an inorganic layered compound, or the like may be included. It is also possible to use e) as matting particles.

[Transparent support]

As a material for forming the transparent support of the present invention, a polymer excellent in terms of optical performance transparency, mechanical strength, thermal stability, isotropy, and the like is preferable. The so-called transparent in the present invention means that the transmittance of visible light is 60% or more, preferably 80% or more, and particularly preferably 90% or more. Examples thereof include polycarbonate polymers, polyester polymers such as polyethylene terephthalate and polyethylene terephthalate, and (meth) groups such as polymethyl methacrylate. Acrylic polymers, styrene polymers such as polystyrene or acrylonitrile-styrene copolymer (AS resin), and the like. Other examples include polyolefins such as polyethylene and polypropylene, polyolefin-based polymers such as ethylene-propylene copolymers, vinyl chloride-based polymers, and nylon-based polymers such as nylon and aromatic polyamines. , Fluorene-based polymer, fluorene-based polymer, polyether fluorene-based polymer, polyetheretherketone-based polymer, polyphenylene sulfide Based polymer, polyvinylidene chloride based polymer, vinyl butyral based polymer, allyl ester based polymer, polyoxymethylene based polymer, epoxy based polymer, or polymerization in which these polymers are mixed Thing as an example. In addition, a film in which two or more resin films are laminated can also be used.

In addition, as a material for forming the transparent support of the present invention, a cellulose-based polymer typified by triethylammonium cellulose (particularly trioxane), which is currently used as a transparent protective film for polarizing plates, can also be preferably used. Cellulose). In addition, an acrylic film that has been proposed as a polarizing plate protective film in recent years can also be preferably used.

The thickness of the transparent support can be about 10 μm to 1000 μm, but is preferably 10 m to 80 μm, more preferably 15 μm to 40 μm, and even more preferably 15 μm to 30 μm. By reducing the thickness of the transparent support, the thickness of the entire film can be reduced.

As a transparent support, the aspect which uses the film containing the compound represented by the following general formula I is also preferable. Although the detailed mechanism is not clear, by using a film containing a compound represented by the following general formula I as a transparent support, the visibility of the display device can be improved even when the thickness of the transparent support is reduced. . The combined use with the hard coat layer forming composition of the present invention is effective because it effectively suppresses the decrease in the visibility of a display device accompanying the passage of the wet heat time.

(Compound represented by Formula I)

In the general formula I, R ¹ , R ³ and R ⁵ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aromatic group. The alkyl group, cycloalkyl group, alkenyl group, and aromatic group may have a substituent. However, any one of R ¹ , R ^3, and R ⁵ is an alkyl group or a cycloalkyl group substituted with a group having a ring structure, and a total of three or more ring structures are present in R ¹ , R ^3, and R ⁵ .

The carbon number of the alkyl group in the above-mentioned R ¹ , R ³ and R ⁵ is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 5, particularly preferably 1 to 3, of which the most preferable is A. Or ethyl. However, in the case of an alkyl group substituted with a group having a ring structure, the number of carbon atoms is preferably 7 to 20, more preferably 7 to 12, and even more preferably 7 to 10. The ring structure in the alkyl group having a ring structure may be an aromatic ring (including an aromatic heterocyclic ring) or an aliphatic ring, but is preferably an aromatic hydrocarbon ring or an aliphatic ring.

The number of carbon atoms of the cycloalkyl group in R ¹ , R ^3, and R ⁵ is preferably 3 to 20, more preferably 3 to 10, even more preferably 4 to 8, and particularly preferably 5 or 6. Specific examples of the cycloalkyl group include cyclopropyl, cyclopentyl, and cyclohexyl. Particularly preferred is cyclohexyl.

The carbon number of the alkenyl group in R ¹ , R ³ and R ⁵ is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 5. Examples include vinyl and allyl.

The aromatic group in R ¹ , R ^3, and R ⁵ may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group. The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 16, and even more preferably from 6 to 12.

Among the aromatic groups, the aromatic hydrocarbon group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

Each of the aforementioned groups of R ¹ , R ³ and R ⁵ may have a substituent.

The substituent is not particularly limited, and examples thereof include an alkyl group (preferably a carbon number of 1 to 10, for example, methyl, ethyl, isopropyl, tertiary butyl, pentyl, heptyl, 1- Ethylpentyl, benzyl, etc.), alkenyl (preferably carbon number 2-20, for example, vinyl, allyl, olealkenyl, etc.), alkynyl (preferably carbon number 2-20, for example , Ethynyl, 2-butynyl, phenylethynyl, etc.), cycloalkyl (preferably 3-20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc. ), Aryl (preferably 6 to 26 carbons, for example, phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), heterocyclyl (A heterocyclic group having 0 to 20 carbon atoms is preferred, and the hetero atoms constituting the ring are preferably an oxygen atom, a nitrogen atom, and a sulfur atom. A 5 or 6-membered ring can be used to condense the ring on the benzene ring or heterocyclic ring. It may be a saturated ring, an unsaturated ring, an aromatic ring, for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2- Azolyl, etc.), alkoxy (preferably carbon number 1-20, for example, methoxy, ethoxy, isopropoxy, benzyloxy, etc.), aryloxy (preferably carbon number 6- 26, for example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkylthio (preferably carbon number 1-20, for example, methylthio Group, ethylthio, isopropylthio, benzylthio, etc.), arylthio (preferably 6 to 26 carbon atoms, for example, phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), sulfonyl (preferably alkyl or arylsulfonyl), carbon number is preferably 1-20, for example, methylsulfonyl, ethylsulfonyl Group, benzenesulfonyl group, tosylsulfonyl group, etc.), fluorenyl group (including alkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heterocyclic carbonyl group, the number of carbon is preferably 20 or less, for example, ethylamyl Ethylethenyl, propenyl, methacryl, benzoyl, nicotinyl, etc.), alkoxycarbonyl (preferably carbon number 2-20, for example, ethoxycarbonyl, 2- Ethylhexyloxycarbonyl, etc.), aryloxycarbonyl (preferably 7 to 20 carbons, for example, phenoxycarbonyl, naphthyloxycarbonyl, etc.), amine (including Group, alkylamino group, arylamino group, heterocyclic amino group, preferably 0 to 20 carbon atoms, for example, amine group, N, N-dimethylamino group, N, N-diethylamino group, N -Ethylamino, aniline, 1-pyrrolyl, pyridyl, morpholinyl, etc.), sulfonamido (preferably alkyl or arylsulfonamido, carbon number is preferably 0-20) For example, N, N-dimethylsulfonamido, N-phenylsulfonamido, etc.), sulfamoyl (preferably alkyl or arylsulfamoyl, carbon The number is preferably 0-20, for example, N, N-dimethylaminesulfonyl, N-phenylaminesulfonyl, etc.), fluorenyloxy (preferably carbon number 1-20, for example, acetamidine (Oxy, benzamyloxy, etc.), carbamoyl (preferably alkyl or aryl carbamoyl), carbon number is preferably 1-20, for example, N, N-dimethyl Methylaminomethylamino, N-phenylaminomethylamino, etc.), acylamino group (preferably carbon number 1-20, for example, ethylamino, acrylamino, benzene Formamylamino, nicotinamide, and the like), cyano, hydroxyl, mercapto, carboxyl, or halogen atoms (for example, fluorine, chlorine, bromine, iodine, etc.).

The aforementioned substituents may be further substituted with the aforementioned substituents. To be replaced. Examples thereof include an alkyl group substituted with a perfluoroalkyl group such as a trifluoromethyl group, an aralkyl group, and a fluorenyl group.

These substituents are not only substituents which each of R ¹ , R ³ , and R ⁵ may have, but are also applicable to the substituents in the compounds described in this specification.

Here, among the above-mentioned substituents that each of R ¹ , R ³ and R ⁵ may have, alkyl, aryl, alkoxy, alkylthio, alkylsulfonyl, halogen atom, fluorenyl, and the like are more preferable. Alkyl, aryl, alkoxy, and fluorenyl are preferred, and alkyl and alkoxy are even more preferred.

In the compound represented by the general formula I, any of R ¹ , R ^3, and R ⁵ is an alkyl group or a cycloalkyl group substituted with a group having a ring structure, and preferably any one is substituted with a ring group having a ring structure. Alkyl.

Among them, an alkyl group or a cycloalkyl group in which R ⁵ is substituted with a group having a ring structure is preferred.

Here, the ring having a ring structure group is preferably a benzene ring, a naphthalene ring, a cyclopentane ring, a cyclohexane ring, a nitrogen-containing heteroaromatic ring (for example, a pyrrole ring, a pyrazole ring, an imidazole ring, Azole ring, thiazole ring, pyridine ring, indole ring, isoindole ring).

The compound represented by Formula I is preferably an alkyl group or a cycloalkyl group having a ring structure as any of R ¹ , R ^3, and R ⁵ as a substituent. It is preferable that R ¹ and R ³ are each independently an alkyl group which may have a substituent, an aromatic group which may have a substituent, or a cycloalkyl group.

The compound represented by Formula I is more preferably a total of four ring structures existing in the substituents of R ¹ , R ^3, and R ⁵ .

R ^{5 is} preferably an alkyl group or a cycloalkyl group which may be substituted with a ring structure or a fluorenyl group, more preferably an alkyl group substituted with an aryl group, an alkyl group substituted with a fluorenyl group, or a cycloalkyl group, and even more preferably It is an aryl-substituted alkyl group or a cycloalkyl group.

Hereinafter, the above-mentioned preferred alkyl group and cycloalkyl group in R ⁵ will be further described.

Among the alkyl groups, examples of the unsubstituted alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, n-hexyl, 2-ethylhexyl, and n-octyl.

Examples of the alkyl group substituted with a ring structure group include aralkyl groups such as benzyl, phenethyl, 3-phenylpropyl, and naphthylmethyl, pyridin-2-ylmethyl, and pyridin-3. -Ylmethyl, pyridin-4-ylmethyl, indol-3-ylmethyl.

The fluorenyl group in the alkyl group substituted with a fluorenyl group is preferably an alkylcarbonyl group, a cycloalkylcarbonyl group, or an arylcarbonyl group. Among them, a cycloalkylcarbonyl group and an arylcarbonyl group having a ring structure are the most preferable. Carbonyl.

Examples of the alkylcarbonyl group include ethenyl, propionyl, butylfluorenyl, and trimethylethylfluorenyl. Examples of the cycloalkylcarbonyl group include cyclopropylcarbonyl and cyclopentyl. Examples of the carbonyl group and the cyclohexylcarbonyl group include an arylcarbonyl group, a benzamyl group, a tolylmethyl group, and a naphthoyl group.

Examples of the alkyl group substituted with a fluorenyl group include 2-fluorenylethyl, 3-fluorenylpropyl, and 2-fluorenylpropyl, and 2-fluorenylethyl is preferred.

Examples of the cycloalkyl group include the groups exemplified for R ¹ , R ³ and R ⁵ .

Although the mechanism is not clear, it is thought that by suppressing the expansion of the resonance structure caused by R ⁵ , the absorption wavelength of the compound represented by the general formula I becomes shorter. It is thought that by forming such a compound, it can effectively interact with the material forming the transparent support, which helps to suppress the coloration over time or to improve the adhesion with the hard coat layer.

Among the compounds represented by the general formula I, preferred compounds are as follows.

‧ Compounds in which at least one of R ¹ , R ³ and R ⁵ is substituted with an aromatic alkyl group

Among the alkyl groups substituted with an aromatic ring, one or two aryl groups are preferably substituted on the alkyl group (in the case where two aryl groups are substituted, they are preferably substituted on the same carbon atom. ). In addition, those substituted with an aryl group and a fluorenyl group (preferably an arylfluorenyl group) on the alkyl group are also preferable.

‧ At least one of R ¹ , R ³ and R ⁵ is a group containing a cycloalkyl group, and a compound containing a cycloalkyl group based on a cycloalkyl group is preferred.

Except for the case where the ring structure of the substituents of R ¹ , R ³ or R ⁵ itself adopts a ring structure, the ring structure in the case where "the total number of ring structures existing in R ¹ , R ³ and R ⁵ is three or more" As already indicated by examples, the substituents having R ¹ , R ³ or R ^{5 also} have a morphology of a ring structure.

The ring structure is preferably a cyclic saturated hydrocarbon structure or an aromatic ring structure (aromatic hydrocarbon structure or aromatic heterocyclic structure). The ring structure may be a condensed ring structure.

When the ring structure is a cyclic saturated hydrocarbon structure, the cyclic saturated hydrocarbon structure is preferably a cycloalkyl group having 3 to 20 carbon atoms. More specifically, it is more preferably present as cyclopropyl, cyclopentyl or cyclohexyl, and particularly preferably present as cyclohexyl.

When the ring structure is an aromatic ring structure, an aromatic hydrocarbon structure is preferred. The aromatic hydrocarbon structure is preferably an aromatic hydrocarbon having 6 to 20 carbon atoms. Foundation exists. More specifically, the benzene ring and the naphthalene ring are more preferable, and the benzene ring is particularly preferable.

The above-mentioned ring structure may have a substituent, but when it has a substituent, its preferred range is the same as the substituent that each of R ¹ , R ^3, and R ⁵ may have.

In the compound represented by the general formula I, it is more preferable that R ¹ , R ³ and R ⁵ are an alkyl group, an alkenyl group or an aryl group. In addition, it is more preferable that R ¹ , R ^3, and R ⁵ each have one or more ring structures, and even more preferably one each has one ring structure.

The molecular weight of the compound represented by Formula I is preferably 250 to 1200, more preferably 300 to 800, and particularly preferably 350 to 600.

By setting the molecular weight within such a preferable range, a film having excellent volatility suppression and high transparency of the film derived from the compound represented by Formula I can be obtained.

Specific examples of the compound represented by the general formula I used in the present invention are shown below, but are not limited thereto.

It is known that the compound represented by general formula I can be synthesized using a barbituric acid synthesis method in which a urea derivative and a malonic acid derivative are condensed. Barbituric acid with two substituents on the nitrogen atom is heated by heating N, N'-disubstituted urea and chloromalonic acid, or N, N'-disubstituted urea and malonic acid It is obtained by mixing with an activator such as acetic anhydride and heating. For example, the Journal of the American Chemical Society, Vol. 61, p. 1015 (1939), Medicinal Chemistry can be preferably used. Journal of Medicinal Chemistry, Volume 54, 2409 (2011), Tetrahedron Letters, Volume 40, 8029 (1999), International Publication No. 2007/150011, and other methods .

In addition, the malonic acid used in the condensation may be unsubstituted or may have a substituent. If malonic acid having a substituent equivalent to R ⁵ is used, it can be synthesized by constructing barbituric acid. A compound represented by Formula I. In addition, if an unsubstituted malonic acid and a urea derivative are condensed, an unsubstituted barbituric acid at the 5-position can be obtained. Therefore, a compound represented by the general formula I can also be synthesized by modifying it.

