JP2010139824A - Sheet polarizer, liquid crystal display device and ips (in-plane switching) type liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sheet polarizer, having high-hardness surface and preventing crack and splinter trouble in punching the sheet polarizer, and also to provide a liquid crystal display device having excellent smoothness (flatness) by using the above sheet polarizer. <P>SOLUTION: In this sheet polarizer, a first protective film, a polarization film, and a second protective film are stacked in this order. The second protective film is formed of a laminate of a substantially vertically aligned polymerizable liquid crystal compound layer, acrylic polymer, and a transparent film containing cellulose ester containing at least one kind selected from a sugar ester compound which has one to twelve structures of at least one kind between a pyranose structure and a furanose structure, all or some of OH group in its structure being esterificated. The first protective film has a hard coat layer on the side remoter from the polarization film. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polarizing plate, a liquid crystal display device using the polarizing plate, and an IPS liquid crystal display device.

  As the performance of the outermost surface of the liquid crystal display device, it is easy to be physically damaged, and when it is damaged, the display image quality is impaired. Therefore, it is desired to enhance the surface hardness of the surface protective film. Moreover, when producing a polarizing plate (a laminated product in which a protective film is bonded to both or one side of a polarizing film having polarizing ability) constituting a liquid crystal display device, the surface is easily damaged when transported or cut out. There was a problem. Also from this fact, a high surface hardness (high hardness) is required. Moreover, a polarizing plate is produced by stamping the polarizing plate generally manufactured with a roll form.

  In recent years, the liquid crystal display device has been increased in screen size, and the polarizing plate needs to have a large size. However, when manufacturing a polarizing plate of a particularly large size, a polarizing plate using a protective film having a hard coating film with high hardness causes quality problems such as cracking and flaking of the punched end portion in the punching process. It was easy and caused a decrease in productivity. In addition, there is a problem that the quality such as the planar characteristics of the polarizing plate deteriorates.

  In particular, the above-described problems are easily manifested in a polarizing plate of an in-plane switching mode (IPS) liquid crystal display device to which optical compensation means is added.

  Patent Document 1 discloses a method for producing a polarizing plate which is excellent in smoothness in the polarizing plate punching process, is inexpensive and has high productivity. In Patent Document 1, a polarizing plate having a transparent protective film, a polarizing film, and an optical compensation layer in this order, the optical compensation layer including a transparent support and an optically anisotropic layer, It contains liquid crystal molecules and is characterized in that the absorption axis of the polarizing film is neither parallel nor perpendicular to the slow axis of the transparent support.

With the above-described technique, a certain level of smoothness and high productivity can be obtained, but with a protective film using a hard coat film with a hard surface hardness on the outermost surface, a sufficient improvement effect cannot be obtained, and punching is performed. Quality issues such as cracking and rolling at the edge of the polarizing plate were not improved.
JP 2005-513521 Gazette

  Accordingly, an object of the present invention is to provide a polarizing plate which has a high surface hardness and is free from cracks and whirling failures when punching the polarizing plate, and a liquid crystal having excellent surface smoothness (flatness) by using the polarizing plate. A display device is provided.

  The above object of the present invention is achieved by the following configurations.

  1. In the polarizing plate in which the first protective film, the polarizing film, and the second protective film are laminated in this order, the polymerizable liquid crystal compound layer in which the second protective film is substantially vertically aligned, and the following general formula (1) Or a transparent film containing a cellulose ester having at least one repeating unit represented by (2), and the first protective film has at least a hard coat layer on the side far from the polarizing film. A polarizing plate characterized by having.

[In formula, A and B represent a C1-C12 bivalent hydrocarbon group or a C1-C12 bivalent hydrocarbon group substituted by the hydroxyl group. However, A and B may be the same or different. ]
2. ^2. The polarizing plate as described in 1 above, wherein the hard coat layer has a Martens hardness (HMs) of 400 N / mm ² or more and 800 N / mm ² or less.

  3. 3. The polarizing plate as described in 1 or 2 above, wherein the hard coat layer contains a cationic polymerizable compound.

  4). 4. A liquid crystal display device using the polarizing plate according to any one of 1 to 3 on at least one side of a liquid crystal cell.

  5. 4. An IPS liquid crystal display device using the polarizing plate according to any one of 1 to 3 on at least one side of an in-plane switching mode (IPS) liquid crystal cell.

  According to the present invention, a liquid crystal having a high hardness on the surface, which can provide a polarizing plate that does not have cracks or sag failure when punched, and has excellent surface smoothness (flatness) by using the polarizing plate. A display device is provided.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  The polarizing plate of the present invention is a polarizing plate in which a first protective film, a polarizing film, and a second protective film are laminated in this order, and the polymerizable liquid crystal compound layer in which the second protective film is substantially vertically aligned. And a laminate of a transparent film containing a cellulose ester having at least one repeating unit represented by the following general formula (1) or (2), and the first protective film is far from the polarizing film It has at least a hard coat layer on the side.

  In order to solve the above problems, a laminate in which the first protective film has a hard coat layer on the surface on the viewing side, and a transparent film using a polymerizable liquid crystal compound layer and a cellulose ester having the specific structure as the second protective film is used. By disposing the polarizing plate, it is possible to provide a polarizing plate having a high hardness on the surface and free from cracks and crushing failures when punching the polarizing plate.

  Even if it has a high hardness hard coat layer on the viewing side surface of the first protective film, by using the second protective film of the present invention, the stress applied to the plane of the polarizing plate is made constant, As a result, when punching the polarizing plate, shear strain is less likely to be locally applied (uniformized), and surface quality such as suppression of phenomena such as cracks and rolling of the end portion punched by the polarizing plate and flatness are also achieved. Estimated to improve.

  Hereinafter, the present invention will be described in detail.

<Cellulose ester having at least one repeating unit represented by formula (1) or (2)>
The cellulose ester having at least one repeating unit represented by the general formula (1) or (2), which is one of the features of the present invention constituting the second protective film (hereinafter also referred to as retardation film), will be described. . By using the cellulose ester as a transparent film substrate, film deformation is unlikely to occur, smoothness is maintained, and by adopting the configuration of the present invention described in detail below, the surface has high hardness, and at the time of punching a polarizing plate It is possible to provide a polarizing plate that is free from cracks and cracks.

  The cellulose ester having at least one repeating unit represented by the following general formula (1) or (2) will be described in detail.

[In formula, A and B represent a C1-C12 bivalent hydrocarbon group or a C1-C12 bivalent hydrocarbon group substituted by the hydroxyl group. However, A and B may be the same or different. ]
A cellulose ester having at least one repeating unit represented by formula (1) or (2).

Specific examples of A are given below.
A-1-CH ₂ CH _{2-
A-2 -CH 2 CH 2 CH} 2 -
A-3 -CH = CH-

A-6 —CH ₂ C (CH ₃ ) ₂ —
Specific examples of B are given below.
B-1 _{-CH 2} CH 2 -
B-2-CH ₂ CH ₂ CH ₂ CH _2-

  The cellulose ester having a repeating unit represented by the general formula (1) or (2) is already partially substituted by cellulose having an unsubstituted hydroxyl group or an acyl group such as an acetyl group, a propionyl group, a butyryl group, or a phthalyl group. Esterification reaction of polybasic acid or its anhydride and polyhydric alcohol in the presence of cellulose ester substituted with hydroxyl group, or ring-opening polymerization of L-lactide, D-lactide, L-lactic acid, D-lactic acid Can be obtained by carrying out self-condensation.

  Examples of the polybasic acid anhydride used in the esterification reaction include, but are not limited to, maleic anhydride, phthalic anhydride, and fumaric anhydride.

  Examples of the polyhydric alcohol that can be used in the esterification reaction include glycerin, ethylene glycol, and propylene glycol, but are not particularly limited.

  As the catalyst used for the esterification reaction, the reaction can be carried out without a catalyst, but a known Lewis acid catalyst or the like can be used. Examples of catalysts that can be used include metals such as tin, zinc, titanium, bismuth, zirconium, germanium, antimony, sodium, potassium, and aluminum, and derivatives thereof. Particularly, the derivatives include metal organic compounds, carbonates, oxides, halides. Is preferred. Specific examples include octyl tin, tin chloride, zinc chloride, titanium chloride, alkoxy titanium, germanium oxide, zirconium oxide, antimony trioxide, and alkyl aluminum. Moreover, an acid catalyst typified by p-toluenesulfonic acid can also be used as the catalyst. Moreover, in order to accelerate | stimulate the dehydration reaction of carboxylic acid and alcohol, you may add well-known compounds, such as carbodiimide and dimethylaminopyridine.

  Such a reaction may be a reaction in an organic solvent capable of dissolving cellulose ester and other compounds to be reacted, or a reaction using a batch kneader capable of heating and stirring while adding a shearing force. It may be by reaction using a uniaxial or biaxial extruder.

  The repeating unit represented by the general formula (1) or (2) can be appropriately contained in the range of 0.5 to 190% by mass with respect to cellulose.

  Although the substitution degree of this cellulose ester can be selected suitably, it is preferable that it is 2.2-3 from the point of thermoplasticity and heat workability.

  In the cellulose ester having at least one repeating unit represented by the general formula (1) or (2), when the hydrogen atom of the hydroxyl group of cellulose is a fatty acid ester with an aliphatic acyl group, the aliphatic acyl group is carbon. Specific examples thereof include acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, octanoyl, lauroyl, stearoyl and the like.

  The polymerization degree of the cellulose ester having at least one repeating unit represented by the general formula (1) or (2) is not particularly limited, and is, for example, a viscosity average polymerization degree of 70 or more (for example, 80 to 800). It can be selected from a range, and may be 100 to 500, preferably 110 to 400, and more preferably about 120 to 350.

The repeating unit represented by the general formula (1) or (2) is, for example, 80 to 10,000, preferably 100 to 5000, more preferably about 200 to 2000, particularly 300 to 1500, as the number average molecular weight of the portion. Usually, it may be less than 1000. The number average molecular weight of repeating unit in which the cellulose ester has the cellulose ester after the reaction with the previous cellulose ester esterifying polystyrene-converted GPC (gel permeation chromatography) data, or by ^{1 H-NMR} Obtained by comparison.

  An oligomer or polyester having a repeating unit represented by formula (1) or (2) as a side reaction when the repeating unit represented by formula (1) or (2) is introduced into cellulose or cellulose ester However, since these compounds act as plasticizers, they need not be completely removed by purification. If content is 30 mass% or less with respect to a cellulose ester, there will be little change in the property of a cellulose ester. From the viewpoint of plasticity, it is preferably 0.5 to 20% by mass. These oligomers and polyesters have a number average molecular weight of 300 to 10,000, and preferably 500 to 8,000 from the viewpoint of plasticity.

  Also, a graft copolymerized modified glucan derivative (modified cellulose derivative) described in JP-A-2008-197561 can be used as a cellulose ester having a repeating unit represented by the general formula (1) or (2) of the present invention. I can do it.

  Further, a transparent film having a cellulose ester having a repeating unit represented by the general formula (1) or (2) (hereinafter, a cellulose ester film having a repeating unit represented by the general formula (1) or (2), or It is preferable that it is also called a cellulose ester film) having the following characteristics.

Transmittance: 80% or more Film thickness: 20-100 μm
0nm ≦ Ro ≦ 330nm
−100 nm ≦ Rt ≦ 340 nm
Ro = (nx−ny) × d
Rt = ((nx + ny) / 2−nz) × d
(Where nx is the refractive index in the slow axis direction in the plane of the cellulose ester film, ny is the refractive index in the direction perpendicular to the slow axis in the plane, nz is the refractive index in the thickness direction, and d is the refractive index in the thickness direction) Represents the thickness (nm) of the cellulose ester film.The measurement wavelength of the refractive index is 590 nm.) The refractive index is 23 ° C. and 55% RH using, for example, KOBRA-21ADH (Oji Scientific Instruments). The wavelength can be obtained at 590 nm under the following environment.

  The cellulose ester film has a length of 100 m to 9000 m, more preferably 1000 m to 7000 m, and a width of 1.2 m or more, more preferably 1.4 to 4 m. By making the length and width of the base film within the above ranges, the handleability and productivity are excellent.

  Moreover, the roll shape is preferable from the point of storage and handling property.

The cellulose ester film having a repeating unit represented by the general formula (1) or (2) is preferably one having few bright spot foreign substances. The bright spot foreign matter preferably has a bright spot diameter of 0.01 mm or more and 200 pieces / cm ² or less, more preferably 100 pieces / cm ² or less, and preferably 50 pieces / cm ² or less. 30 / cm ² or less, preferably 10 / cm ² or less, and most preferably none.

Moreover, it is preferable that it is 200 pieces / cm < ² > or less also about a bright spot of 0.005-0.01 mm or less, Furthermore, it is preferable that it is 100 pieces / cm < ² > or less, and it is 50 pieces / cm < ² > or less. The number is preferably 30 pieces / cm ² or less, more preferably 10 pieces / cm ² or less, and most preferably none.

<Additives>
The cellulose ester film having a repeating unit represented by the general formula (1) or (2) has at least one of an acrylic polymer and at least one of a pyranose structure or a furanose structure and has an OH of the structure. You may contain at least 1 type selected from the sugar ester compound which esterified all or one part of group.

<Sugar ester compound>
Examples of the sugar ester compound include glucose, galactose, mannose, fructose, xylose, arabinose, lactose, sucrose, cellobiose, cellotriose, maltotriose, raffinose and the like, and those having both a furanose structure and a pyranose structure are particularly preferable. An example is sucrose.

  The sugar ester compound is one in which part or all of the hydroxyl groups of the sugar compound are esterified or a mixture thereof.

The sugar ester compound is a compound obtained by condensing 1 or more and 12 or less of at least one pyranose structure or furanose structure represented by the following general formula (A). However, R < ₁₁ > -R < ₁₅ >, R < ₂₁ > -R < ₂₅ > represents a C2-C22 acyl group or a hydrogen atom, m and n represent the integer of 0-12 respectively, and m + n represents the integer of 1-12.

R _{11 to} R ₁₅ and R _{21 to} R ₂₅ are preferably a benzoyl group or a hydrogen atom. The benzoyl group may further have a substituent R26 (p is 0 to 5), and examples thereof include an alkyl group, an alkenyl group, an alkoxyl group, and a phenyl group. Further, these alkyl groups, alkenyl groups, and phenyl groups are It may have a substituent. Oligosaccharides can also be produced by a similar method.

  As a commercial item, monopet SB (Daiichi Kogyo Seiyaku Co., Ltd. product) etc. are mentioned, for example.

<Acrylic polymer>
You may add an acrylic polymer to the cellulose-ester film which has a repeating unit represented by General formula (1) or (2). Here, the acrylic polymer includes a methacrylic polymer. When an acrylic polymer is contained, it preferably exhibits negative birefringence in the stretching direction as a function, and the structure is not particularly limited, but is obtained by polymerizing an ethylenically unsaturated monomer. It is preferable that the polymer has a weight average molecular weight of 500 to 30,000. The acrylic polymer having a weight average molecular weight of 500 to 30,000 may be an acrylic polymer having an aromatic ring in the side chain or an acrylic polymer having a cyclohexyl group in the side chain.