As a method for modifying the 5-position, a nucleophilic substitution reaction with a halogenated alkyl group or the like or an addition reaction such as a Michael Addition reaction can be used. In addition, a method of dehydrating condensation with an aldehyde or a ketone to form an alkylene or arylidene compound and then reducing a double bond can also be preferably used. For example, zinc-induced reduction methods are described in Tetrahedron Communication, Vol. 44, 2203 (2003), contact reduction methods are described in Tetrahedron Communication, Volume 42, 4103 (2001) or the United States Journal of the Chemical Society, vol. 119, page 12849 (1997), and the reduction method by NaBH ₄ are described in Tetrahedron Newsletter, vol. 28, page 4173 (1987). They are all synthetic methods which can be preferably used in the case of having an aralkyl group at the 5-position or the case of having a cycloalkyl group at the 5-position.

The method for synthesizing the compound represented by Formula I is not limited to the above.

The content of the compound represented by Formula I in the transparent support is not particularly limited. However, in contrast to trees that form transparent substrates, 100 parts by mass of fat, preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, and particularly preferably 0.3 to 10 parts by mass.

By setting the addition amount of the compound represented by the general formula I in the above range, it is possible to effectively reduce the moisture permeability and to suppress the generation of haze.

The compound represented by the general formula I may be added in the form of a hydrate, a solvate, or a salt. In the present invention, the hydrate may include an organic solvent, and the hydrate may include water. That is, the "hydrate" and "medium" include a mixed vehicle containing either water or an organic solvent.

Examples of the solvent contained in the vehicle include any of general organic solvents. Specific examples include alcohols (for example, methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, tertiary butanol), and esters (for example, ethyl acetate ), Hydrocarbons (which can be either aliphatic or aromatic hydrocarbons, such as toluene, hexane, heptane), ethers (such as diethyl ether, tetrahydrofuran), nitriles (such as acetonitrile), ketones ( For example, acetone, 2-butanone) and the like. Preferred are alcohol solvates, and more preferred are methanol, ethanol, 2-propanol, and 1-butanol. These solvents may be reaction solvents used in the synthesis of the compound represented by the general formula I, solvents used in the crystallization and purification after synthesis, or mixed solvents thereof.

In addition, two or more solvents may be contained at the same time, and water and a solvent (for example, water and an alcohol (for example, methanol, ethanol, tertiary butanol), etc.) may be included.

The salt includes an acid addition salt formed using an inorganic or organic acid. Examples of the inorganic acid include hydrogen halide acids (hydrochloric acid, hydrogen bromide) , Sulfuric acid, phosphoric acid, etc. Examples of the organic acid include acetic acid, trifluoroacetic acid, oxalic acid, and citric acid, and examples thereof include alkanesulfonic acid (methanesulfonic acid), arylsulfonic acid (benzenesulfonic acid, 4-toluenesulfonic acid, 1,5-naphthalenedisulfonic acid).

Examples of the salt include: the acidic part of the parent compound is metal ion (for example, alkali metal salt, for example, sodium or potassium salt, alkaline earth metal salt, for example, calcium or magnesium salt, ammonium salt, alkali metal ion, alkaline earth Metal-like ions or aluminum ions), or salts formed with organic bases (ethanolamine, diethanolamine, triethanolamine, morpholine, piperidine), are not limited thereto. Among these, sodium salt and potassium salt are preferred.

(Polycondensate Plasticizer)

As a transparent support, the aspect using the film which further contains a polycondensation compound is also preferable. In more detail, it is preferable to contain a polycondensation plasticizer as a polycondensation compound. By containing a polycondensate plasticizer, the visibility of a display device can be improved even when the thickness of a transparent support is reduced.

The polycondensation plasticizer can be obtained by polycondensing at least one dicarboxylic acid represented by the following general formula (a) and at least one diol represented by the following general formula (b).

In the general formulae (a) and (b), X represents a divalent aliphatic group having 2 to 18 carbon atoms or a divalent aromatic group having 6 to 18 carbon atoms, and Z represents a divalent carbon number 2 ~ 8 aliphatic group.

Here, the divalent aliphatic group having 2 to 18 carbon atoms in X may be saturated or unsaturated, and may be a divalent chain or a cyclic aliphatic group (for example, cycloalkane Base, etc.). Moreover, when it is a divalent chain-like aliphatic group, it may be linear or branched. The carbon number of the divalent aliphatic group is more preferably 2 to 12, and still more preferably 2 to 6. Among them, the divalent aliphatic group having 2 to 18 carbon atoms is preferably a divalent chain saturated aliphatic group, more preferably a linear alkylene group, and even more preferably a linear alkylene group. . Examples of the chain aliphatic group having 2 to 18 carbon atoms include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and heptamethylene , Octamethylene, decamethylene, dodecyl methylene, propylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene, cyclopentyl, cyclopentyl Jiji et al.

The divalent aromatic group having 6 to 18 carbon atoms in X may be a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group. As the divalent aromatic group, the carbon number is preferably from 6 to 15, more preferably from 6 to 12. The aromatic ring in the divalent aromatic hydrocarbon group is preferably a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl ring or The terphenyl ring is more preferably a benzene ring, a naphthalene ring or a biphenyl ring. The aromatic heterocyclic ring in the divalent aromatic heterocyclic group preferably contains at least one of an oxygen atom, a nitrogen atom, or a sulfur atom as an atom constituting a ring. The aromatic heterocyclic ring is preferably a furan ring, a pyrrole ring, a thiophene ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyridine Ring Ring, triazole ring, three Ring, indole ring, indazole ring, purine ring, thiazoline ring, thiadiazole ring, Oxazoline ring, Azole ring, Diazole ring, quinoline ring, isoquinoline ring, fluorene ring, Pyrimidine, quinine Phthaloline ring, quinazoline ring, Porphyrin ring, pteridine ring, acridine ring, phenanthroline ring, brown Ring, tetrazole ring, benzimidazole ring, benzo Azole ring, benzothiazole ring, benzotriazole ring and tetrazaindene ring, more preferably pyridine ring, triazole ring Ring and quinoline ring.

Z represents a divalent aliphatic group having 2 to 8 carbon atoms. The divalent aliphatic group having 2 to 8 carbon atoms may be saturated or unsaturated, and may be a divalent chain or a cyclic aliphatic group (for example, a cycloalkylene group). One. Moreover, when it is a divalent chain-like aliphatic group, it may be a divalent linear or branched. The carbon number of the divalent aliphatic group is more preferably 2 to 6, and still more preferably 2 to 4. Among them, the divalent aliphatic group having 2 to 8 carbon atoms is preferably a divalent saturated aliphatic aliphatic group, more preferably a linear alkylene group, and even more preferably a linear alkylene group. . Examples of the linear alkylene group having 5 to 10 carbon atoms include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene. Group, decamethylene, propylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene, and the like.

Examples of the divalent cycloalkylene group include cyclopentyl, cyclohexyl, and the like.

The aliphatic diol represented by the general formula (b) is more preferably at least one selected from the group consisting of ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol, and prevents crystallization of a polycondensation plasticizer. From the viewpoint of chemical conversion, at least one selected from ethylene glycol and 1,2-propylene glycol is particularly preferred.

Among the aliphatic diol residues of the polycondensation plasticizer, it is preferable to include 10 to 100 mol% of ethylene glycol residues, and it is more preferable to include 20 to 100 mol%.

The polycondensation plasticizer is preferably at least one kind of dicarboxylic acid (also referred to as aromatic dicarboxylic acid) of the above-mentioned divalent aromatic group of the X series, and a diol of the above-mentioned aliphatic group of the Z series. (Also referred to as aliphatic diol) at least one of the obtained compounds. The average carbon number of the aliphatic diol used is preferably 2.5 to 8.0. In addition, a mixture of at least one aromatic dicarboxylic acid and at least one dicarboxylic acid (also referred to as an aliphatic dicarboxylic acid) of the X-based divalent aliphatic group described above, and at least one Polycondensation plasticizer obtained from an aliphatic diol having an average carbon number of 2.5 to 8.0.

In the description of the polycondensate plasticizer, the average carbon number of the dicarboxylic acid or dicarboxylic acid residue is the total dicarboxylic acid residue in all the dicarboxylic acid or polycondensate plasticizer to be used. The total number of carbons divided by the mole number of the dicarboxylic acid used or the mole number of the dicarboxylic acid residue in the polycondensation plasticizer. For example, in the case where all of the dicarboxylic acid residues are composed of adipic acid residues and phthalic acid residues each at 50 mol%, the average carbon number of the dicarboxylic acid residues is 7.0. The average carbon number of a diol or a diol residue is calculated similarly. For example, when it consists of 50 mol% of ethylene glycol residues and 50 mol% of 1,2-propanediol residues, the average carbon number of a diol residue becomes 2.5.

The number average molecular weight (Mn) of the polycondensation plasticizer is preferably 500 to 2000, more preferably 600 to 1500, and even more preferably 700 to 1200. If the number average molecular weight of the polycondensation plasticizer is 500 or more, the volatility becomes low, and film failure or process contamination due to volatilization under high temperature conditions when the transparent support film is stretched is suppressed.

Moreover, when it is 2000 or less, compatibility with a transparent support will become high, and the outflow at the time of film formation and the heat-stretching is suppressed.

The number average molecular weight of the polycondensation plasticizer can be measured and evaluated by gel permeation chromatography. In addition, in the case of a polyester polyol having no closed end, it can also be calculated from the amount of hydroxyl groups per unit mass (hereinafter, also referred to as a hydroxyl value). In the present invention, the hydroxyl value can be obtained by measuring the amount (mg) of potassium hydroxide required to neutralize excess acetic acid after the polyester polyol is acetylated.

When a mixture of an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid is used as the dicarboxylic acid component, the average carbon number of the dicarboxylic acid component is preferably 5.5 to 10.0, and more preferably 5.6 to 8.

By setting the average carbon number to 5.5 or more, a polarizing plate having more excellent durability can be obtained. In addition, by setting the average carbon number to 10.0 or less, the compatibility with the transparent support is more excellent, and the outflow is suppressed during the film formation process.

The polycondensate obtained by using an aromatic dicarboxylic acid contains an aromatic dicarboxylic acid residue.

Among the dicarboxylic acid residues of the polycondensation plasticizer, the ratio of the aromatic dicarboxylic acid residues is preferably 40 mol% or more, more preferably 40 mol% to 100 mol%.

By setting the ratio of the aromatic dicarboxylic acid residues in the dicarboxylic acid residues to 40 mol% to 100 mol%, when the material forming the transparent support is a cellulose polymer, it is compatible with fibers The elementary polymer has excellent compatibility and suppresses outflow even during film formation and heat stretching.

The dicarboxylic acid residue is a partial structure of a polycondensate, for example, a dicarboxylic acid residue-C (= O) -XC (= O) formed from a dicarboxylic acid HOC (= O) -X-CO ₂ H -.

Aromatic dicarboxylic acids that can be used to synthesize polycondensate plasticizers are preferably from phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, At least one selected from 1,8-naphthalenedicarboxylic acid, 2,8-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. Among them, at least one selected from phthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid is more preferable, and at least one selected from phthalic acid and terephthalic acid is even more preferable.

The polycondensate obtained using an aliphatic dicarboxylic acid contains an aliphatic dicarboxylic acid residue.

The aliphatic dicarboxylic acid used for the synthesis of the polycondensation polyester plasticizer is preferably selected from oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, and adipic acid. At least one selected from pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and 1,4-cyclohexanedicarboxylic acid.

The average carbon number of the aliphatic dicarboxylic acid residue is preferably 5.5 to 10.0, more preferably 5.5 to 8.0, and even more preferably 5.5 to 7.0. If the average number of carbon atoms of the aliphatic dicarboxylic acid residue is 10.0 or less, the heating loss of the compound can be reduced, and it is possible to prevent the occurrence of planar failures that are believed to be caused by the step contamination caused by the outflow during drying of the web. Moreover, if the average carbon number of an aliphatic dicarboxylic acid residue is 5.5 or more, it is excellent in compatibility, and precipitation of a polycondensation plasticizer is hard to occur, and it is preferable.

It is preferable that the aliphatic dicarboxylic acid residue in a polycondensation plasticizer contains a succinic acid residue specifically ,. When the polycondensate plasticizer contains two or more types of aliphatic dicarboxylic acid residues, the aliphatic dicarboxylic acid residue preferably contains a succinic acid residue and an adipic acid residue.

Polyester plasticizers contain diol residues.

Formed by a diol compound (HO-Z-OH) represented by the general formula (b) The diol residue is -O-Z-O-.

The polycondensation plasticizer preferably contains an aliphatic diol residue having an average carbon number of 2.0 to 7.0, and more preferably contains an aliphatic diol residue having an average carbon number of 2.0 to 4.0.

When the average carbon number of the aliphatic diol residue is 7.0 or less and the material is a cellulose-based polymer that forms a transparent support, the compatibility with the cellulose-based polymer is improved, and it becomes difficult to generate efflux. In addition, it becomes difficult to increase the heating loss of the compound, which suppresses occurrence of a planar failure that is thought to be due to step contamination when the film is dried. In addition, if the average carbon number of the aliphatic diol residue is 2.0 or more, the synthesis is easy. The aliphatic diol residue in the polycondensation plasticizer preferably contains ethylene glycol, propylene glycol, and cyclohexanedimethanol.

The end of the polycondensation plasticizer can be made unblocked and still be a diol or carboxylic acid (that is, the end of the polymer chain length is -OH or -CO ₂ H), or a monocarboxylic acid can be further added to the -OH end. The reaction or reaction of a monohydric alcohol to the -CO ₂ H terminal, that is, terminal blocking is performed. In addition, by closing the ends of the polycondensation plasticizer, it is difficult for the state at room temperature to become a solid shape, and handling is improved. In addition, the visibility of the display device can be improved even when the thickness of the transparent support is reduced.

The monocarboxylic acid used for blocking is preferably at least one selected from acetic acid, propionic acid, butyric acid, and benzoic acid. As the monohydric alcohol used for blocking, at least one selected from methanol, ethanol, propanol, isopropanol, butanol, and isobutanol is preferable, and methanol is most preferable. If the carbon number of the monocarboxylic acid used at the terminal of the polycondensation is 7 or less, the heating loss of the compound will be small. It is excellent to suppress the occurrence of planar faults.

Specific examples J-1 to J-44 of the polycondensation plasticizer are given in Table 1 below. However, the present invention is not limited to this.

Here, in the abbreviations in Table 1 above, PA stands for benzenediene. Formic acid and TPA represent terephthalic acid, AA represents adipic acid, SA represents succinic acid, and 2,6-NPA represents 2,6-naphthalenedicarboxylic acid.