  By controlling the composition of the polymer so that the weight average molecular weight of the polymer is 500 or more and 30000 or less, the compatibility between the cellulose ester and the polymer can be improved.

  As for the acrylic polymer having an aromatic ring in the side chain or the acrylic polymer having a cyclohexyl group in the side chain, if the weight average molecular weight is 500 or more and 10,000 or less, in addition to the above, cellulose after film formation The transparency of the ester film is excellent, the moisture permeability is extremely low, and it exhibits excellent performance as a protective film for polarizing plates.

  Since the polymer has a weight average molecular weight of 500 or more and 30000 or less, it is considered to be between the oligomer and the low molecular weight polymer. In order to synthesize such a polymer, it is difficult to control the molecular weight in normal polymerization, and it is desirable to use a method that can align the molecular weight as much as possible by a method that does not increase the molecular weight too much.

  Examples of the acrylic polymer include an ethylenically unsaturated monomer Xa having no aromatic ring and a hydroxyl group in the molecule, an ethylenically unsaturated monomer Xb having no aromatic ring in the molecule and a hydroxyl group, and Xa and Xb. Polymer X having a weight average molecular weight of 2000 or more and 30000 or less obtained by copolymerization with a copolymerizable ethylenically unsaturated monomer, or ethylenically unsaturated monomer Ya having no aromatic ring and copolymerized with Ya The polymer Y is preferably a polymer Y having a weight average molecular weight of 500 or more and 3000 or less obtained by polymerizing a possible ethylenically unsaturated monomer.

[Polymer X, Polymer Y]
As a method for adjusting Ro and Rt of the cellulose ester film having a repeating unit represented by the general formula (1) or (2), an ethylenically unsaturated monomer Xa having no aromatic ring and no hydroxyl group in the molecule, Weight average molecular weight 2000 or more, 30000 obtained by copolymerizing ethylenically unsaturated and nomeric Xb having a hydroxyl group and copolymerizable ethylenically unsaturated monomer excluding Xa and Xb The following high molecular weight polymer X, and more preferably a weight average obtained by polymerizing an ethylenically unsaturated monomer Ya having no aromatic ring and an ethylenically unsaturated monomer copolymerizable with Ya It is preferable to contain a low molecular weight polymer Y having a molecular weight of 500 or more and 3000 or less.

  Polymer X can be copolymerized with ethylenically unsaturated monomer Xa having no aromatic ring and hydroxyl group in the molecule and ethylenically unsaturated monomer Xb having no aromatic ring in the molecule and having a hydroxyl group, excluding Xa and Xb It is a polymer having a weight average molecular weight of 2000 or more and 30000 or less obtained by copolymerization with an ethylenically unsaturated monomer.

  Preferably, Xa is an acrylic or methacrylic monomer having no aromatic ring and hydroxyl group in the molecule, and Xb is an acrylic or methacrylic monomer having no aromatic ring and having a hydroxyl group in the molecule.

  The polymer X is represented by the following general formula (X).

Formula (X)
-[Xa] m- [Xb] n- [Xc] p-
In the general formula (X), Xa represents an ethylenically unsaturated monomer having no aromatic ring and hydroxyl group in the molecule, and Xb represents an ethylenically unsaturated monomer having no aromatic ring and having a hydroxyl group in the molecule. Xc represents a copolymerizable ethylenically unsaturated monomer excluding Xa and Xb. m, n, and p each represent a molar composition ratio. However, m ≠ 0 and m + n + p = 100.

  Furthermore, the polymer X is preferably a polymer represented by the following general formula (X-1).

Formula (X-1)
_{- [CH 2 -C (-R1)} (- CO 2 R2)] m- [CH 2 -C (-R3) (- CO 2 R4-OH) -] n- [Xc] p-
In the general formula (X-1), R1 and R3 each represent a hydrogen atom or a methyl group. R2 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group. R4 is _{-CH 2 -, - C 2 H} 4 - or _-C 3 _{H 6} - represents a. Xc _{is, [CH 2 -C (-R1)} (- CO 2 R2)] representing the a polymerizable monomer unit or _{[CH 2 -C (-R3) (} - - CO 2 R4-OH)]. m, n, and p represent a molar composition ratio. However, m ≠ 0 and m + n + p = 100.

  Although the monomer as a monomer unit which comprises the polymer X is mentioned below, it is not limited to this.

  In X, the hydroxyl group means not only a hydroxyl group but also a group having an ethylene oxide chain. Examples of the ethylenically unsaturated monomer Xa having no aromatic ring and hydroxyl group in the molecule include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), and butyl acrylate (n-, i-, s). -, T-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i -), Nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone), etc. The thing changed into acid ester can be mentioned. Among these, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate (i-, n-) are preferable.

  The ethylenically unsaturated monomer Xb having no hydroxyl ring in the molecule and having a hydroxyl group is preferably acrylic acid or methacrylic acid ester as a monomer unit having a hydroxyl group, such as acrylic acid (2-hydroxyethyl), acrylic acid. (2-hydroxypropyl), acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), or those obtained by replacing these acrylic acids with methacrylic acid. Preferred are acrylic acid (2-hydroxyethyl) and methacrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), and acrylic acid (3-hydroxypropyl).

  Xc is not particularly limited as long as it is a monomer other than Xa and Xb and is a copolymerizable ethylenically unsaturated monomer, but preferably has no aromatic ring.

  The molar composition ratio m: n of Xa and Xb is preferably in the range of 99: 1 to 65:35, more preferably in the range of 95: 5 to 75:25. P of Xc is 0-10. Xc may be a plurality of monomer units.

  When there are many X and molar composition ratios, compatibility with a cellulose ester will improve, but the retardation value Rt of a film thickness direction will become large. When the molar composition ratio of Xb is large, the compatibility is deteriorated, but the effect of reducing Rt is high.

  Further, if the molar composition ratio of Xb exceeds the above range, haze tends to occur during film formation, and it is preferable to optimize these and determine the molar composition ratio of Xa and Xb.

  The molecular weight of the high molecular weight polymer X is more preferably 5000 or more and 30000 or less, and still more preferably 8000 or more and 25000 or less.

  By setting the weight average molecular weight to 5,000 or more, it is preferable because advantages such as little dimensional change under high temperature and high humidity of the cellulose ester film having the repeating unit represented by the general formula (1) or (2) are obtained.

  When the weight average molecular weight is 30000 or less, the compatibility with the cellulose ester is further improved, and bleeding out under high temperature and high humidity and further haze generation immediately after film formation are suppressed.

  The weight average molecular weight of the polymer X according to the present invention can be adjusted by a known molecular weight adjusting method. Examples of such a molecular weight adjusting method include a method of adding a chain transfer agent such as carbon tetrachloride, lauryl mercaptan, octyl thioglycolate, and the like.

  The polymerization temperature is usually from room temperature to 130 ° C., preferably from 50 ° C. to 100 ° C., and this temperature or the polymerization reaction time can be adjusted.

  In addition, a weight average molecular weight etc. can be calculated | required according to the above-mentioned method.

  The polymer Y is a polymer having a weight average molecular weight of 500 or more and 3000 or less obtained by polymerizing an ethylenically unsaturated monomer Ya having no aromatic ring. A weight average molecular weight of 500 or more is preferred because the residual monomer in the polymer is reduced.

  Moreover, it is preferable to set it as 3000 or less in order to maintain retardation value Rt fall performance. Ya is preferably an acrylic or methacrylic monomer having no aromatic ring.

  The polymer Y is represented by the following general formula (Y).

General formula (Y)
-[Ya] k- [Yb] q-
In the general formula (Y), Ya represents an ethylenically unsaturated monomer having no aromatic ring, and Yb represents an ethylenically unsaturated monomer copolymerizable with Ya. k and q each represent a molar composition ratio. However, k ≠ 0 and k + q = 100.