The polycondensation plasticizer can be synthesized by a conventional method using a thermal melting condensation method based on a polyesterification reaction or a transesterification reaction of a diol and a dicarboxylic acid, or an interface condensation of chlorinated acids of these acids and glycols Either method can be easily synthesized. In addition, polycondensates are described in detail in "Theories and Applications of Plasticizers" edited by Takayuki Murai (fortunately, Shusho Co., Ltd., first edition, March 1, Showa 48). These compounds can also be used.

In the present invention, as a polycondensation plasticizer, Japanese Patent Application Laid-Open No. 05-155809, Japanese Patent Application Laid-Open No. 05-155810, Japanese Patent Application Laid-Open No. 5-197073, Japanese Patent Application Laid-Open No. 2006-259494, and Japanese Patent Application Laid-Open No. Compounds described in various publications of 07-330670, Japanese Patent Application Laid-Open No. 2006-342227, and Japanese Patent Application Laid-Open No. 2007-003679.

(Carb derivative plasticizer)

The transparent support is also preferably in the form of using a film further containing a carbohydrate derivative plasticizer. By including a carbohydrate derivative plasticizer, the visibility of the display device can be improved even when the thickness of the transparent support is reduced.

As a carbohydrate derivative plasticizer, a monosaccharide or a carbohydrate containing 2 to 10 monosaccharide units is preferred.

Monosaccharides or polysaccharides that preferably constitute carbohydrate derivative plasticizers, and some or all of the substitutable groups (for example, hydroxyl, carboxyl, amine, and mercapto) in the molecule are substituted with substituents. Examples of the substituent that the carbohydrate derivative plasticizer may have include an alkyl group, Aryl, fluorenyl, etc. will be described in detail later. In addition, an ether structure in which a hydroxyl group is substituted with an alkyl group or an aryl group, an ester structure in which a hydroxyl group is substituted with a fluorenyl group, a fluorenamine structure or a fluorinimine structure formed by an amine group substitution, and the like.

Monosaccharides or carbohydrates containing 2 to 10 monosaccharide units are preferably erythritol, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, fructose, mannose , Gulose, idose, galactose, tyrolose, trehalose, isotrehalose, neotrehalose, trehalosamine, trehalose, nigerose, maltose, maltitol, Isomalt, sophorose, kelp disaccharide, cellobiose, gentiobiose, lactose, lactosamine, lactitol, lactulose, melibiose, primrose, rutose, squill diose, sucrose, sucrose Vegetarian, sucrose, vicianose, cellotriose, chacotriose, gentiotriose, isomaltose, isoglucose, isomaltose, Mannose, melezitose, pannoose, planteose, raffinose, solatriose, umbrella sugar, lycoristetraose, maltotetraose, stachyose, malt Pentasaccharide, verbascum, maltohexaose, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, xylitol, and mountain Sugar alcohol.

More preferred are ribose, arabinose, xylose, lyxose, glucose, fructose, mannose, galactose, trehalose, maltose, cellobiose, lactose, sucrose, sucralose, α-cyclodextrin, β-ring Dextrin, γ-cyclodextrin, δ-cyclodextrin, xylitol, sorbitol, more preferably arabinose, xylose, glucose, fructose, mannose, galactose, maltose, cellobiose, sucrose , Β-cyclodextrin, and γ-cyclodextrin, particularly preferred are xylose, glucose, fructose, mannose, galactose, maltose, and fiber double Sugar, sucrose, xylitol, and sorbitol.

In addition, the substituent of the carbohydrate derivative plasticizer is preferably an alkyl group (preferably 1 to 22 carbons, more preferably 1 to 12 carbons, and particularly preferably 1 to 8 carbons, for example Methyl, ethyl, propyl, hydroxyethyl, hydroxypropyl, 2-cyanoethyl, benzyl, etc.), aryl (preferably 6 to 24 carbons, more preferably 6 to 18 carbons) Particularly preferred are aryl groups having 6 to 12 carbon atoms, such as phenyl, naphthyl, and fluorenyl (including alkylcarbonyl, arylcarbonyl, and heterocyclic carbonyl groups, preferably 1 to 22 carbon atoms, and more preferably carbon atoms) Numbers 2 to 12, especially preferred are fluorenyl groups having 2 to 8 carbon atoms, such as ethenyl, propionyl, butylfluorenyl, pentamyl, hexyl, octyl, benzyl, tolylmethyl, o-phenyl Dimethylfluorenyl, naphthylmethyl, etc.). In addition, as a preferable structure formed by substitution of an amine group, a fluorene amine structure (preferably having 1 to 22 carbon atoms, more preferably having 2 to 12 carbon atoms, and particularly preferably having 2 to 8 carbon atoms) Fluorene, such as formamide, acetamide, etc., or fluorene imine structure (preferably 4 to 22 carbons, more preferably 4 to 12 carbons, and particularly preferably 4 to 8 carbons) , Such as succinimide, phthalimide, etc.).

The carbohydrate derivative plasticizer preferably has at least one selected from an alkyl group, an aryl group, and a fluorenyl group, and more preferably a fluorenyl group.

Preferred examples of the carbohydrate derivative plasticizer include the following. However, the present invention is not limited to these examples.

From xylose tetraacetate, glucose pentaacetate, fructose pentaacetate, mannose pentaacetate, galactose pentaacetate, maltose octaacetate, cellobiose octaacetate, sucrose octa Acetate, xylitol pentaacetate, sorbitol hexaacetate, xylose tetrapropionate, glucose pentapropionate, fructose pentapropionate, mannose pentapropionate, galactose pentapropionate Acid ester, Maltose octapropionate, cellobiose octapropionate, sucrose octapropionate, xylitol pentapropionate, sorbitol hexapropionate, xylose tetrabutyrate, glucose pentabutyrate, fructose Pentabutyrate, mannose pentabutyrate, galactose pentabutyrate, maltose octanoate, cellobiose octanoate, sucrose octanoate, xylitol pentabutyrate, sorbitol hexabutyrate Ester, xylose tetrabenzoate, glucose pentabenzoate, fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose At least one selected from the group consisting of octabenzoate, sucrose octabenzoate, xylitol pentabenzoate, and sorbitol hexabenzoate.

More preferably from xylose tetraacetate, glucose pentaacetate, fructose pentaacetate, mannose pentaacetate, galactose pentaacetate, maltose octaacetate, cellobiose octaacetate , Sucrose octaacetate, xylitol pentaacetate, sorbitol hexaacetate, xylose tetrapropionate, glucose pentapropionate, fructose pentapropionate, mannose pentapropionate, half Lactose pentapropionate, maltose octapropionate, cellobiose octapropionate, sucrose octapropionate, xylitol pentapropionate, sorbitol hexapropionate, xylose tetrabenzoate, Glucose pentabenzoate, fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose octabenzoate, sucrose octabenzoate At least one selected from the group consisting of an acid ester, xylitol pentabenzoate, and sorbitol hexabenzoate.

Even more preferred are maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylose tetrapropionate, glucose pentapropionate, fructose pentapropionate, and mannose pentapropionate. , Galactose pentapropionate, maltose octapropionate, cellobiose octapropionate, sucrose octapropionate, Xylose tetrabenzoate, glucose pentabenzoate, fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose octabenzene At least one selected from formate, sucrose octabenzoate, xylitol pentabenzoate, and sorbitol hexabenzoate.

The carbohydrate derivative plasticizer preferably has a pyranose structure or a furanose structure.

As the carbohydrate derivative plasticizer, particularly preferred are the compounds shown below. However, the carbohydrate derivative plasticizer that can be used in the present invention is not limited to this.

In the following structural formulae, R each independently represents an arbitrary substituent, and a plurality of Rs may be the same or different.

In the following Tables 2 to 5, for example, Table 2 shows a group in which 8 hydroxyl groups (R are each a hydrogen atom) are amidated with two types of amination agents, and one of R introduced by the two types of amination agents is shown. Is "substituent 1", the other R is represented as "substituent 2", and the degree of substitution represents the number of all 8 hydroxyl groups.

The total number of R is 5 in Table 3 and 8 in Tables 4 and 5. Here, "phenethylfluorenyl" means -C (= O) -CH ₂ -C ₆ H ₅ .

As a commercial product, carbohydrate derivative plasticizers can be obtained, for example, manufactured by Tokyo Chemical Industry Co., Ltd. or Aldrich, and can be esterified by a commercially available carbohydrate (for example, Japanese Patent Application Laid-Open No. 8-245678). Method described in Japanese Patent Publication (Kokai).

The content of the plasticizer in the transparent support is preferably 1 to 20 parts by mass relative to 100 parts by mass of the material forming the transparent support. The improvement effect of the present invention can be easily obtained by setting the content of the plasticizer to 1 part by mass or more with respect to 100 parts by mass of the material forming the transparent support. In addition, bleed out is suppressed by setting the content to 20 parts by mass or less. The generation. The content of the plasticizer in the transparent support is more preferably 2 to 15 parts by mass, and particularly preferably 5 to 15 parts by mass with respect to 100 parts by mass of the material forming the transparent support.

These plasticizers may be added in two or more kinds. When two or more kinds are added, the specific examples and preferable ranges of the added amounts are the same as those described above.

(Anti-deterioration agent)

As the transparent support, it is also preferable to use a film containing an anti-deterioration agent (for example, an antioxidant, a peroxide decomposition agent, a radical inhibitor, a metal deactivator, an acid scavenger, and an amine). In addition, the ultraviolet absorber is also one kind of anti-deterioration agent. These anti-deteriorating agents are listed in Japanese Patent Application Laid-Open No. 60-235852, Japanese Patent Application Laid-Open No. 3-199201, same as 5-1907073, same as 5-194789, same as 5-271471, same as 6-107854, and 6- Nos. 118233, 6-148430, 7-11056, 7-11055, 7-11056, 8-29619, 8-239509, and JP 2000-204173 Documented.

In addition, commercially available stabilizers described in "Polymer Additive Handbook" (published by CMC) on pages 21 to 69 can be preferably used.

(Antioxidants)

As a transparent support, the aspect using the film containing an antioxidant is also preferable. By containing an antioxidant, the compound represented by the general formula I effectively functions, and a better improvement effect can be obtained.

Examples of the antioxidant include 2,6-di-tertiary-butyl-4-methylphenol and 4,4'-thiobis- (6-tertiary-butyl-3-methylphenol). , 1,1'-bis (4-hydroxyphenyl) cyclohexane, 2,2'-methylenebis (4-ethyl-6-tertiarybutylphenol), 2,5-di-tertiary Phenol-based and hydroquinone-based antioxidants such as butyl hydroquinone, neopentaerythritol-methyl [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] .

It is also preferable to use ginseng (4-methoxy-3,5-diphenyl) phosphite, ginseng (nonylphenyl) phosphite, ginseng (2,4-di-tert-butylphenyl) ) Phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) neopentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) new Phosphate-based antioxidants such as pentaerythritol diphosphite, and hydroxylamine-based antioxidants such as N, N-di-octadecylhydroxyamine and N, N-dibenzylhydroxyamine. Regarding the hydroxylamine-based compound, the compounds described in paragraphs 0005 to 0020 and paragraphs 0022 to 0026 in Japanese Patent Application Laid-Open No. 8-62767 can be preferably used.

Moreover, it is also preferable that the reducing ketone represented by the following general formula (A) or the general formula (B) mentioned later is an antioxidant used for a transparent support.

In the general formula (A), R ^A1 and R ^A2 each independently represent a hydroxyl group, an amine group, a fluorenylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, and a mercapto group. Or alkylthio. Y is composed of a carbon atom, an oxygen atom, and / or a nitrogen atom, and represents a non-metal atom group of 5 to 6 members, which together with -C (= O) -C (R ^A1 ) = C (R ^A2 )-.

R ^A1 and R ^{A2 are} preferably a hydroxyl group, an amine group, an alkylsulfonylamino group, or an arylsulfonylamino group, more preferably a hydroxyl group or an amine group, and even more preferably a hydroxyl group.

Y preferably has at least one -O- bond, and -C (R ^A3 ) (R ^A4 )-, -C (R ^A5 ) =, -C (= O)-, -N (Ra)-, and- It is constituted by one or two or more types of N =. Here, R ^A3 to R ^A5 and Ra are each independently a hydrogen atom, an alkyl group having a substituent having 1 to 10 carbon atoms, an aryl group having a substituent having 6 to 15 carbon atoms, a hydroxyl group, or a carboxyl group. .

The 5- to 6-membered ring formed through Y includes, for example, a cyclopentenone ring (2-cyclopenten-1-one ring; the formed compound becomes a reducing acid), a furanone ring [2 ( 5H) -furanone ring], dihydropyrone ring [3,4-dihydro-2H-pyran-4-one ring (2,3-dihydro-4H-pyranone ring), 3,6 -Dihydro-2H-pyran-2-one ring, 3,6-dihydro-2H-pyran-6-one ring (5,6-dihydro-2-pyranone ring)], 3,4 -A dihydro-2H-pyranone ring, preferably a cyclopentenone ring, a furanone ring, a dihydropyrone ring, more preferably a furanone ring, a dihydropyranone ring, and particularly preferably a furanone ring.

These rings may be condensed, and the ring to be condensed may be either a saturated ring or an unsaturated ring.

Among the reduced ketones represented by the general formula (A), compounds represented by the following general formula (A1) are preferred, and among these, compounds represented by the following general formula (A2) are preferred.

In the general formula (A1), R ^a1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and these may have a substituent.

R ^{a1 is} preferably an alkyl group which may have a substituent, and more preferably -CH (OR ^a3 ) CH ₂ OR ^a2 . In this case, R ^a1 is a compound represented by the general formula (A2).

In the general formula (A2), R ^a2 and R ^a3 each independently represent a hydrogen atom, an alkyl group, a fluorenyl group, or an alkoxycarbonyl group, and R ^a2 and R ^a3 may be bonded to each other to form a ring. The formed ring is preferably a ring. It is a 1,3-dioxolane ring, and the ring may further have a substituent. The compound having a dioxolane ring can be synthesized by acetalization or ketalization based on the reaction of ascorbic acid with ketones or aldehydes, and the ketones or aldehydes of the raw materials can be used without particular limitation.

One of the particularly preferred combinations of substituents is a compound in which R ^a2 is a fluorenyl group and R ^a3 is a hydrogen atom. The fluorenyl group may be any of an aliphatic fluorenyl group and an aromatic fluorenyl group. In this case, it is preferably 2 to 30 carbon atoms, more preferably 4 to 24 carbon atoms, and even more preferably 8 to 18 carbon atoms. In the case of an aromatic fluorenyl group, it is preferably 7 to 24 carbon atoms, more preferably 7 to 22 carbon atoms, and even more preferably 7 to 18 carbon atoms. Specific examples of preferred fluorenyl groups include butylfluorenyl, hexamethylene, 2-ethylhexanyl, decyl, lauryl, myristyl, palmityl, stearyl, Palmene fluorenyl, myristyl fluorenyl, oleyl fluorenyl, benzamyl, 4-methylbenzyl and 2-methylbenzyl.