  The polymer Y is more preferably a polymer represented by the following general formula (Y-1).

General formula (Y-1)
_{- [CH 2 -C (-R5)} (- CO 2 R6)] k- [Yb] q-
In the general formula (Y-1), R5 represents a hydrogen atom or a methyl group, respectively. R6 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group. Yb represents a monomer unit copolymerizable with [CH ₂ —C (—R 5) (— CO ₂ R 6)]. k and q each represent a molar composition ratio. However, k ≠ 0 and k + q = 100.

Yb is a _{Ya [CH 2 -C (-R5)} (- CO 2 R6)] and is not particularly limited as long as it is copolymerizable ethylenically unsaturated monomers. Yb may be plural. k + q = 100, q is preferably 0-30.

  The ethylenically unsaturated monomer Ya constituting the polymer Y obtained by polymerizing the ethylenically unsaturated monomer having no aromatic ring is, for example, methyl acrylate, ethyl acrylate, propyl acrylate ( i-, n-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), acrylic Acid heptyl (n-, i-), octyl acrylate (n-, i-), nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), cyclohexyl acrylate, acrylic acid ( 2-ethylhexyl), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropiyl) ), Acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), methacrylic acid ester, the above acrylic acid ester changed to methacrylic acid ester; unsaturated acid, for example, acrylic acid, methacrylic acid And maleic anhydride, crotonic acid, itaconic acid and the like.

  Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl pivalate, and vinyl caproate. Vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl octylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl cinnamate and the like are preferred. Yb may be plural.

  In order to synthesize the polymers X and Y, it is difficult to control the molecular weight in normal polymerization, and it is desirable to use a method that can make the molecular weight as uniform as possible by a method that does not increase the molecular weight too much.

  Such polymerization methods include a method using a peroxide polymerization initiator such as cumene peroxide and t-butyl hydroperoxide, a method using a polymerization initiator in a larger amount than normal polymerization, and a mercapto compound in addition to the polymerization initiator. And a method using a chain transfer agent such as carbon tetrachloride, a method using a polymerization terminator such as benzoquinone and dinitrobenzene in addition to the polymerization initiator, and further disclosed in JP 2000-128911 or 2000-344823 Examples thereof include a method of bulk polymerization using a compound having one thiol group and a secondary hydroxyl group, or a polymerization catalyst in which the compound and an organometallic compound are used in combination, and any of them is preferably used.

  In particular, the polymer Y is preferably a polymerization method using a compound having a thiol group and a secondary hydroxyl group in the molecule as a chain transfer agent. In this case, the terminal of the polymer Y has a hydroxyl group and a thioether resulting from the polymerization catalyst and the chain transfer agent. The compatibility between Y and cellulose ester can be adjusted by this terminal residue.

  The hydroxyl values of the polymers X and Y are preferably 30 to 150 [mgKOH / g].

  The hydroxyl value is measured in accordance with JIS K 0070 (1992). This hydroxyl value is defined as the number of mg of potassium hydroxide required to neutralize acetic acid bound to the sample 1 and acetylated and bound to the hydroxyl group.

  Specifically, sample Xg (about 1 g) is precisely weighed in a flask, and 20 ml of an acetylating reagent (a solution obtained by adding pyridine to 20 ml of acetic anhydride to 400 ml) is accurately added thereto. An air cooling tube is attached to the mouth of the flask and heated in a glycerin bath at 95-100 ° C.

  After 1 hour and 30 minutes, the mixture is cooled, 1 ml of purified water is added from an air condenser, and acetic anhydride is decomposed into acetic acid.

  Next, titration is performed with a 0.5 mol / L potassium hydroxide ethanol solution using a potentiometric titrator, and the inflection point of the obtained titration curve is set as the end point.

  Further, as a blank test, titration is performed without a sample, and an inflection point of the titration curve is obtained. The hydroxyl value is calculated by the following formula.

Hydroxyl value = {(BC) × f × 28.05 / X} + D
In the formula, B is the amount (ml) of 0.5 mol / L potassium hydroxide ethanol solution used for the blank test, C is the amount (ml) of 0.5 mol / L potassium hydroxide ethanol solution used for titration, f is a factor of a 0.5 mol / L potassium hydroxide ethanol solution, D is an acid value, and 28.05 is 1/2 of 1 mol amount 56.11 of potassium hydroxide.

  The above-mentioned polymer X and polymer Y are both excellent in compatibility with the cellulose ester film having the repeating unit represented by the general formula (1) or (2), excellent in productivity without evaporation and volatilization, and polarized Retention property as a protective film for plates is good, moisture permeability is small, and dimensional stability is excellent.

The content of the polymer X and the polymer Y in the cellulose ester film is preferably in a range satisfying the following formulas (i) and (ii). When the content of the polymer X is Xg (mass% = (mass of polymer X / mass of cellulose ester) × 100) and the content of the polymer Y is Yg (mass%),
Formula (i) 5 ≦ Xg + Yg ≦ 35 (mass%)
Formula (ii) 0.05 ≦ Yg / (Xg + Yg) ≦ 0.4
A preferable range of (Xg + Yg) in the formula (i) is 10 to 35% by mass. If the polymer X and the polymer Y are 5 mass% or more as a total amount with respect to the total mass of the cellulose ester, the polymer X and the polymer Y have a sufficient effect for adjusting the retardation value Rt.

  The polymer X and the polymer Y are directly added and kneaded as a material constituting the melting described later.

  The cellulose ester film having the repeating unit represented by the general formula (1) or (2) is a plasticizer that imparts processability to the film, an antioxidant that prevents deterioration of the film, and an ultraviolet absorption that imparts an ultraviolet absorbing function. An additive such as an agent, fine particles (matting agent) for imparting slipperiness to the film, and a retardation adjusting agent for adjusting the retardation of the film may be contained.

<Other additives>
As other additives, it is necessary to appropriately select a plasticizer.

<Plasticizer>
In the production of a cellulose ester film having a repeating unit represented by the general formula (1) or (2), it is preferable to contain at least one plasticizer in the film-forming material.

  The plasticizer can be used alone or in combination of two or more, but at least one is a polyhydric alcohol ester plasticizer having a molecular weight of 350 to 1500 having a structure in which an organic acid and a trivalent or higher alcohol are condensed. Is preferred.

  Other plasticizers that can be used are not particularly limited, but are preferably polyhydric alcohol ester plasticizers, aromatic-terminated polyester plasticizers, glycolate plasticizers, phthalate ester plasticizers, fatty acid esters. It is selected from system plasticizers, polymer plasticizers, sugar ester compounds and the like.

  If the amount of the plasticizer used is less than 1% by mass relative to the cellulose derivative, the effect of reducing the moisture permeability of the film is small, which is not preferable. If the amount exceeds 20% by mass, the physical properties of the film at high temperature durability deteriorate. -20 mass% is preferable. Hereinafter, preferred plasticizers will be described.

(Polyhydric ester plasticizer)
The polyhydric alcohol ester plasticizer is an ester of an organic acid and a polyhydric alcohol, and the organic acid is represented by the following general formula (3).

In the formula, R _{1 to} R ₅ represent a hydrogen atom or a cycloalkyl group, an aralkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, a carbonyloxy group, an oxycarbonyl group, or an oxycarbonyloxy group. These may be further substituted. L represents a linking group and represents a substituted or unsubstituted alkylene group, an oxygen atom, or a direct bond.

The cycloalkyl group represented by R ₁ to R _5, preferably a cycloalkyl group having 3 to 8 carbon atoms, specifically cyclopropyl, cyclopentyl, groups such as cyclohexyl. These groups may be substituted, and preferred substituents include halogen atoms such as chlorine atom, bromine atom, fluorine atom, hydroxyl group, alkyl group, alkoxy group, cycloalkoxy group, aralkyl group (this phenyl group). The group may be further substituted with an alkyl group or a halogen atom), an alkenyl group such as a vinyl group or an allyl group, or a phenyl group (this phenyl group may be further substituted with an alkyl group or a halogen atom). Phenoxy group (this phenyl group may be further substituted by an alkyl group or a halogen atom), an acyl group having 2 to 8 carbon atoms such as an acetyl group or a propionyl group, an acetyloxy group, or a propionyloxy group. And an unsubstituted carbonyloxy group having 2 to 8 carbon atoms such as a group.

The aralkyl group represented by R _{1 to} R ₅ represents a group such as a benzyl group, a phenethyl group, and a γ-phenylpropyl group, and these groups may be substituted. Preferred substituents include The group which may be substituted with the said cycloalkyl group can be mentioned similarly.

Examples of the alkoxy group represented by R _{1 to} R ₅ include an alkoxy group having 1 to 8 carbon atoms, specifically, methoxy, ethoxy, n-propoxy, n-butoxy, n-octyloxy, isopropoxy. , Alkoxy groups such as isobutoxy, 2-ethylhexyloxy, or t-butoxy.

  These groups may be substituted, and preferred substituents include halogen atoms such as chlorine atom, bromine atom, fluorine atom, hydroxyl group, alkoxy group, cycloalkoxy group, aralkyl group (this phenyl group). May be substituted with an alkyl group or a halogen atom), an alkenyl group, a phenyl group (this phenyl group may be further substituted with an alkyl group or a halogen atom), an aryloxy group (for example, phenoxy) An acyl group such as an acetyl group or a propionyl group, or an aryl group such as an acetyloxy group or a propionyloxy group (the phenyl group may be further substituted with an alkyl group or a halogen atom). Arylcarbonyl groups such as unsubstituted acyloxy groups and benzoyloxy groups Shi group.

Examples of the cycloalkoxy group represented by R _{1 to} R ₅ include an unsubstituted cycloalkoxy group having 1 to 8 carbon atoms, specifically cyclopropyloxy, cyclopentyloxy, cyclohexyloxy. And the like.

  In addition, these groups may be substituted, and preferable examples thereof include the same groups that may be substituted with the cycloalkyl group.

Examples of the aryloxy group represented by R _{1 to} R ₅ include a phenoxy group, and the phenyl group includes a substituent that may be substituted with the cycloalkyl group such as an alkyl group or a halogen atom. May be substituted.

Examples of the aralkyloxy group represented by R _{1 to} R ₅ include a benzyloxy group and a phenethyloxy group, and these substituents may be further substituted. Preferred substituents include the above cycloalkyl The group which may be substituted with a group can be mentioned similarly.

Examples of the acyl group represented by R _{1 to} R ₅ include an unsubstituted acyl group having 2 to 8 carbon atoms such as an acetyl group and a propionyl group (the hydrocarbon group of the acyl group includes alkyl, alkenyl, alkynyl). These substituents may be further substituted, and preferred substituents include the same groups that may be substituted with the cycloalkyl group.

As the carbonyloxy group represented by R _{1 to} R ₅ , an unsubstituted acyloxy group having 2 to 8 carbon atoms such as acetyloxy group and propionyloxy group (the hydrocarbon group of the acyl group is alkyl, alkenyl, alkynyl). And arylcarbonyloxy groups such as a benzoyloxy group, and these groups may be further substituted with the same groups as those which may be substituted with the cycloalkyl group.

The oxycarbonyl group represented by R _{1 to} R ₅ represents an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group or a propyloxycarbonyl group, or an aryloxycarbonyl group such as a phenoxycarbonyl group.

  These substituents may be further substituted, and preferred examples of the substituent include the same groups that may be substituted with the cycloalkyl group.

The oxycarbonyloxy group represented by R _{1 to} R ₅ represents an alkoxycarbonyloxy group having 1 to 8 carbon atoms such as a methoxycarbonyloxy group, and these substituents may be further substituted and are preferably substituted. Examples of the group include the same groups that may be substituted on the cycloalkyl group.

Any one of R _{1 to} R ₅ may be connected to each other to form a ring structure.

The linking group represented by L represents a substituted or unsubstituted alkylene group, an oxygen atom, or a direct bond, and the alkylene group is a group such as a methylene group, an ethylene group, or a propylene group. These groups may be further substituted with the groups mentioned as groups that may be substituted with the groups represented by R _{1 to} R ₅ .

  Among these, a direct bond and an aromatic carboxylic acid are particularly preferable as the linking group represented by L.

Further, the organic acid represented by the general formula (3) constituting the ester compound serving as a plasticizer includes at least R ₁ or R ₂ having the alkoxy group, acyl group, oxycarbonyl group, carbonyloxy group, oxy Those having a carbonyloxy group are preferred. A compound having a plurality of substituents is also preferred.

  In addition, the organic acid which substitutes the hydroxyl group of trihydric or more alcohol may be single type, or may be multiple types.

  The trihydric or higher alcohol compound that reacts with the organic acid represented by the general formula (3) to form a polyhydric alcohol ester compound is preferably a 3-20 valent aliphatic polyhydric alcohol. As for the above alcohol, what is represented by following General formula (4) is preferable.

Formula (4) R '-(OH) m
In the formula, R ′ represents an m-valent organic group, m represents a positive integer of 3 or more, and the OH group represents an alcoholic hydroxyl group. Particularly preferred is a polyhydric alcohol having 3 or 4 as m.

  Examples of preferred polyhydric alcohols include, but are not limited to, the following.

  Adonitol, arabitol, 1,2,4-butanetriol, 1,2,3-hexanetriol, 1,2,6-hexanetriol, glycerin, diglycerin, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, ga Examples include lactitol, inositol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, and xylitol.

  In particular, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol are preferable.

  The ester of the organic acid represented by the general formula (3) and the trihydric or higher polyhydric alcohol represented by the general formula (4) can be synthesized by a known method. In the examples, typical synthesis examples are shown. For example, the organic acid represented by the general formula (3) and the polyhydric alcohol represented by the general formula (4) are condensed and esterified in the presence of an acid, for example. There are a method, a method in which an organic acid is preliminarily converted into an acid chloride or an acid anhydride and a reaction with a polyhydric alcohol, a method in which a phenyl ester of an organic acid is reacted with a polyhydric alcohol, and the like. It is preferable to select a method with good yield.

  As a plasticizer comprising an organic acid represented by the general formula (3) and an ester of a trihydric or higher polyhydric alcohol represented by the general formula (4), a compound represented by the following general formula (5) is preferable. .

In the formula, R _{6 to} R ₂₀ represent a hydrogen atom or a cycloalkyl group, an aralkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, a carbonyloxy group, an oxycarbonyl group, or an oxycarbonyloxy group. These may be further substituted. R ₂₁ represents a hydrogen atom or an alkyl group.

Cycloalkyl groups R ₆ to R _20, aralkyl group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, carbonyloxy group, an oxycarbonyl group, for oxy carbonyloxy group, the general formula ( The same group as R < ₁ > -R < ₅ > of 3) is mentioned.

  Below, the specific compound of a polyhydric alcohol ester is illustrated.

<Aromatic terminal polyester plasticizer>
An aromatic terminal polyester plasticizer represented by the following general formula (6) can be used.

General formula (6) B- (GA) n-GB
(In the formula, B is an arylcarboxylic acid residue, G is an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms, A Represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.)
In general formula (6), an arylcarboxylic acid residue represented by B and an alkylene glycol residue or oxyalkylene glycol residue or arylglycol residue represented by G, an alkylenedicarboxylic acid residue or aryldicarboxylic acid represented by A And is obtained by the same reaction as a normal polyester compound.