As the antioxidant used for the transparent support, a compound represented by the following general formula (B) is also preferred together with a compound represented by the general formula (A).

In the general formula (B), R ^B1 and R ^B2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a fluorenyl group, a carboxyl group, an amino group, an alkoxy group, an alkoxycarbonyl group, or a heterocyclic group. The cyclic group, R ^B3 and R ^B4 each independently represent a hydroxyl group, an amine group, a fluorenylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, or a mercapto group.

The alkyl group in R ^B1 and R ^B2 is preferably 1 to 10 carbon atoms, and more preferably methyl, ethyl, or tertiary butyl.

The alkyl group in R ^B1 and R ^B2 is preferably 1 to 10 carbon atoms.

The alkenyl group in R ^B1 and R ^B2 is preferably 2 to 10 carbon atoms, preferably vinyl group and allyl group, and particularly preferably vinyl group.

The cycloalkyl group in R ^B1 and R ^B2 is preferably 3 to 10 carbon atoms, and more preferably cyclopropyl, cyclopentyl, and cyclohexyl.

These alkyl groups, alkenyl groups, and cycloalkyl groups may have a substituent. The substituent is preferably at least one selected from a hydroxyl group, a carboxyl group, and a sulfo group.

In the case where the alkenyl group is a vinyl group, a carboxyl group is also preferably substituted. Vinyl.

The aryl group in R ^B1 and R ^B2 is preferably 6 to 12 carbon atoms. The aryl group may have a substituent, and the substituent is preferably at least one selected from an alkyl group, a hydroxyl group, a carboxyl group, a sulfo group, a halogen atom, a nitro group, and a cyano group.

The fluorenyl group in R ^B1 and R ^B2 is preferably a methyl fluorenyl group, an ethyl fluorenyl group, an isobutyl fluorenyl group, and a benzyl fluorenyl group.

The amine group in R ^B1 and R ^B2 includes an amine group, an alkylamine group, and an arylamine group, and is preferably an amine group, a methylamine group, a dimethylamino group, an ethylamine group, a diethylamine group, and a dipropylamine group. , Aniline, N-methyl-N-aniline.

The alkoxy group in R ^B1 and R ^B2 is preferably 1 to 10 carbon atoms, and more preferably a methoxy group or an ethoxy group.

The alkoxycarbonyl group in R ^B1 and R ^B2 is preferably a methoxycarbonyl group.

As the heterocyclic group in R ^B1 and R ^B2 , the hetero atoms constituting the ring are preferably an oxygen atom, a sulfur atom, and a nitrogen atom, and the ring structure is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be an aromatic heterocyclic group or a saturated heterocyclic group, and may be ring-condensed.

The heterocyclic ring in the heterocyclic group is preferably a pyridine ring, a pyrimidine ring, a pyrrole ring, a furan ring group, a thiophene ring, a pyrazole ring, a pyridine ring, or a pyrene ring. Ring and morpholine ring.

R ^B1 and R ^{B2 are more} preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.

The amine group in R ^B3 and R ^B4 includes an amine group, an alkylamine group, and an arylamine group, preferably an amine group or an alkyl group such as methylamino group, ethylamino group, n-butylamino group, and hydroxyethylamino group Amine.

The fluorenylamino group in R ^B3 and R ^B4 is preferably an ethenylamino group or a benzamidineamino group.

The alkylsulfonylamino group in R ^B3 and R ^B4 is preferably a methylsulfonylamino group.

The arylsulfonylamino group in R ^B3 and R ^B4 is preferably a benzenesulfonylamino group or a p-toluenesulfonylamino group.

The alkoxycarbonylamino group in R ^B3 and R ^B4 is preferably a methoxycarbonylamino group.

R ^B3 and R ^{B4 are more} preferably a hydroxyl group, an amine group, an alkylsulfonylamino group, and an arylsulfonylamino group.

The antioxidant used in the present invention is more preferably a reduced ketone, and specific examples thereof include compounds exemplified in Japanese Patent Application Laid-Open No. 6-27599, paragraphs 0014 to 0034, and Japanese Patent Laid-Open No. 6-110163 Compounds exemplified in paragraph numbers 0012 to 0020, and compounds exemplified in paragraph numbers 0022 to 0031 of Japanese Patent Application Laid-Open No. 8-114899.

Among these, L-ascorbic acid myristate, palmitate, and stearate are particularly preferred.

The timing of adding the antioxidant to the transparent support film is not particularly limited as long as it is added at the time when the film formation is performed. For example, it may be added at the stage of mixing the transparent support and the solvent, or may be added after the mixed solution is prepared using the transparent support and the solvent.

The content of the antioxidant in the transparent support film is preferably 0.0001 to 5.0 parts by mass relative to 100 parts by mass of the transparent support. By setting the content of the antioxidant within this range, it is possible to obtain a sufficient antioxidant effect and durability of the polarizing plate. Even more preferably, the content of the antioxidant in the transparent support film is 0.001 to 1.0 parts by mass relative to 100 parts by mass of the transparent support. , And more preferably 0.01 to 0.5 parts by mass.

(Free radical trapping agent)

As the transparent support, a film containing a radical scavenger is also preferably used. By containing a radical scavenger, decomposition of the compound represented by the general formula I can be suppressed, and better polarizer durability can be obtained.

As the radical scavenger, a compound (HALS) represented by the following general formula (H) is preferred.

In the general formula (H), R ^H1 and R ^H2 each independently represent a hydrogen atom or a substituent, and R ^H01 to R ^H04 each independently represent an alkyl group.

The substituent in R ^H1 is not particularly limited. However, an alkyl group or a substituent bonded to a pyridine ring with a nitrogen atom or an oxygen atom is preferred. The substituent bonded to the pyridine ring with a nitrogen atom or an oxygen atom is preferably an amine group, a fluorenylamino group, a hydroxyl group, an alkoxy group, an aryloxy group, or a fluorenyl group. These groups may have a substituent.

The substituent in R ^H1 is preferably an alkyl group, an aryl group or an amine group having a heterocyclic group, and more preferably a hydroxy group, an alkoxy group or a fluorenyl group.

The substituent in R ^H2 is not particularly limited, but is preferably an alkyl group (preferably 1 to 20 carbons, more preferably 1 to 12 and even more preferably 1 to 8, among which methyl, ethyl, Isopropyl, tertiary butyl, n-octyl, 2-ethylhexyl, n-decyl, n-hexadecyl), alkenyl (preferably carbon number 2-20, more preferably 2-12, and even more It is preferably 2 to 8, still more preferably vinyl, allyl, 2-butenyl, or 3-pentenyl), alkynyl (preferably 2 to 20 carbons, more preferably 2 to 12, and More preferably 2 to 8, still more preferably propargyl or 3-pentynyl), cycloalkyl (preferably 3 to 20 carbons, more preferably 3 to 12, and even more preferably 3 to 8 , Cyclopropyl, cyclopentyl or cyclohexyl), aryl (preferably 6-30 carbons, more preferably 6-20, even more preferably 6-12, even more preferably phenyl, biphenyl Or naphthyl), amine (including amine, alkylamino, and arylamino), preferably 0-20, more preferably 0-10, even more preferably 0-6, even more preferably Amine, methylamino, dimethylamino, diethylamino, aniline, N-methyl-N-aniline or dibenzylamino), alkoxy (preferably carbon number 1-20, more It is preferably 1-12, even more preferably 1-8, and even more preferably methoxy and ethyl. Group, butoxy), cycloalkoxy (cycloalkyl ring in cycloalkoxy group is preferably a 3 to 8 member ring, preferably 3 to 20 carbon atoms, and cycloalkoxy group is preferably cyclopropoxy Group, cyclopentyloxy, cyclohexyloxy), fluorenyl (including alkylcarbonyl, arylcarbonyl, preferably 2 to 20 carbons, more preferably 2 to 16, even more preferably 2 to 8, and More preferred are ethenyl, propionyl, 2-ethylhexyl, or benzyl), a hydroxyl group, and an oxygen radical (-O ").

R ^H01 to R ^{H04 are} preferably an alkyl group having 1 to 6 carbon atoms, more preferably ethyl or methyl, and even more preferably all of R ^H01 to R ^H04 are methyl.

The compound represented by the general formula (H) is preferably at least one selected from the group consisting of 4-hydroxy-2,2,6,6-tetramethylpyridine and 1-allyl-4-hydroxyl. -2,2,6,6-tetramethylpyridine, 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpyridine, 1- (4-tert-butyl-2-butene ) -4-hydroxy -2,2,6,6-tetramethylpyridine, 4-stearylpyridyloxy-2,2,6,6-tetramethylpyridine, 1-ethyl-4-salicyloxy-2, 2,6,6-tetramethylpyridine, 4-methacrylmethyloxy-1,2,2,6,6-pentamethylpyridine, 1,2,2,6,6-pentamethylpyridyl 4-yl-β (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, 1-benzyl-2,2,6,6-tetramethylpyridin-4-yl Maleate, bis (2,2,6,6-tetramethylpyridin-4-yl) adipate, bis (2,2,6,6-tetramethylpyridin-4-yl) Sebacate, bis (1,2,3,6-tetramethyl-2,6-diethyl-pyridin-4-yl) sebacate, bis (1-allyl-2,2, 6,6-tetramethyl-pyridine-4-yl) phthalate, 1-ethylfluorenyl-4-ethylfluorenyloxy-2,2,6,6-tetramethylpyridine, trimellitic acid -Ginseng (2,2,6,6-tetramethylpyridin-4-yl) ester, 1-propenyl-4-benzyloxy-2,2,6,6-tetramethylpyridine, dibutyl Malonic acid-bis (1,2,2,6,6-pentamethyl-pyridin-4-yl) ester, dibenzylmalonic acid-bis (1,2,3,6-tetramethyl-2) , 6-diethyl-pyridin-4-yl) ester, dimethyl-bis (2,2,6,6-tetramethylpyridin-4-yloxy) -silane, ginseng (1-propyl- 2,2,6,6-tetramethylpyridyl-4-yl) -phosphite, ginseng (1-propyl-2,2,6,6-tetramethylpyridine) -4-yl) -phosphate, N, N'-bis (2,2,6,6-tetramethylpyridin-4-yl) -hexamethylene-1,6-diamine, (2, 2,6,6-tetramethylpyridin-4-yl) -1,2,3,4-butanetetracarboxylic acid ester, (1,2,2,6,6-pentamethylpyridine-4- ) -1,2,3,4-butanetetracarboxylic acid ester, N, N'-bis- (2,2,6,6-tetramethylpyridin-4-yl) -hexamethylene-1 , 6-diethylamidine, 1-ethylamido-4- (N-cyclohexylacetamido) -2,2,6,6-tetramethyl-pyridine, 4-benzylamino-2,2, 6,6-tetramethylpyridine, N, N'-bis- (2,2,6,6-tetramethylpyridin-4-yl) -N, N'-dibutyl-hexanediamine, N , N'-bis (2,2,6,6-tetramethylpyridin-4-yl) -N, N'-dicyclohexyl- (2-hydroxy) propylenediamine, N, N'-bis -(2,2,6,6-tetramethylpyridin-4-yl) -p-xylylene -Diamine, 4-bis (2-hydroxyethyl) amino-1,2,2,6,6-pentamethylpyridine, 4-methacrylamido-1,2,2,6,6- Pentamethylpyridine and α-cyano-β-methyl-β- [N- (2,2,6,6-tetramethylpyridin-4-yl)]-amino-methyl acrylate.

In addition, N, N ', N ", N'''-肆-[4,6-bis- [butyl- (N-methyl-2,2,6,6-tetramethylpyridine- 4-yl) amino] -tri -2-yl] -4,7-diazadecane-1,10-diamine, dibutylamine and 1,3,5-tri ˙N, N'-bis (2,2,6,6-tetramethyl-4-pyridyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl Condensate of phenyl-4-pyridyl) butylamine (CHIMASSORB 2020FDL manufactured by BASF), dibutylamine, and 1,3,5-tris Polycondensates with N, N'-bis (2,2,6,6-tetramethyl-4-pyridyl) butylamine, poly [((1,1,3,3-tetramethylbutyl) amine Base-1,3,5-tri -2,4-diyl} {(2,2,6,6-tetramethyl-4-pyridyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4 -Pyridyl) imino}) (CHIMASSORB 944FDL manufactured by BASF), 1,6-hexanediamine-N, N'-bis (2,2,6,6-tetramethyl-4-pyridyl) And morpholine-2,4,6-trichloro-1,3,5-tri Polycondensate, poly [(6-morpholinyl-s-tri -2,4-diyl) [(2,2,6,6-tetramethyl-4-pyridyl) imino] -hexamethylene [(2,2,6,6-tetramethyl- 4-pyridyl) imino]] A high molecular weight HALS having a plurality of pyridine rings bonded to a backbone; in addition, a polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-pyridine ethanol can be suitably used. , 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-pyridinol and 3,9-bis (2-hydroxy-1,1-dimethyl Ethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane is a high molecular weight HALS having a pyridine ring bonded to it through an ester bond. However, the present invention is not limited to this.

Among them, from dibutylamine and 1,3,5-tri Polycondensates with N, N'-bis (2,2,6,6-tetramethyl-4-pyridyl) butylamine, poly [((1,1,3,3-tetramethylbutyl) amine Base-1,3,5-tri -2,4-diyl} {(2,2,6,6-tetramethyl-4-pyridyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4 -Pyridyl) imino} and polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-pyridineethanol are selected, and the number average molecular weight is preferably 2000 ~ 5000.

As the radical scavenger, a compound represented by the following structure (Hα) (trade name, Sunlizer HA-622, manufactured by SORT Corporation) and a compound represented by the following structure (Hβ) are also suitable.

Moreover, m in the said structure (H (alpha)) is 2-30.

The compound of the above structure (Hα) or (Hβ) can be marketed under the trade name CHIMASSORB 2020FDL (CAS-No. 192268-64-7), CHIMASSORB 944FDL (CAS-No. .71878-19-8) and TINUVIN 770DF (CAS-No. 52829-07-9), trade name Cyasorb UV-3346 (CAS-No. 82541-48-7) manufactured by Sun Chemical Co., Ltd., same as Cyasorb UV- 3529 (CAS-No. 193098-40-7).

In addition, the compound represented by the following general formula (H1) can be particularly suitably used as a transparent support of the present invention because of its low basicity and low side effects on polarizing performance.