  Examples of the arylcarboxylic acid component of the aromatic-terminated polyester plasticizer include benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, normal propylbenzoic acid, amino There exist benzoic acid, acetoxybenzoic acid, etc., These can be used as a 1 type, or 2 or more types of mixture, respectively.

  Examples of the alkylene glycol component having 2 to 12 carbon atoms of the aromatic terminal polyester plasticizer include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, and 1,3-butanediol. 1,2-propanediol, 2-methyl 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl -1,5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl 1,3-pentanediol, 2- There are til 1,3-hexanediol, 2-methyl 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, and the like. Used as a mixture of two or more.

  In particular, an alkylene glycol having 2 to 12 carbon atoms is particularly preferable because of excellent compatibility with a cellulose ester.

  Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms of the aromatic terminal polyester plasticizer include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol. Can be used as one or a mixture of two or more.

  Examples of the alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the aromatic terminal polyester plasticizer include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. These are each used as one or a mixture of two or more.

  Examples of the arylene dicarboxylic acid component having 6 to 12 carbon atoms include phthalic acid, terephthalic acid, isophthalic acid, 1,5 naphthalene dicarboxylic acid, and 1,4 naphthalene dicarboxylic acid.

  In the aromatic terminal polyester plasticizer, n is preferably 1 or more and 100 or less, and the number average molecular weight is preferably 300 to 1500, more preferably 400 to 1000.

  The acid value is 0.5 mgKOH / g or less, the hydroxyl value is 25 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less, and the hydroxyl value is 15 mgKOH / g or less.

  The aromatic terminal polyester plasticizer represented by the general formula (6) is preferably contained in an amount of 0.5 to 30% by mass with respect to the cellulose ester.

  Although the specific compound of an aromatic terminal polyester plasticizer is shown, it is not limited to this.

(Polymer plasticizer)
The cellulose ester film preferably uses a polymer plasticizer other than the acrylic polymer.

  Specifically, aliphatic hydrocarbon polymers, alicyclic hydrocarbon polymers, polyvinyl isobutyl ether, vinyl polymers such as poly N-vinyl pyrrolidone, copolymers of methyl methacrylate and N-vinyl pyrrolidone (for example, Copolymerization ratio (any ratio between 1:99 and 99: 1), polystyrene, styrene-based polymers such as poly-4-hydroxystyrene, polybutylene succinate, polyesters such as polyethylene terephthalate, polyethylene naphthalate, polyethylene oxide, polypropylene Examples include polyethers such as oxides, polyamides, polyurethanes, and polyureas.

  The number average molecular weight is preferably about 1,000 to 500,000, particularly preferably 5,000 to 200,000. If it is 1,000 or less, the volatility becomes large, and if it exceeds 500,000, the plasticizing ability tends to decrease, which may adversely affect the mechanical properties of the cellulose ester retardation film.

  These polymer plasticizers may be a homopolymer composed of one monomer repeating unit or a copolymer having a repeating structure of a plurality of monomers. Two or more of the above polymers may be used in combination.

  Further, the method for measuring the amount of plasticizer on the surface is not particularly limited. For example, a knife or the like is used to quantitatively analyze the surface of the film by cutting it about 20 nm or the amount of plasticizer in the thickness direction of the film is measured by IR or atomic absorption It is quantified using a method such as scanning with the above.

  As acrylic polymers, Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd.), Dianal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) ) And the like.

<Antioxidant>
As the antioxidant, those which are generally known can be used. In particular, lactone, sulfur, phenol, double bond, hindered amine, and phosphorus compounds can be preferably used.

  For example, the thing containing what is marketed by the brand name "IrgafosXP40" and "IrgafosXP60" from Ciba Japan KK is preferable.

  The phenolic compound preferably has a 2,6-dialkylphenol structure. For example, Ciba Japan Co., Ltd., “Irganox 1076”, “Irganox 1010”, ADEKA “ADEKA STAB AO-50” And those commercially available.

  The phosphorous compounds are, for example, from Sumitomo Chemical Co., Ltd., “Sumilizer GP” (from ADEKA, Inc., “ADK STAB PEP-24G”, “ADK STAB PEP-36”, “ADK STAB 3010”, Ciba Japan Co., Ltd. The product name “GGA-P101” from the company “IRGAFOS P-EPQ” and “GSY-P101” from Sakai Chemical Industry Co., Ltd. and those commercially available are preferred.

  The hindered amine compound is preferably commercially available from Ciba Japan Co., Ltd. as “Tinuvin 144 (AO2)” and “Tinvin 770”, and from ADEKA Co., Ltd. as “ADK STAB LA-52”.

  As the sulfur compound, for example, those commercially available from Sumitomo Chemical Co., Ltd. under the trade names of “Sumilizer TPL-R” and “Sumilizer TP-D” are preferable.

  The above-mentioned double bond type compounds are preferably those commercially available from Sumitomo Chemical Co., Ltd. under the trade names “Sumilizer GM” and “Sumilizer GS”.

  Furthermore, it is possible to include a compound having an epoxy group as described in US Pat. No. 4,137,201 as an acid and an agent.

  The amount of these antioxidants and the like to be appropriately added is determined in accordance with the process at the time of recycling, but generally 0.05 to 20% by mass, preferably with respect to the resin as the main raw material of the film Is added in the range of 0.1 to 1% by mass.

  These antioxidants can obtain a synergistic effect by using several different types of compounds in combination rather than using only one kind. For example, the combined use of lactone, phosphorus, phenol and double bond compounds is preferred.

<Retardation adjuster>
You may contain the compound for adjusting retardation in the cellulose-ester film which has a repeating unit represented by General formula (1) or (2).

  As the compound to be added for adjusting the retardation, an aromatic compound having two or more aromatic rings as described in EP 911,656A2 can also be used.

  Two or more aromatic compounds may be used in combination. The aromatic ring of the aromatic compound includes an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring. An aromatic heterocyclic ring is particularly preferred, and the aromatic heterocyclic ring is generally an unsaturated heterocyclic ring. Of these, compounds having a 1,3,5-triazine ring are particularly preferred.

<Colorant>
It is preferred to use a colorant. The colorant means a dye or a pigment, and refers to a colorant having an effect of making the color tone of a liquid crystal screen blue or adjusting a yellow index and reducing haze. Various dyes and pigments can be used as the colorant, but anthraquinone dyes, azo dyes, phthalocyanine pigments and the like are effective.

<Ultraviolet absorber>
The ultraviolet absorber is not particularly limited, and examples thereof include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders, and the like. . It is good also as a polymer type ultraviolet absorber.

<Matting agent>
It is preferable to add a matting agent in order to impart the slipperiness of the film. As the matting agent, any inorganic compound or organic compound may be used as long as it has heat resistance at the time of melting without impairing the transparency of the resulting film. For example, talc, mica, zeolite, diatomaceous earth, calcined siliceous earth, Kaolin, sericite, bentonite, smectite, clay, silica, quartz powder, glass beads, glass powder, glass flake, milled fiber, wollastonite, boron nitride, boron carbide, titanium boride, magnesium carbonate, heavy calcium carbonate, Light calcium carbonate, calcium silicate, aluminum silicate, magnesium silicate, magnesium aluminosilicate, alumina, silica, zinc oxide, titanium dioxide, iron oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, calcium sulfate , Barium sulphate, silicon carbide, aluminum carbide, titanium carbide, aluminum nitride, silicon nitride, titanium nitride, and white carbon. These matting agents can be used alone or in combination of two or more. By using particles having different particle sizes and shapes (for example, acicular and spherical), both transparency and slipperiness can be made highly compatible.

  Among these, silicon dioxide is particularly preferably used since it has a refractive index close to that of cellulose ester and is excellent in transparency (haze). Specific examples of silicon dioxide include Aerosil 200V, Aerosil R972V, Aerosil R972, R974, R812, 200, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.), Sea Hoster KEP-10, Sea Hoster KEP-30, Commercial products having trade names such as Seahoster KEP-50 (above, made by Nippon Shokubai Co., Ltd.), Silo Hovic 100 (made by Fuji Silysia), Nip Seal E220A (made by Nippon Silica Kogyo), Admafine SO (made by Admatechs), etc. Can be preferably used.

  The shape of the particles can be used without particular limitation, such as indefinite shape, needle shape, flat shape, spherical shape, etc. However, the use of spherical particles is particularly preferable because the transparency of the resulting film can be improved. When the particle size is close to the wavelength of visible light, light is scattered and the transparency is deteriorated. Therefore, the particle size is preferably smaller than the wavelength of visible light, and more preferably ½ or less of the wavelength of visible light. .

  If the size of the particles is too small, the slipperiness may not be improved, so the range of 80 nm to 180 nm is particularly preferable.

  The particle size means the size of the aggregate when the particle is an aggregate of primary particles. Moreover, when a particle is not spherical, it means the diameter of a circle corresponding to the projected area.

<Viscosity reducing agent>
For the purpose of reducing the melt viscosity, a hydrogen bonding solvent can be added. The hydrogen bonding solvent is J.I. N. As described in Israel Ativili, “Intermolecular Forces and Surface Forces” (Takeshi Kondo, Hiroyuki Oshima, Maglow Hill Publishing, 1991) and electrically negative atoms (oxygen, nitrogen, fluorine, chlorine) An organic solvent capable of producing a hydrogen atom-mediated “bond” between a hydrogen atom covalently bonded to an electronegative atom, ie, a bond having a large bond moment and containing hydrogen, such as O—H (Oxygen hydrogen bond), N—H (nitrogen hydrogen bond), and organic solvent that can arrange adjacent molecules by including F—H (fluorine hydrogen bond).

  These have the ability to form stronger hydrogen bonds with cellulose than intermolecular hydrogen bonds of cellulose resin. In the melt casting method performed in the present invention, the glass transition temperature of the cellulose resin used alone is higher than that. The melting temperature of the cellulose resin composition can be lowered by adding a hydrogen bonding solvent.

  Alternatively, the melt viscosity of the cellulose resin composition containing a hydrogen bonding solvent can be lowered than that of the cellulose resin at the same melting temperature.

  Examples of the hydrogen bonding solvent include alcohols: for example, methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, t-butanol, 2-ethylhexanol, heptanol, octanol, nonanol, dodecanol, ethylene glycol, Propylene glycol, hexylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, hexyl cellosolve, glycerin, etc., ketones: acetone, methyl ethyl ketone, etc., carboxylic acids: eg formic acid, acetic acid, propionic acid, Butyric acid, etc., ethers: eg, diethyl ether, tetrahydrofuran, dioxane, etc., Pyrrolidones: eg, N-methyl Pyrrolidone, etc., amines: for example, can be exemplified trimethylamine, pyridine, etc., and the like.

  These hydrogen bonding solvents can be used alone or in admixture of two or more. Among these, alcohol, ketone, and ether are preferable, and methanol, ethanol, propanol, isopropanol, octanol, dodecanol, ethylene glycol, glycerin, acetone, and tetrahydrofuran are particularly preferable. Furthermore, water-soluble solvents such as methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerin, acetone, and tetrahydrofuran are particularly preferable. Here, water-soluble means that the solubility in 100 g of water is 10 g or more. These solvents are volatilized at the time of melt film formation, and finally the content of the solvent is 0.01% by mass or less.

  Hereinafter, the film forming method of the cellulose ester film described above will be described.

<Melt casting method>
Melt casting is a process in which a composition containing an additive such as a cellulose ester and a plasticizer is heated and melted to a temperature showing fluidity, and then a melt containing the flowable cellulose ester is cast. Defined as melt film formation. More specifically, the heat melting molding method can be classified into a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, a stretch molding method, and the like. Among these, in order to obtain a cellulose ester film excellent in mechanical strength and surface accuracy, the melt extrusion method is excellent.

  Hereinafter, the melt casting film forming method will be described.

(Process for producing molten pellets of cellulose ester and additives)
It is preferable that a plurality of raw materials used for melt extrusion are usually kneaded and pelletized in advance. Pelletization may be performed by a known method. For example, dry cellulose ester, plasticizer, and other additives are fed to an extruder using a feeder, kneaded using a single or twin screw extruder, and extruded from a die into a strand. Can be done by water cooling or air cooling and cutting. It is important to dry the raw material before extruding to prevent decomposition of the raw material. In particular, since the cellulose ester easily absorbs moisture, it is preferable to dry it at 70 to 140 ° C. for 3 hours or more with a dehumidifying hot air dryer or a vacuum dryer to keep the moisture content at 200 ppm or less, and further 100 ppm or less.

  The additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders. A small amount of additives such as antioxidants are preferably mixed in advance in order to mix more uniformly.

  Mixing of the antioxidants may be performed by mixing solids, and if necessary, the antioxidant may be dissolved in a solvent, impregnated with cellulose ester and mixed, or sprayed and mixed. Also good.

  A vacuum nauter mixer or the like is preferable because drying and mixing can be performed simultaneously. Moreover, when touching with air, such as an exit from a feeder part or die | dye, it is preferable to set it as atmosphere, such as dehumidified air and dehumidified N2 gas.

  In addition, it is preferable to keep the supply hopper and the like to the extruder warm because moisture absorption can be prevented.

  Matting agents, UV absorbers, and the like may be applied to the obtained pellets or added in an extruder during film formation.

  The extruder is preferably processed at as low a temperature as possible so as to be able to be pelletized so that the shearing force is suppressed and the resin does not deteriorate (decrease in molecular weight, coloring, gel formation, etc.). For example, in the case of a twin screw extruder, it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.

  Kneader discs can improve kneadability, but care must be taken against shearing heat generation. Mixability is sufficient without using a kneader disk. The suction from the vent hole may be performed as necessary. Since there is almost no volatile component at low temperatures, there may be no vent hole.

(Process of extruding a melt of cellulose ester and additive from the die)
The polymer dried after dehumidifying hot air, vacuum or reduced pressure was removed using a uniaxial or biaxial extruder, the melting temperature during extrusion was about 200 to 300 ° C, and filtered through a leaf disk type filter to remove foreign matter. Then, it is cast into a film from a T die and solidified on a cooling roll.

  When introducing from the supply hopper to the extruder, it is preferable to prevent oxidative decomposition or the like under vacuum, reduced pressure, or inert gas atmosphere.

  The extrusion flow rate is preferably performed stably by introducing a gear pump or the like. Further, a stainless fiber sintered filter is preferably used as a filter used for removing foreign substances.

  The stainless steel fiber sintered filter is a united stainless steel fiber body that is intricately intertwined and compressed, and the contact points are sintered and integrated. The density of the fiber is changed depending on the thickness of the fiber and the amount of compression, and the filtration accuracy is improved. Can be adjusted.

  It is preferable to use a multilayer body in which the filtration accuracy is repeated coarsely and densely multiple times. Further, it is preferable to adopt a configuration in which the filtration accuracy is sequentially increased or a method in which coarse and dense filtration accuracy is repeated, so that the filtration life of the filter can be extended and the accuracy of capturing foreign matters and gels can be improved.

  If flaws or foreign matter adhere to the die, streaky defects may occur. Such defects are also referred to as die lines, but in order to reduce surface defects such as die lines, it is preferable that the piping from the extruder to the die has a structure in which the resin retention portion is minimized. It is preferable to use a die that has as few scratches as possible inside the lip.