In the general formula (H1), Z ^H1 represents an alkyl group, a cycloalkyl group, or an aryl group, and Y ^H1 represents a hydrogen atom or a substituent. R ^H01 ~ R ^H04 meaning as the general formula (H) is the same as R ^H01 ~ R ^H04, a preferred embodiment thereof is also the same.

Z ^{H1 is} preferably an alkyl group or a cycloalkyl group which may have a substituent, more preferably an unsubstituted alkyl group having a branched structure, an alkyl group or a cycloalkyl group having an aryl group as a substituent, and even more preferably a ring. alkyl. Moreover, the substituent which Z ^H1 has is not specifically limited.

The carbon number of the alkyl group in Z ^H1 is preferably 1 to 20, and more preferably 1 to 14. The carbon number of the cycloalkyl group in Z ^H1 is preferably 3 to 20, and more preferably 3 to 14. The carbon number of the aryl group in Z ^H1 is preferably 6 to 20, and more preferably 6 to 14.

Y ^{H1 is} preferably a substituent. The substituent in Y ^H1 is not particularly limited. However, a substituent in which a nitrogen atom or an oxygen atom is bonded to a pyridine ring is preferred, and an amino group, a hydroxyl group, and an alkoxy group (carbon number is preferably 1 to 20, more preferably) which may have a substituent. Preferably 1 to 14), aryloxy (carbon number is preferably 6 to 20, more preferably 6 to 12), or oxo (carbon number is preferably 2 to 20, more preferably 2 to 14), Even more preferred is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms or an amine group having a heterocyclic group as a substituent, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or 2 to 10 carbon atoms. 10 methoxy groups.

The compound represented by the general formula (H1) is particularly characterized in that the nitrogen (N) system of the pyridine ring is fluorene-bonded to an alkyl group or an aryl group which may have a substituent represented by Z ^H1 . In this specification, a compound having a pyridine skeleton represented by the general formula (H1) including the structure of "NOZ ^H1 " is referred to as "NOZ ^H1 type".

In addition, a compound in which only hydrogen is directly bonded to the nitrogen (N) of the pyridine ring is referred to as "NH type", and a compound in which only a methyl group is directly bonded to the nitrogen (N) is referred to as "NCH ₃ type". NH and NCH ₃ are more alkaline than NOZ ^H1 . By forming a transparent support using a weakly basic NOZ ^H1 type compound, it is possible to more effectively suppress the deterioration of the performance of the polarizer when it is used in a polarizer for a long time under high temperature and high humidity.

The NOZ ^H1 type compound represented by the general formula (H1) is not limited as long as it has a predetermined pyridine skeleton. However, a compound represented by the following general formula (H1-1) or (H1-2) is preferred.

Formula (H1-1), (H1-2) of, R ^H01 ~ R ^H04 meaning as the general formula (H) in the same R ^H01 ~ R ^H04, preferred ranges are also the same. Z ^H2 represents an alkyl group or an aryl group which may have a substituent. R ^H11 and R ^H12 each independently represent an alkyl group, an aryl group, a fluorenyl group, or a heterocyclic group. R ^H13 represents a hydrogen atom, an alkyl group, a fluorenyl group, or an aryl group.

The preferable range of Z ^{H2 is} the same as Z ^{H1 of the} general formula (H1).

R ^{H11 is more} preferably a hydrogen atom or an alkyl group, still more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a propyl group or a butyl group.

R ^{H12 is more} preferably an alkyl group or a heterocyclic group, particularly preferably an alkyl group having 1 to 6 carbon atoms or a heterocyclic group containing a nitrogen atom having 1 to 2 ring members, particularly preferably three .

R ^{H13 is} preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a fluorenyl group having 1 to 12 carbon atoms, and particularly preferably a fluorenyl group having 1 to 12 carbon atoms.

Each of the aforementioned groups in R ^H11 to R ^H13 may be substituted with a substituent. Such a substituent may have, for example, a substituent in which Y ^H1 is removed from the general formula (H1).

The compound represented by the general formula (H1-1) or (H1-2) is preferably a compound represented by any one of the following general formulae (H1-a) to (H1-c).

In the general formulae (H1-a) to (H1-c), R ^H11 and R ^H12 , R ^H13 , Z ^H1 and Z ^H2 are respectively the same as the above-mentioned R ^H11 and R ^H12 , R ^H13 , Z ^H1 and Z ^H2 , The best range is the same. R ^H01 ~ R ^H04 meaning as the general formula (H) in the same R ^H01 ~ R ^H04, preferred ranges are also the same.

In the general formula (H1-c), R ^H05 to R ^H08 each independently represent an alkyl group, R ^Ha and R ^Hb each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and W ^H1 represents a substituent.

Preferred examples of the compound represented by the general formula (H) are shown below. However, the present invention is not limited to this.

Compound HA-1 (product name "TINUVIN 123", manufactured by BASF, CAS-No. 129757-67-1), compound HA-11 ( Product name "TINUVIN 152", manufactured by BASF, CAS-No. 1917 43-75-6) and compound HA-12 (product name "FLAMESTAB NOR 1 16 FF", manufactured by BASF, CAS-No. 191680-81- 6) Available on the market.

The compound represented by the general formula (H) can be obtained commercially as described above, or it can be produced by synthesis. The method for synthesizing the compound represented by the general formula (H) is not particularly limited, and it can be synthesized by a method in a general organic synthesis. Moreover, as a purification method, the method of distillation, recrystallization, reprecipitation, and the use of a filter agent and an adsorbent can be used suitably. In addition, the commercially available compounds that are generally available at low cost are not only compounds represented by the general formula (H), but may be a mixture. However, in the present invention, as long as it functions as a radical scavenger, it can be used regardless of the production method, composition, melting point, acid value, and the like.

The molecular weight of the compound represented by the general formula (H) is not limited, but from the viewpoint of suppressing volatilization from the transparent support film, it is preferably a polymer to some extent as the following molecular weight. By adjusting to a moderate molecular weight, it is excellent in compatibility with a transparent support, and a highly transparent film can be obtained.

Therefore, the molecular weight of the compound represented by the general formula (H) is preferably 300 to 100,000, more preferably 500 to 50,000, and particularly preferably 700 to 30,000.

The timing for adding the compound represented by the general formula (H) to the transparent support film is not particularly limited as long as it is added at the time when the film formation is performed. For example, it may be added at the stage of mixing the transparent support and the solvent, or it may be added at the stage of mixing the transparent support and the solvent. After the liquid was added.

The content of the compound represented by the general formula (H) in the transparent support film is preferably 0.0001 to 5.0 parts by mass based on 100 parts by mass of the transparent support. When the content of the compound represented by the general formula (H) in the transparent support film is within the above range, a sufficient antioxidant effect and polarizer durability characteristics can be obtained. Still more preferably, the content of the compound represented by the general formula (H) in the transparent support film is 0.001 to 2.0 parts by mass, and still more preferably 0.01 to 1.0 part by mass relative to 100 parts by mass of the transparent support.

(Ultraviolet absorbent)

As a transparent support, it is also preferable to use the film containing an ultraviolet absorber from a viewpoint of preventing deterioration of a polarizing plate, a liquid crystal, etc. From the viewpoint of excellent absorption of ultraviolet rays having a wavelength of 370 nm or less and good display properties, the ultraviolet absorbent is preferably one which has a small absorption of visible light having a wavelength of 400 nm or more. The ultraviolet absorber used in the present invention is preferably selected from a hindered phenol compound, a hydroxybenzophenone compound, a benzotriazole compound, a salicylate compound, a benzophenone compound, a cyanoacrylate compound, and a nickel oxide. At least one kind of salt compound.

The hindered phenol compound is not particularly limited. However, it is preferably selected from 2,6-di-tertiary-butyl-p-cresol, neopentaerythritol-tris [3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propene Acid esters], N, N'-hexamethylenebis (3,5-di-tertiarybutyl-4-hydroxy-hydrocinnamidine), 1,3,5-trimethyl-2,4, 6-gins (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and ginseng- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate At least 1 species.

The benzotriazole compound is not particularly limited. However, it is preferably selected from 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethyl) Butyl) -6- (2H-benzotriazol-2-yl) phenol], (2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tri Butylaniline) -1,3,5-tri , Triethylene glycol-bis [3- (3-tertiarybutyl-5-methyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-bis -Tertiary butyl-4-hydroxy-hydrocinnamidine), 1,3,5-trimethyl-2,4,6-para (3,5-di-tertiary butyl-4-hydroxybenzyl) ) Benzene, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di -Tertiary pentylphenyl) -5-chlorobenzotriazole, 2,6-di-tertiary butyl-p-cresol, and neopentaerythritol-3- [3- (3,5-di-tri Butyl-4-hydroxyphenyl) propionate, 2- (3,5-di-tertiarypentyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazole-2 -Yl) at least one of 6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol)].

These compounds include TINUVIN 99-2, TINUVIN 109, TINUVIN 171, TINUVIN 320, TINUVIN 326, TINUVIN 327, TINUVIN 328, TINUVIN 329, TINUVIN 343, TINUVIN 900, TINUVIN 928, TINUVIN P, TINUVIN PS, etc. TINUVIN, they are all products of BASF company, can be better used.

On a mass basis, the content of the ultraviolet absorber in the transparent support film is preferably 1 ppm to 10%, more preferably 1 ppm to 5.0%, and even more preferably 10 ppm to 3.0%.

(Matting agent)

From the viewpoint of film smoothness and stable production, a film containing a matting agent can be used as the transparent support. The matting agent may be a matting agent of an inorganic compound or a matting agent of an organic compound.

Matting agents for inorganic compounds are preferably selected from inorganic compounds containing silicon (E.g. silicon dioxide, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, etc.), titanium oxide, zinc oxide, aluminum oxide, barium oxide, zirconia, strontium oxide, antimony oxide, tin oxide At least one of tin, antimony oxide, calcium carbonate, talc, clay, calcined kaolin and calcium phosphate, more preferably at least one selected from inorganic compounds containing silicon and zirconia. From the viewpoint of further reducing the turbidity of the transparent support, it is particularly preferable to use silicon dioxide.

As the fine particles of silicon dioxide, for example, a commercially available product having a trade name such as Aerosil R972, R974, R812, 200, 300, R202, OX50, TT600 (above, manufactured by Japan Aerosil Corporation) can be used. As the fine particles of zirconia, for example, those marketed under the trade names of Aerosil R976 and R811 (above, manufactured by Japan Aerosil Corporation) can be used.

The matting agent of the organic compound is not particularly limited. However, at least one polymer selected from the group consisting of a silicone resin, a fluororesin, and an acrylic resin is preferred, and among these, a silicone resin is preferred. Among silicone resins, those having a three-dimensional network structure are particularly preferred. For example, Tospearl 103, Tospearl 105, Tospearl 108, Tospearl 120, Tospearl 145, Tospearl 3120, and Tospearl 240 (above, manufactured by Toshiba Silicones) can be used. And other commercially available products.

The timing at which these matting agents are added to the transparent support is not particularly limited as long as it is added at the time of film formation. For example, an additive may be added at the stage of mixing the material forming the transparent support and the solvent, or the additive may be added after preparing a mixed solution using the material forming the transparent support and the solvent.

In addition, it is also possible to add mixing just before the dope is cast. The mixing is preferably performed by setting a spiral kneading method on-line. get on. Specifically, a static mixer such as an in-line mixer is preferably used. In addition, as the on-line mixer, for example, a static mixer SWJ (Toray Static In-tube Mixer Hi-Mixer) (manufactured by Toray Engineering) is preferred.

For on-line addition, the method described in Japanese Patent Application Laid-Open No. 2003-053752 can be used in order to eliminate uneven concentration, particle aggregation, and the like. In addition, in order to create a transparent support with little outflow of additives, no interlayer peeling, and good smoothness and excellent transparency, the method described in Japanese Patent Application Laid-Open No. 2003-014933 can also be used.

The content of the matting agent in the transparent support is particularly preferably 0.05 to 1.0% by mass. By setting such a value, the haze of the film does not increase, and when it is actually used in a liquid crystal display device, it contributes to suppressing disadvantages such as a decrease in contrast and generation of bright spots. In addition, squeaking and abrasion resistance can be achieved. From these viewpoints, the content of the matting agent in the transparent support is particularly preferably 0.05 to 1.0% by mass.

(Peel Accelerator)

The transparent support is also preferably in the form of using a film containing a release promoter. As the peeling promoter, for example, a compound described in Japanese Patent Application Laid-Open No. 2006-45497, paragraph No. 0048 to 0081, a compound described in Japanese Patent Application Laid-Open No. 2002-322294, Japanese Patent Laid-Open No. Compounds and the like described in paragraphs 0030 to 0056 of the 2012-72348 publication.

(Organic acid)

The transparent support is also preferably in the form of using a film containing an organic acid.

Examples of the organic acid include Japanese Patent Application Laid-Open No. 2002-322294 Examples of the compound described in paragraph numbers 0079 to 0082 include citric acid, oxalic acid, adipic acid, succinic acid, malic acid, and tartaric acid.

In addition, as the organic acid, amino acids are also preferred, and examples thereof include aspartic acid, aspartic acid, adenine, alanine, β-alanine, spermine, and isoleucine. Acid, Glycine, Glutamine, Glutamine, Serine, Tyrosine, Tryptophan, Threonine, N-Leucine, Valine, Phenylalanine, Methionine , Lysine, leucine and so on.

Organic acids can also be used as the free acid, and examples thereof include alkali metal salts, alkaline earth metal salts, and salts of heavy metals containing transition metals. Among the metals of the salts, alkali metals can be exemplified: lithium, potassium, sodium, etc., and alkaline earth metals can be exemplified: calcium, magnesium, barium, strontium, and the like. Examples of heavy metals including transition metals include aluminum, zinc, tin, nickel, iron, lead, copper, and silver. In addition, substituted or unsubstituted amine salts having a carbon number of 5 or less are also preferred. Examples of the salt-forming amine include ammonium, methylamine, ethylamine, propylamine, butylamine, dimethylamine, trimethylamine, triethylamine, hydroxyethylamine, bis (hydroxyethyl) amine, and Ethyl) amine and the like. Preferred metals are sodium in the case of alkali metals, and calcium and magnesium in the case of alkaline earth metals. These alkali metals and alkaline earth metals can be used individually or in combination of 2 or more types, and an alkali metal and an alkaline earth metal can also be used together.

(Polycarboxylic acid derivative)

The transparent support is also preferably in the form of using a film containing a polycarboxylic acid derivative.

As the polycarboxylic acid derivative, an ester compound and an amidine compound are preferred.

The carboxylic acid component is a polycarboxylic acid, and the carboxylic acid may be an aliphatic or aromatic carboxylic acid. However, an aliphatic carboxylic acid is preferred. The aliphatic carboxylic acid may be a saturated or unsaturated, preferably a linear, branched or cyclic aliphatic carboxylic acid, and may have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, an amine group, an alkoxy group, an alkenyloxy group, a fluorenyloxy group, and a fluorenylamino group.

Examples of the aromatic carboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, and 1,3,5-benzenetricarboxylic acid. Examples of the aliphatic carboxylic acid include oxalic acid, malonic acid, and succinic acid. , Glutaric acid, adipic acid, and sebacic acid. Examples of the aliphatic carboxylic acid having a substituent include malic acid, citric acid, and tartaric acid.

The polycarboxylic acid ester is a substituted or unsubstituted alkyl group of the alcohol component and a -C (= O) -O- oxygen atom-bonded group [eg, methyl, ethyl, iso Propyl, tertiary butyl, 2-ethylhexyl, -CH ₂ CH ₂ O- (CH ₂ CH ₂ ) nC ₂ H ₅ etc.], alkenyl (e.g. vinyl, allyl, 2-methyl Propylene, 2-butenyl, oleenyl, etc.), the total carbon number of the alcohol component (the group bonded to the oxygen atom) is preferably 1 to 200, more preferably 1 to 100, and even more preferably 1 to 50. The substituent which the alkyl group and the alkenyl group may have is preferably an alkoxy group, an alkenyloxy group, a hydroxyl group, or a fluorenyloxy group, and more preferably an alkoxy group. The alkoxy or alkenyl group preferably contains a (poly) oxyalkenyl group. In particular, the (poly) oxyalkenyl group is preferably a poly (oxyethylene) group, a (poly) oxypropylene group, or a (poly) oxy group. Butenyl.

In addition, the alcohol of the raw material in the alcohol component may be monovalent or polyhydric. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerol, and neopentyl alcohol. These hydroxyl groups (-OH) are also preferable. To be a polyoxyalkoxy group [for example,-(OCH ₂ CH ₂ ) n-OH,-(OC ₃ H ₆ ) nOH].

The polycarboxylic acid ammonium amine and the amine compound which is an amine component may be either a primary amine or a secondary amine, and are not particularly limited. The substituent substituted on the nitrogen atom of -C (= O) -N <of a fluorene functional group is preferably an alkyl group [e.g. methyl, ethyl, isopropyl, tertiary butyl, 2-ethylhexyl , -CH ₂ CH ₂ O- (CH ₂ CH ₂ ) nC ₂ H ₅ etc.], alkenyl (e.g. vinyl, allyl, 2-methyl-2-propenyl, 2-butenyl, etc.) The total carbon number of the amine compound of the amine component is preferably 1 to 200, more preferably 1 to 100, and even more preferably 1 to 50. The substituent which the alkyl group and alkenyl group may have is preferably an alkoxy group, an alkenyloxy group, a hydroxyl group, a fluorenyloxy group, an amine group, or a fluorenylamino group, and more preferably an alkoxy group. The alkoxy or alkenyl group preferably contains a (poly) oxyalkenyl group. In particular, the (poly) oxyalkenyl group is preferably a poly (oxyethylene) group, a (poly) oxypropylene group, or a (poly) oxy group. Butenyl. In addition, such a polyoxyalkenyl partial structure is also preferably a branched polyoxyalkenyl group through glycerol.

The amine compound of the raw material in the amine component may be monovalent or plural.

Among the polycarboxylic acid derivatives, particularly preferred is an organic acid monoglyceride having an unreacted and free carboxyl group. As a commercially available product, for example, Poem K-37V (available from Riken Vitamin Co., Ltd.) Glycerol citrate oleate), Kao's Step SS (glycerol stearic acid / palmitate succinate), and the like.

(Surfactant)

The transparent support of the present invention is also preferably in the form of using a film containing a surfactant.

As the surfactant, Japanese Patent Application Laid-Open can be preferably used Compounds described in paragraph numbers 0050 to 0051 of Japanese Patent Publication No. 2006-45497, and compounds described in paragraph numbers 0127 to 0128 of Japanese Patent Application Laid-Open No. 2002-322294. Specific examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene-polyoxypropylene glycols, polyhydric alcohol fatty acid partial esters, and polyalkylene glycols. Oxyethylene polyol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerol fatty acid ester, fatty acid diethanolamine, triethanolamine fatty acid partial ester, polyetheramine. Moreover, as a commercial item, NYMEEN L-202, STAFOAM DO, STAFOAM DL (Japanese oil), etc. are mentioned.

(Chelating agent)

The transparent support of the present invention is also preferably in the form of using a film containing a chelating agent.

Chelating agents are compounds capable of coordinating (chelating) metal ions such as iron ions or alkaline earth metal ions such as calcium ions. Amino polycarboxylic acids and amino polyphosphonic acids can be used. Any of various chelating agents typified by alkylphosphonic acid and phosphinophosphonic acid. As the chelating agent, JP 6-8956, JP 11-190892, JP 2000-18038, JP 2010-158640, JP 2006-328203, and JP 2005 can be used. -68246, Japanese Unexamined Patent Publication No. 2006-306969.

Specific examples include ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, and cyclohexane. Diamine tetraacetic acid, hydroxyethylimine diacetic acid, ethylene glycol bis (2-amino ether) tetraacetic acid, 1,3-diaminopropane tetraacetic acid, phosphonic acid, 1-hydroxyethylene-1 ,1- Diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-bis (o-hydroxyphenylacetic acid) ), DL-alanine-N, N-diacetic acid, aspartic acid-N, N-diacetic acid, glutamic acid-N, N-diacetic acid, serine-N, N-diacetic acid, polyacrylic acid , Isopentene-maleic acid copolymer, acrylic acid-maleic acid copolymer, acrylic acid-methacrylic acid copolymer, silicic acid, gluconic acid, hydroxybenzyl iminodiacetic acid, iminodi Acetic acid and so on. Their commercial products can be obtained from Chelest AG, Nagase chemtex AG, Tongren Chemical Research Institute, etc.

It is also preferable to use an oil-soluble chelating agent. As commercially available products, Techrun DO (Nagase chemtex), Chelest MZ-2, and Chelest MZ-8 (Chelest) can be used.

[Hard coating film]

The hard-coat film of this invention is manufactured by the manufacturing method of the said hard-coat film of this invention.

In general, the hard coating film of the present invention has a simplest configuration in which a hard coating is applied to a transparent support.

Examples of preferred layer configurations of the hard coat film of the present invention are shown below, but they are not limited to these layer configurations.

‧Support / hard coating

‧Support / hard coating / low refractive index layer

‧Support / hard coating / anti-glare layer (antistatic layer) / low refractive index layer, ‧Support / hard coating / anti-glare layer / antistatic layer / low refractive index layer, ‧support / hard coating / Antistatic layer / Antiglare layer / Low refractive index layer, ‧Support / Hard coating (antistatic layer) / Antiglare layer / Low refractive index layer, ‧Support / Hard coating / High refractive index layer / Anti Electrostatic layer / low refractive index Layer, ‧support / hard coating / high refractive index layer (antistatic layer) / low refractive index layer, ‧support / hard coating / antistatic layer / high refractive index layer / low refractive index layer, ‧support / Hard coating / Medium refractive index layer / High refractive index layer (antistatic layer) / Low refractive index layer, ‧Support / Hard coating / Medium refractive index layer (antistatic layer) / High refractive index layer / Low refractive index Rate layer, ‧support / hard coating (antistatic layer) / medium refractive index layer / high refractive index layer / low refractive index layer, ‧support / antistatic layer / hard coating / medium refractive index layer / high refractive Rate layer / low refractive index layer, ‧antistatic layer / support / hard coating / medium refractive index layer / high refractive index layer / low refractive index layer, here, the antistatic layer and anti-glare layer may also have hard coating Sex.

The film thickness of the hard coat layer of the present invention can be selected in accordance with the target hardness, but is preferably 1 to 50 μm. This is because the curl of the hard coating film of the present invention is very small, so that even if the hard coating is thickened, there is no problem in handling. When used as a polarizer protective film, the thickness of the hard coat layer is preferably designed to be 3 to 10 μm.

In the hard coating film of the present invention, the ratio t _H / t _T of the thickness t _{T of the} transparent support and the thickness t _H of the hard coat layer is preferably 0.1 or more and 1.0 or less, and more preferably 0.2 or more and 0.7 or less.

[Low refractive index layer]

The present invention can also form a low-refractive index layer on the hard coat layer for the purpose of imparting a reflectance reduction effect. The low refractive index layer has a lower refractive index than the hard coat layer, and the thickness is preferably 50 to 200 nm, more preferably 70 to 150 nm, and most preferably 80 to 120 nm.

The refractive index of the low-refractive index layer is lower than that of the layer directly below, preferably 1.20 to 1.55, more preferably 1.25 to 1.46, and particularly preferably 1.30 to 1.40. The thickness of the low refractive index layer is preferably 50 to 200 nm, and more preferably 70 to 100 nm. The low refractive index layer is preferably obtained by curing a curable composition for forming a low refractive index layer.

Preferred aspects of the composition of the hardenable material of the low refractive index layer include (1) a composition containing a fluorine-containing compound having a crosslinkable or polymerizable functional group, and (2) a fluorine-containing compound A composition containing a hydrolyzed condensate of an organic silane material as a main component, (3) a composition containing a monomer having two or more ethylenically unsaturated groups, and an inorganic fine particle (particularly, an inorganic fine particle having a hollow structure), etc. .

Regarding (1) and (2), it is also preferable to contain inorganic fine particles. If inorganic fine particles having a hollow structure with a low refractive index are further used, from the viewpoint of lowering the refractive index, adjusting the amount of inorganic fine particles added, and adjusting the refractive index, etc. The words are exceptional.

(1) Fluorinated compound having a crosslinkable or polymerizable functional group

Fluorine-containing compound as a functional group having crosslinkability or polymerizability Examples include copolymers of a fluorine-containing monomer and a monomer having a crosslinkable or polymerizable functional group. Specific examples of these fluoropolymers are described in Japanese Patent Application Laid-Open No. 2003-222702, Japanese Patent Application Laid-Open No. 2003-183322, and the like.

You may use together the said polymer the hardening | curing agent which has a polymerizable unsaturated group as described in Unexamined-Japanese-Patent No. 2000-17028. In addition, it is also preferably used in combination with a fluorine-containing compound having a polyfunctional polymerizable unsaturated group as described in Japanese Patent Application Laid-Open No. 2002-145952. Examples of the compound having a polyfunctional polymerizable unsaturated group include a monomer having two or more ethylenically unsaturated groups as the curable resin compound of the antiglare layer described above. In addition, a hydrolyzed condensate of an organic silane described in Japanese Patent Application Laid-Open No. 2004-170901 is also preferable, and a hydrolyzed condensate of a (meth) acrylfluorenyl-containing organic silane is particularly preferable. These compounds, especially when a compound having a polymerizable unsaturated group in the polymer itself is used, has a large combined effect for improving abrasion resistance and is preferred.

When the polymer itself does not have sufficient hardenability, by blending a crosslinkable compound, the desired hardenability can be imparted. For example, when the polymer itself contains a hydroxyl group, it is preferable to use various amine compounds as the hardener. The amine compound that is used as the crosslinkable compound is, for example, a compound that contains one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total. Specifically, for example, Out: melamine-based compounds, urea-based compounds, benzoguanamine-based compounds, glycoluril-based compounds, and the like. For curing these compounds, an organic acid or a salt thereof is preferably used.

(2) A composition containing a hydrolyzed condensate of a fluorine-containing organosilane material as a main component

It is also preferable that the composition containing a hydrolyzed condensate of a fluorine-containing organosilane compound as a main component has a low refractive index and high hardness on the surface of the coating film. A condensate of a compound containing a hydrolyzable silanol at one or both ends of a fluorinated alkyl group and a tetraalkoxysilane is preferred. Specific compositions are described in Japanese Patent Application Laid-Open No. 2002-265866 and Japanese Patent No. 317152.

(3) A composition containing a monomer having two or more ethylenically unsaturated groups and an inorganic fine particle having a hollow structure

Moreover, as another preferable aspect, the low-refractive-index layer which consists of a low-refractive-index particle and a binder is mentioned. The low-refractive index particles may be either organic or inorganic, but are preferably particles having pores inside. Specific examples of the hollow particles are described in silicon oxide described in Japanese Patent Application Laid-Open No. 2002-79616. The particle refractive index is preferably 1.15 to 1.40, and more preferably 1.20 to 1.30. Examples of the binder include a monomer having two or more ethylenically unsaturated groups described on the antiglare layer page.

The composition for a low-refractive index layer used in the present invention is preferably added with the aforementioned photoradical polymerization initiator or thermal radical polymerization initiator. When a radically polymerizable compound is contained, a polymerization initiator can be used in an amount of 1 to 10 parts by mass, preferably 1 to 5 parts by mass, with respect to the compound.

The low refractive index layer used in the present invention can use inorganic particles in combination. In order to impart scratch resistance, 15% to 150% of the thickness of the low refractive index layer can be used, preferably 30% to 100%, and more preferably 45% ~ 60% particle size.

The low-refractive index layer of the present invention can suitably add a well-known polysiloxane-based or fluorine-based antifouling agent and smoothing agent for the purpose of imparting characteristics such as antifouling, water resistance, chemical resistance, and smoothness. Wait.

As the additive having a polysiloxane structure, it is also preferable to add a polysiloxane containing a reactive group {for example, "KF-100T", "X-22-169AS", "KF-102", "X- 22-3701IE "," X-22-164B "," X-22-5002 "," X-22-173B "," X-22-174D "," X-22-167B "," X-22- 161AS "(trade name), above Shin-Etsu Chemical Industry Co., Ltd .;" AK-5 "," AK-30 "," AK-32 "(trade name), above, East Asia Synthetic Co., Ltd .;" Silaplane FM0725 " "," Silaplane FM0721 "(trade name), Chisso (stock) system, etc.}. In addition, the silicone compounds described in Tables 2 and 3 of Japanese Patent Application Laid-Open No. 2003-112383 can also be preferably used.

The fluorine-based compound is preferably a compound having a fluoroalkyl group. The fluoroalkyl group is preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and may be a straight chain (for example, -CF ₂ CF ₃ , -CH ₂ (CF ₂ ) ₄ H, -CH ₂ (CF ₂ ) ₈ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.) or branch structures (for example, CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.) can also be alicyclic structure (preferably 5-membered ring or 6-membered ring, such as perfluorocyclohexyl, perfluorocyclopentyl Or an alkyl group substituted by them), or may have an ether bond (for example, 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 C ₈ F ₁₇ , CH ₂ CH ₂ OCF ₂ OCF ₂ CF ₂ H, etc.). The fluoroalkyl group may include a plurality of them in the same molecule.

It is preferable that the fluorine compound further has The film of the emissivity layer forms a bond or a compatible substituent. The above-mentioned substituents may be the same or different, and it is preferable to have a plurality of them. Preferable substituents include acrylfluorenyl, methacrylfluorenyl, vinyl, aryl, cassia fluorenyl, epoxy, oxetanyl, hydroxyl, polyoxyalkenyl, and carboxyl , Amine and so on. The fluorine-based compound may be a polymer or a oligomer with a compound containing no fluorine atom, and the molecular weight is not particularly limited. The fluorine atom content of the fluorine-based compound is not particularly limited, but it is preferably 20% by mass or more, particularly preferably 30 to 70% by mass, and most preferably 40 to 70% by mass. Examples of preferred fluorine-based compounds include: R-2020, M-2020, R-3833, M-3833, OPTOOL DAC (the above are trade names) by Daikin Chemical Industry Co., Ltd. (Stock) Megafac F-171, F-172, F-179A, DEFENSA MCF-300, MCF-323 (the above are trade names), etc., but are not limited thereto.

It is preferable that these polysiloxane fluorinated compounds or compounds having a polysiloxane structure are added in a range of 0.1 to 10% by mass of the total solid content of the low refractive index layer, and particularly preferably 1 to 5% by mass. under.

[Coating method]

Each layer of the hard coating film of the present invention can be formed by the following coating method, but is not limited to this method. Can be used: dip coating method, air knife coating method, curtain coating method, roll coating method, wire rod coating method, gravure coating method, sliding coating method or extrusion coating method (mold coating method) (refer to Japanese Patent Application Laid-Open 2003) -164788), a known method such as a micro gravure coating method, and the micro gravure coating method and the die coating method are preferred.

[Drying and hardening conditions]

In the case of forming a layer such as a hard coat layer in the present invention by coating The drying and hardening method in this case will be described below as a preferred example.

The present invention is effective by combining: curing by ionizing radiation; and heat treatment before, simultaneously with, or after irradiation.

Hereinafter, the mode of several manufacturing steps is shown, but it is not limited to these. ("-" Below indicates that no heat treatment is performed.)

Before irradiation → Simultaneous with irradiation → After irradiation

(1) heat treatment → ionizing radiation hardening →-

(2) heat treatment → ionizing radiation hardening → heat treatment

(3)-→ Ionizing radiation hardening → Heat treatment

In addition, it is also preferable to perform a step of simultaneously performing heat treatment when the ionizing radiation is hardened.

In the present invention, as described above, the heat treatment is preferably performed in combination with irradiation by ionizing radiation. The heat treatment is not particularly limited as long as it does not damage the support of the hard coat film and the constituent layer including the hard coat layer, but it is preferably 40 to 150 ° C, and more preferably 40 to 80 ° C.

The time required for heat treatment varies depending on the molecular weight of the components used, interaction with other components, viscosity, etc., but it is 15 seconds to 1 hour, preferably 20 seconds to 30 minutes, and most preferably 30 seconds to 5 minutes.

The type of the ionizing radiation is not particularly limited, and examples thereof include X-rays, electron rays, ultraviolet rays, visible light, and infrared rays, but ultraviolet rays are widely used. For example, if the coating film is ultraviolet curable, it is preferable to irradiate ultraviolet rays with an irradiation amount of 10 mJ / cm ² to 1000 mJ / cm ² with an ultraviolet irradiator to harden each layer. In the case of irradiation, the above-mentioned energy may be exposed at one time, or the irradiation may be performed in multiple times. In particular, from the viewpoint of reducing uneven performance in the surface of the coating film or improving curl, it is preferably divided into two or more irradiations, and an initial irradiation with a low irradiation amount of ultraviolet light of 150 mJ / cm ² or less is preferred After that, a high irradiation amount of ultraviolet light of 50 mJ / cm ² or more is irradiated, and the exposure amount in the later period is higher than that in the initial period.

[Polarizer]

The hard coating film of the present invention is one or both of the protective films for a polarizing plate including a polarizing film and a protective film disposed on both sides thereof, and can be used to form a polarizing plate having a hard coating property.

The hard coating film of the present invention can be used as one protective film, and a normal cellulose acetate film can be used as the other protective film. However, the other protective film is preferably produced by a solution film method. The cellulose acetate film is stretched in a width direction in a roll film form at a stretching ratio of 10 to 100%.

In addition, among the two protective films of the polarizing film, an optical compensation film having an optical compensation layer including an optical anisotropy layer in the film system other than the hard coat film of the present invention is also a preferable aspect. An optical compensation film (a retardation film) can improve the viewing angle of a liquid crystal display screen. As the optical compensation film, a well-known person can be used, but in terms of widening the viewing angle, the optical compensation film described in Japanese Patent Application Laid-Open No. 2001-100042 is preferable.

The polarizing film includes an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, or a polyene-based polarizing film. Iodine-based polarizing films and dye-based polarizing films are generally manufactured using polyvinyl alcohol-based films.

In addition, as the polarizing film, a well-known polarizing film or an absorption axis from the polarizing film is neither parallel to the long side direction nor long side. A polarizing film cut from a long polarizing film with a vertical direction. A long polarizing film system in which the absorption axis of the polarizing film is neither parallel to the longitudinal direction nor perpendicular to the longitudinal direction is produced by the following method.

That is, it can be manufactured by a stretching method in which both ends of a polymer film such as a polyvinyl alcohol-based film that is continuously supplied are held by a holding means, while being stretched by applying tension, at least in the film width direction It is 1.1 to 20.0 times, and the difference in the lengthwise traveling speed of the holding devices at both ends of the film is within 3%. The angle between the film's travel direction and the substantial stretching direction of the film at the exit of the step of holding both ends of the film is 20 to The 70 ° inclination method bends the film traveling direction while holding both ends of the film. In particular, from the viewpoint of productivity, a 45 ° incline is preferably used.

The method for stretching a polymer film is described in detail in paragraph numbers 0020 to 0030 of Japanese Patent Application Laid-Open No. 2002-86554.

[Image display device]

The hard coating film or polarizing plate of the present invention can be used in an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode tube display device (CRT).

Particularly preferred is a liquid crystal display device comprising a liquid crystal cell and a polarizing plate of the present invention arranged on at least one side of the liquid crystal cell, and the hard coating film of the present invention is arranged on the outermost surface.

[Example]

In order to explain the present invention in detail, examples are described below, but the present invention is not limited to these examples.

(Preparation of hard coat coating liquid)

Each component was added with the composition shown in the following Tables 6 to 8, and filtered with a polypropylene filter having a pore size of 10 μm to prepare a hard coat coating liquid (composition for forming a hard coat) A01 to A39, A50, A51 . The numerical value in a table | surface shows the "mass% of solid content" of each component.

For materials diluted with a solvent such as ELECOM V-8802, adjustments and additions are performed so that the solid content ratio becomes the content described in the table. The solvent was adjusted so that the solvent ratio became the ratio described in the table to prepare a coating liquid having a solid content ratio of 35% by mass.

‧Epoxy Compound A:

‧DPHA: KAYARD DPHA (made by Nippon Kayaku Co., Ltd.)

‧ATMMT: neopentaerythritol tetraacrylate (made by Shin Nakamura Chemical Industry Co., Ltd.)

‧UV 1700B: Urethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd.)

‧IRGACURE 127: Alkyl phenone-based photopolymerization initiator (BASF (manufactured))

‧IRGACURE 819: fluorenyl phosphine oxide-based photopolymerization initiator (BASF (manufactured))

‧IRGACURE 290: phosphonium salt cationic polymerization initiator (BASF (manufactured))

‧IRGACURE 270: phosphonium salt cationic polymerization initiator (BASF (manufactured))

‧B2380: phosphonium salt cationic polymerization initiator (manufactured by Tokyo Chemical Industry Co., Ltd.)

‧CGI 725: Nonionic cationic polymerization initiator (BASF (manufactured))

‧ELECOM V-8802: MiBK dispersion (manufactured by Nikkei Co., Ltd.) with an average particle diameter of 12 nm, a solid content of spherical silica particles with a polymerizable group of 40% by mass

‧ELECOM V-8803: with a polymerizable group and a special shape (connected with a chain) The shape of the knot) 40% by mass of the solid content of the silicon oxide microparticles, a MiBK dispersion (manufactured by Niwa Corporation)

‧MiBK-ST: MiBK dispersion (manufactured by Nissan Chemical Co., Ltd.) with an average particle diameter of 10 to 20 nm and a solid content of 30% by mass of the silica particles having no reactive group.

‧FP-1: The following fluorine-containing compounds

‧Tinuvin460, Tinuvin466, Tinuvin928: UV absorbers (manufactured by BASF)

‧Celloxide 2021P: 3 ’, 4’-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Daicel (share))

‧Bisphenol A diepoxy acrylate: epoxy ester 3000A manufactured by Kyoeisha Chemical Co., Ltd.

(Coating of hard coat)

Triethyl cellulose cellulose films with a thickness of 40 μm, 25 μm, and 20 μm are rolled out in rolls, and the coating liquids A01 to A39, A50, and A51 for hard coating are used. The film thickness of the hard coating after hard coating is to be Table 9 ~ Table 11 The thickness method was adjusted to produce hard coating films S01 to S39, S50, and S51. In addition, S16 is a 300 μm-thick Technolloy C-101 (three-layer structure of PMMA film / polycarbonate film / PMMA film) manufactured by Sumika ACRYL Co., Ltd., and a hard coat layer is formed using A16 solution.

In addition, S40 to S44 are A01, A14, A18, or A27 liquids on the acrylic substrate film prepared by the method described later, and S45 to S47 are tritiated cellulose substrate films prepared by the method described below. A01 solution was used to form a hard coating on the support.

Specifically, each coating liquid is applied by a die coating method using a slot die described in Example 1 of Japanese Patent Application Laid-Open No. 2006-122889, at a transfer speed of 30 m / min, and dried at 60 ° C. After 150 seconds, an air-cooled metal halide irradiator (manufactured by Eyegraphics) was used under an oxygen concentration of about 0.1% by volume under nitrogen flushing to irradiate 400 mW / cm ² and 500 mJ / cm ² of light. After the coating layer is hardened with ultraviolet rays to form a hard coat layer, it is wound up.

(Production of 40 μm acrylic substrate film)

Into a 30-liter reaction vessel equipped with a stirring device, a temperature sensor, a cooling pipe, and a nitrogen introduction pipe, 8000 g of methyl methacrylate (MMA), 2000 g of methyl 2- (hydroxymethyl) acrylate (MHMA), and 10,000 g of toluene as a polymerization solvent was passed through nitrogen and heated up to 105 ° C. After the reflux with temperature rise started, 10.0 g of tertiary pentylperoxy isononanoate as a polymerization initiator was added, and 20.0 g of tertiary pentyl peroxy isononanoate and toluene were added dropwise over a period of 2 hours. A 100 g solution was subjected to solution polymerization under reflux at about 105 to 110 ° C., and further aged for 4 hours. The polymerization rate was 96.6%, and the obtained polymerization The content (weight ratio) of MHMA in the product was 20.0%.

Next, 10 g of a stearyl phosphate / distearyl phosphate mixture (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) was added to the obtained polymerization solution as a cyclization catalyst under reflux at about 80 to 100 ° C. The cyclization condensation reaction was allowed to proceed for 5 hours.

Next, at a processing speed of 2.0 kg / hour in terms of the amount of resin, the obtained polymerization solution was introduced into a bobbin temperature of 260 ° C, a rotation speed of 100 rpm, a degree of pressure reduction of 13.3 to 400 hPa (10 to 300 mmHg), and a rear discharge hole. A discharge hole screw two-shaft extruder (Φ = 29.75mm, L / D = 30) with a number of 1 and a number of front discharge holes, performs cyclization condensation reaction and devolatilization in the extruder. Next, after the devolatilization is completed, the resin in the hot melt state remaining in the extruder is discharged from the front end of the extruder and pelletized by a pelletizer to obtain a resin containing a lactone ring structure on the main chain. Transparent particles of acrylic resin. The weight average molecular weight of this resin is 148,000, and the melt flow rate (calculated in accordance with JIS K7120, the test temperature is set to 240 ° C, and the load is set to 10 kg. The same applies to the following production examples) is 11.0 g / 10 minutes, the glass transition temperature is 130 ° C.

Next, the obtained pellets and AS resin (manufactured by Toyo Styrene, trade name: TOYO AS AS20) were kneaded with a uniaxial extruder (Φ = 30 mm) at a weight ratio of pellets / AS resin = 90/10, so that Transparent particles having a glass transition temperature of 127 ° C were obtained.

The pellets of the resin composition produced above were melt-extruded from a hanger-type T-die using a biaxial extruder to produce a resin film having a thickness of about 160 μm.

Next, the obtained unstretched resin film was simultaneously biaxially stretched twice in the longitudinal direction (longitudinal direction) and twice in the transverse direction (widthwise direction) to produce a polarizer protective film. The thickness of the acrylic substrate film obtained in this manner was 40 μm, the total light transmittance was 92%, the haze was 0.3%, and the glass transition temperature was 127 ° C.

(Production of 30 μm acrylic substrate film)

Using a biaxial extruder, transparent particles having a glass transition temperature of 127 ° C produced in the same manner as the method for producing a 40 μm acrylic substrate film were melt-extruded from a hanger-type T-die to produce a resin film having a thickness of approximately 120 μm.

Next, the obtained unstretched resin film was simultaneously biaxially stretched twice in the longitudinal direction (longitudinal direction) and twice in the transverse direction (widthwise direction) to produce a polarizer protective film. The thickness of the acrylic substrate film obtained in this manner was 30 μm, the total light transmittance was 92%, the haze was 0.25%, and the glass transition temperature was 127 ° C.

(Production of 25 μm tritiated cellulose substrate film)

The support system of Sample No. S45 was prepared by the following method.

The support of S01 to S15, S17 to S39, S50, S51, and S62 was performed in the same manner as the support of sample No. S45 except that the compound represented by the general formula I was removed. The thickness of ~ 12 is adjusted to make the casting amount of the paint.

(Manufacturing of Core Layer Cellulose Coating)

The following composition was put into a mixing tank and stirred to dissolve each component and adjust the cellulose acetate solution.

Molecular weight MW of phthalate oligomer A: 750

Compound (A-1) represented by Formula I

UV absorber

(Fabrication of Outer Layer Cellulose Coating)

10 parts by mass of the matting agent solution described below was added to 90 parts by mass of the core layer halogenated cellulose coating material described above, and the outer layer cellulose acetate solution was adjusted.

(Production of tritiated cellulose film)

From the casting port, 3 layers of the above-mentioned core-cellulose cellulose coating and the outer layer-cellulose cellulose coating on both sides thereof were simultaneously cast on a drum at 20 ° C. Perform stripping at a solvent content of approximately 20% by mass, and fix both ends of the film in the width direction with a tenter clamp, and stretch 1.18 times in the horizontal direction with a residual solvent of 3 to 15%. Dry. After that, it was further dried by conveying between rolls of a heat treatment apparatus to produce a 25 μm-thickened cellulose film.

In addition to substituting the compound represented by Formula I as follows Except for the compound, the same procedure as in the support of sample No. S45 was performed to prepare the support of sample No. S46.

Except that

A support of sample No. S47 was prepared in the same manner as the support of sample No. S46, except that the following compounds were substituted.

Ascorbyl palmitate (6-O-palmitinyl-L-ascorbic acid, manufactured by Tokyo Chemical Industry Co., Ltd.) 0.2 parts by mass

The produced polarizing plate protective films S01 to S47, S50, and S51 were evaluated by the following evaluation methods.

(Film thickness of hard coating)

The film thickness of the hard coat layer was measured by measuring the film thickness of the hard coat film with a contact-type film thickness meter, and subtracting the thickness of the support, which was measured in the same manner, to calculate the film thickness.

(Pencil hardness)

The pencil hardness evaluation described in JIS K 5600-5-4 (1999) was performed. After humidifying the hard coating film at a temperature of 25 ° C and a humidity of 60% RH for 2 hours, the test pencils of 2H to 4H specified in JIS S 6006 (2007) were used, and the numerical values described in the table were under a load of 4.9N. The number of no scratches when scratched 5 times with each pencil.

Based on the number of points, the following criteria were used.

A: When scratched 5 times with a 4H pencil, no scratches occurred 3 or more times.

B: When scratched 5 times with a 3H pencil, no scars were generated 3 or more times.

C: When scratched 5 times with a 3H pencil, a scar was generated 3 or more times.

(Curl evaluation)

The hard coating film was cut out to a size of 60 mm × 60 mm, and humidified for more than 3 hours at 25 ° C and 60% environment. After that, a hammer was placed on the film so that the end surface of the film was exposed by 1 cm, and the height of the end surface lift was measured as the curl value (K). This evaluation was performed on the coating direction and the direction orthogonal to the coating, and the values were averaged. The + warpage value in the table indicates the case where the coated surface (the surface having the hard coat layer) curls inward with respect to the support, and the -warp value indicates the case where the coated surface curls outward with respect to the support.

The evaluation of curl was determined based on the following criteria.

A: The absolute value is less than 3.0mm

B: absolute value is 3.0mm or more and less than 6.0mm

C: Absolute value is 6.0mm or more and less than 8.0mm

D: absolute value is 8.0mm or more

(Damp heat resistance evaluation: 60 ° C, 90% relative humidity, film change after 1000 hours)

The hard coating film was left for 1000 hours under an environment of 60 ° C and a relative humidity of 90%, and then the overview was evaluated when humidification was performed at 25 ° C and 60% for 2 hours or more.

A: The overview has not changed

B: Overview changes such as film turbidity

(Film Transmittance)

The transmittance of the produced hard coating film was measured with a spectrometer UV-3150 from Shimadzu Corporation, and the film transmittance at a wavelength of 380 nm was determined.

[Film saponification treatment]

The hard coat films S01 to S39 and the transparent support used for these hard coat films were immersed in a 2.3 mol / L sodium hydroxide aqueous solution at 55 ° C for 3 minutes. It was washed in a water bath at room temperature, and neutralized with 0.05 mol / L sulfuric acid at 30 ° C. It was washed again in a water bath at room temperature, and further dried with warm air at 100 ° C. In this manner, the surface saponification treatment of the film is performed.

(Production of polarizing plates P01 ~ P39, P45 ~ P47)

Use a PVA-based adhesive to sequentially bond the saponified hard coating films S01 to S39 and S45 to S47 without the laminated hard-coated surface, the stretched iodine-based PVA polarizer, the saponified transparent support, and heat Dry to obtain polarizing plates P01 ~ P39, P45 ~ P47.

At this time, the long side direction of the roll of the produced polarizer was arrange | positioned so that the long side direction of the hard-coat films S01-S39 and S45-S47 may become parallel. Moreover, it arrange | positions so that the longitudinal direction of the roll of a polarizer may become parallel to the longitudinal direction of the roll of the said transparent support body.

(Production of polarizing plates P40 to P43)

Using a microgravure coater (gravure roll: # 180, rotation speed 140% / line speed), an active energy ray-curable acrylic adhesive was applied to the polarizer protective films S40 to S43 so that the thickness was 5 μm. The surface of the hard-coat layer and one side of the transparent support used for these polarizing plate protective films were made into a transparent protective film with an adhesive.

Next, the surface to be bonded to the polarizer was corona treated, and then the transparent protective film with an adhesive was bonded to both sides of the 25 μm iodine-based PVA polarizer using a reel. An electron beam is irradiated from the side (both sides) of the laminated transparent protective film to obtain a polarizing plate having a transparent protective film on both sides of the polarizer. The linear velocity was set to 20 m / min, the acceleration voltage was set to 250 kV, and the irradiation dose was set to 20 kGy.

At this time, the long side direction of the roll of the created polarizer and the long side direction of the polarizing plate protective film were arranged in parallel. Moreover, it arrange | positions so that the longitudinal direction of the roll of a polarizer may become parallel to the longitudinal direction of the roll of the said transparent support body.

[Manufacture of liquid crystal display device]

A commercially available IPS-type LCD TV (42LS5600 manufactured by LG Electronics) was peeled off from the front side, and the absorption axis of the front side polarizer was in the longitudinal direction (left-right direction). The polarizers P01 ~ P47 are attached to the front side by an adhesive. The thickness of the glass used in the liquid crystal cell is 0.5 mm.

In this way, liquid crystal display devices C01 to C47, C50, and C51 were obtained.

[Light leakage evaluation]

For a liquid crystal display device manufactured in this way, the relative humidity at 35 ° C After being humidified at 90% for 24 hours, the backlight of the liquid crystal display device was turned on after being left for 2 hours at 25 ° C and 60% relative humidity. After 10 hours of lighting, the light leakage at the four corners of the panel was evaluated.

The light leakage evaluation was performed using a camera “ProMetric” (manufactured by Radiant Imaging) for brightness measurement. The black display screen was taken from the front of the screen. The average brightness of the entire screen and the difference in brightness between the four corners of the light leakage were determined. 3 stage evaluation.

~ Evaluation Index ~

A: No light leakage is seen at the four corners of the panel.

B: One to two corners of the four corners of the panel are slightly leaky but acceptable.

C: The light leakage at the four corners of the panel is severe and unacceptable.

In addition, the coating liquids A60 and A61 (anti-glare hard coating liquid) for a hard coat layer were prepared as follows. Thereafter, the support shown in the following table was set in the same manner as described for the hard coat film thickness, and a hard coat film of S60 to S62 was produced. A polarizing plate and a liquid crystal display device were fabricated in the same manner as described above using S62, and evaluated in the same manner as described above.

<Preparation of hard coating liquid A60 for anti-glare hard coating>

The cross-linked acrylic-styrene particles (average particle diameter: 6.0 μm, refractive index: 1.525) were mixed so that the content of the cross-linked acrylic-styrene particles was 10% by mass based on the total solid content of the hard coat coating solution. Hard coating liquid A-16. Here, the resin particles are added in a state of a dispersion liquid prepared by the following method. Resin particles were slowly added to the stirring MEK (methyl ethyl ketone) solution until the solid content concentration of the dispersion liquid became 30% by mass, and stirred for 30 minutes to prepare a particle dispersion liquid. The solid content concentration of the hard coat coating liquid was adjusted so that the same solvent ratio as that of A-16 was 35% by mass. Thereafter, it was filtered with a polypropylene filter having a pore diameter of 30 μm to prepare a coating liquid A60 for an anti-glare hard coat layer.

<Preparation of hard coating liquid A61 for anti-glare hard coating>

Except that the content of the cross-linked acrylic-styrene particles was 20% by mass based on the total solids content of the hard coat coating liquid, the anti-glare hard coat coating liquid A60 was prepared in the same manner. Hard coating liquid A61 for glare hard coatings.

The evaluation results of the produced hard coating film, the polarizing plate using the hard coating film, and the liquid crystal display device are shown in the following table. It is understood that the hard coating film pencils of the examples have higher hardness, less curl, and better moisture and heat resistance than the comparative examples. In addition, the hardness of S13 with the addition of reactive silica particles is further improved compared with S10 or S12. In addition, S18 ~ S25 with UV absorber can reduce the transmittance at 380nm. Even S20, which reduces the thickness of the support to 20 μm, maintains a low transmittance by adjusting the amount of UV absorber added, while achieving Low curl and high hardness.

In addition, it is known that a liquid crystal display device using the hard coating film of the present invention has small light leakage and excellent display quality. Although the reason is not clearly understood, it is presumed that the hydrophobicity of the hard coating layer is improved by adding a compound having a molecular weight of 300 or less with an alicyclic epoxy group and an ethylenically unsaturated double bond group in the molecule. To prevent absorption of polarizers under high temperature and high humidity Wet sake.

In addition, the hard coat films S01 to S25, S40 to S43, S45 to S47, and S60 to S62 of the present invention are coated with a low refractive index layer by the method described below. As a result, it was confirmed that development was reduced while maintaining excellent curl and hardness, and more excellent black manageability was achieved.

[Coating of low refractive index layer]

(Preparation of inorganic particle dispersion (B-1))

In Modification Example 4 of Japanese Patent Application Laid-Open No. 2002-79616, the conditions at the time of modulation were changed to produce silicon oxide fine particles with voids inside. The solvent was replaced with methanol from the state of an aqueous dispersion. Finally, the solid content concentration was adjusted to 20% by mass, and particles having an average particle diameter of 45 nm, a shell thickness of about 7 nm, and a refractive index of silicon oxide particles of 1.30 were obtained. Let this be a dispersion liquid (B).

To 500 parts by mass of the above-mentioned dispersion (B), 15 parts by mass of acryloxypropyltrimethoxysilane and 1.5 parts by mass of diisopropoxy aluminum ethyl acetate were added and mixed, and then 9 parts by mass were added. Parts of ion-exchanged water. After reacting at 60 ° C for 8 hours, the mixture was cooled to room temperature, and 1.8 parts by mass of acetamidine was added. Further, MEK was added so that the solvent was replaced with reduced pressure distillation while adding the MEK almost constant, and finally adjusted so that the solid content concentration became 20% by mass to obtain a dispersion (B-1).

(Preparation of coating solution for low refractive index layer)

7.6 g of fluoropolymer (P-12: fluorinated copolymer, exemplified compound of Japanese Patent Application Laid-Open No. 2007-293325), 1.4 g of DPHA, 2.4 g of dispersion (B-1), and photopolymerization initiator ( Irgacure 907) 0.46g, methyl ethyl ketone 190g, propylene glycol monomethyl ether acetate 48g, after stirring, use a pore Filtered by a polypropylene filter with a diameter of 5 μm to prepare a coating solution for a low refractive index layer.

(Coating of low refractive index layer)

The triacetam cellulose film coated with the hard coat layer was rolled out again, and the coating solution for the low refractive index layer was applied at a conveying speed of 30 m / min by the die coating method using the above-mentioned slit die. After drying at 90 ° C for 75 seconds, an air-cooled metal halide irradiator (manufactured by Eyegraphics Co., Ltd.) was used at an oxygen concentration of 0.01 to 0.1% under nitrogen flushing. The irradiation intensity was 400 mW / cm ² and the irradiation volume was 240 mJ / cm ² of ultraviolet rays, a low-refractive-index layer having a thickness of 100 nm was formed, and then rolled up to produce a hard coating film having a low-refractive-index layer. The refractive index of the low refractive index layer is 1.46.

Claims (11)

A method for producing a hard coat film, which is a method for producing a hard coat film having a hard coat layer on at least one side of a transparent support, which comprises at least hardening a hard coat layer forming composition containing the following a) to d) to In the step of forming the hard coat layer, when the total solid content of the hard coat layer forming composition is 100% by mass, the hard coat layer forming composition includes 10 to 40% by mass of the following a), 40 ~ 89.8% by mass of the following b), 0.1 ~ 10% by mass of the following c), 0.1-10% by mass of the following d), a) 1 alicyclic epoxy group and 1 ethylenic in the molecule Compounds having an unsaturated double bond group having a molecular weight of 300 or less; b) compounds having more than 3 ethylenically unsaturated double bond groups in the molecule; c) a radical polymerization initiator; d) a cationic polymerization initiator; The ratio of a) component to b) component is 11 to 100%. The method for manufacturing a hard coating film according to claim 1, wherein when the total solid content of the hard coating layer-forming composition is 100% by mass, the hard coating layer-forming composition further contains 5 to 40% by mass of e ) Inorganic fine particles having reactivity with an epoxy group or an ethylenically unsaturated double bond group. The method for manufacturing a hard coat film according to claim 1, wherein the hard coat layer forming composition further comprises f) an ultraviolet absorbent. The method for manufacturing a hard coating film according to claim 1, wherein the ratio t _H / t _T of the thickness t _{T of} the transparent support to the thickness t _H of the hard coating layer is 0.2 or more and 0.7 or less. The method for manufacturing a hard coating film according to claim 1, wherein a) is epoxy cyclohexyl methyl (meth) acrylate. The method for manufacturing a hard coating film according to any one of claims 1 to 5, wherein the transparent support is a tritiated cellulose film, and the thickness of the transparent support is 25 μm or less. The method for manufacturing a hard coating film according to any one of claims 1 to 5, wherein the transparent support is an acrylic resin film, and the thickness of the transparent support is 40 μm or less. The method for producing a hard coating film according to any one of claims 1 to 5, wherein the transparent support is a tritiated cellulose film and contains at least a compound represented by the following general formula I, In the general formula I, R ¹ , R ³ and R ⁵ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aromatic group, and the alkyl group, the cycloalkyl group, the alkenyl group and the aromatic group may have Any one of R ¹ , R ^3, and R ⁵ is an alkyl group or a cycloalkyl group substituted with a group having a ring structure, and the total of the ring structures existing in R ¹ , R ^3, and R ⁵ is 3 or more. A hard coating film comprising: a transparent support body; and a hard coating layer formed on at least one side of the transparent support body, the hard coating film being formed by the hard coating film according to any one of claims 1 to 6. Manufacturing method. A polarizing plate includes at least one polarizer and a hard coating film as claimed in claim 9 as a protective film for the polarizer. A liquid crystal display device includes a liquid crystal cell and a polarizing plate as claimed in claim 10 arranged on at least one side of the liquid crystal cell. The hard coating film is disposed on the outermost surface.