  The inner surface that is in contact with the molten resin, such as an extruder or a die, is preferably subjected to a surface treatment that makes it difficult for the molten resin to adhere, such as by reducing the surface roughness or using a material with low surface energy. Specifically, a hard chrome plated or ceramic sprayed material is polished so that the surface roughness is 0.2 S or less.

  Additives such as plasticizers may be mixed with the resin in advance, or may be kneaded in the middle of the extruder. In order to add uniformly, it is preferable to use a mixing apparatus such as a static mixer.

(Process of casting while pressing the melt extruded from the die between the cooling roll and the elastic touch roll)
The film temperature on the touch roll side when the film is nipped between the cooling roll and the elastic touch roll is preferably Tg or more and Tg + 110 ° C. or less of the film. A well-known roll can be used for the roll which has the elastic body surface used for such a purpose. When peeling the film from the cooling roll, it is preferable to control the tension to prevent deformation of the film.

(Stretching process)
The film obtained as described above passes through the step of contacting the cooling roll, and then is further stretched in MD and TD at a stretching speed of 400% / min to 1500% / min, and the film is at least in the film forming direction or width. It is preferable to stretch 50% to 200% in either of the hand directions. This stretching step determines the elastic modulus of MD and TD of the present invention. As a method of stretching, a known roll stretching machine or tenter can be preferably used. The stretching temperature is usually preferably performed in the temperature range of Tg to Tg + 60 ° C. of the resin constituting the film.

  The glass transition temperature Tg of the film constituting material can be controlled by varying the material type constituting the film and the ratio of the constituting material. When producing a retardation film, Tg is 110 ° C. or higher, preferably 125 ° C. or higher. If the Tg of the film is too high, the temperature is increased when the film constituent material is made into a film, so that the energy consumption for heating is increased, and the material itself may be decomposed when it is made into a film, resulting in coloring. Therefore, Tg is preferably 250 ° C. or lower.

  The stretching step may be carried out by known heat setting conditions, cooling, and relaxation treatment, and may be appropriately adjusted so as to have the characteristics required for the target retardation film.

  The stretching is preferably performed under a uniform temperature distribution controlled in the width direction. The temperature is preferably within ± 2 ° C, more preferably within ± 1 ° C, and particularly preferably within ± 0.5 ° C.

  Prior to winding, the ends may be slit and cut to the width of the product, and knurling (embossing) may be applied to both ends to prevent sticking or scratching during winding. The knurling method can process a metal ring having an uneven pattern on its side surface by heating or pressing.

  In addition, since the film has deform | transformed and cannot use as a product normally, the holding | grip part of the clip of both ends of a film is cut out and reused.

  The stretch ratio is 1% to 250%, more preferably 2% to 200%, and still more preferably 3% to 150% on at least one side. Although it may be stretched evenly in the vertical and horizontal directions, it is more preferable to stretch one of the stretch ratios more than the other and stretch the same.

  Either length (MD) or width (TD) may be increased, but the smaller draw ratio is preferably 0% to 30%, more preferably 0% to 25%, and still more preferably 0% to 20%. %. The larger draw ratio is 1% to 250%, more preferably 10% to 200%, and still more preferably 30% to 150%.

Stretch ratio (%) = 100 × {(Length after stretching) − (Length before stretching)} / (Length before stretching)
These longitudinal stretching and lateral stretching may be performed independently (uniaxial stretching) or may be performed in combination (biaxial stretching). In the case of biaxial stretching, it may be carried out in the longitudinal and transverse sequential manners (sequential stretching) or simultaneously (simultaneous stretching).

  Following such stretching, it is preferable to relax 0% to 10% in the longitudinal or transverse direction. Furthermore, it is also preferable to heat-fix at 150-250 degreeC for 1 second-3 minutes following extending | stretching.

  Here, Ro indicates in-plane retardation, the difference between the refractive index in the in-plane film forming direction MD and the refractive index in the width direction TD is multiplied by the thickness, and Rt indicates the thickness direction retardation. The difference between the in-plane refractive index (average of the film forming direction MD and the width direction TD) and the refractive index in the thickness direction is multiplied by the thickness.

  Stretching can be performed sequentially or simultaneously with respect to, for example, the film forming direction and the width direction of the film. At this time, if the stretching ratio in at least one direction is too small, a sufficient phase difference cannot be obtained, and if it is too large, stretching becomes difficult and film breakage may occur.

  Stretching in biaxial directions perpendicular to each other is an effective method for bringing the refractive indexes nx, ny, and nz of the film within a predetermined range.

  Here, nx is the refractive index in the film MD direction, ny is the refractive index in the TD direction, and nz is the refractive index in the thickness direction.

  For example, when stretching in the film forming direction, if the shrinkage in the width direction is too large, the value of nz becomes too large. In this case, the width shrinkage of the film can be suppressed or improved by stretching in the width direction. When stretching in the width direction, the refractive index may be distributed in the width direction.

  This distribution may appear when the tenter method is used, and by stretching the film in the width direction, a shrinkage force is generated in the center of the film, and the phenomenon is caused by the end being fixed, It is thought to be a so-called Boeing phenomenon.

  Even in this case, by stretching in the film forming direction, the bowing phenomenon can be suppressed and the distribution of retardation in the width direction can be reduced. By stretching in biaxial directions perpendicular to each other, film thickness fluctuations of the obtained film can be reduced. If the film thickness variation is too large, the phase difference becomes uneven, and unevenness such as coloring may be a problem when used in a liquid crystal display.

  The film thickness variation of the aforementioned cellulose ester film is preferably in the range of ± 3%, more preferably ± 1%.

  After stretching, after slitting the end of the film to a product width with a slitter, the film is subjected to knurling (embossing) on both ends of the film by a knurling device consisting of an embossing ring and a back roll, and a winder By taking up with, it prevents the cellulose ester film (original winding) from sticking and the generation of scratches.

<Solution casting film formation>
In film production by solution casting, a step of preparing a dope by dissolving a resin and an additive in a solvent, a step of casting the dope on a belt-shaped or drum-shaped metal support, and using the cast dope as a web It is performed by a step of drying, a step of peeling from the metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding up the finished film. The resin concentration in the dope is preferably higher because the drying load after casting on the metal support can be reduced, but if the resin concentration is too high, the load during filtration increases and the filtration accuracy deteriorates. . As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%.

  The metal support in the casting (casting) step preferably has a mirror-finished surface. As the metal support, a stainless steel belt or a drum whose surface is plated with a casting is preferably used. The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting step is set to −50 ° C. to a temperature at which the solvent boils and does not foam. A higher temperature is preferable because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate. The preferable support temperature is appropriately determined at 0 to 100 ° C, and more preferably 5 to 30 ° C. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent. The method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When using warm air, considering the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent, there may be cases where wind at a temperature higher than the target temperature is used while preventing foaming. . In particular, it is preferable to perform drying efficiently by changing the temperature of the support and the temperature of the drying air during the period from casting to peeling.

  In order for the cellulose ester film to exhibit good flatness, the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Especially preferably, it is 20-30 mass% or 70-120 mass%.

  The amount of residual solvent is defined by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.

  In the film drying step, the web is peeled off from the metal support, and further dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably. Is 0-0.01 mass% or less.

  In the film drying process, generally, a roll drying method (a method in which a plurality of rolls arranged on the upper and lower sides are alternately passed through and dried) or a method of drying while transporting the web by a tenter method is adopted.

  In the film drying step, it is preferable to carry out the treatment while transporting in an atmosphere with an atmosphere substitution rate of 12 times / hour or more, preferably 12 to 45 times / hour.

The atmosphere substitution rate is defined as follows. When the atmosphere capacity of the heat treatment chamber is V (m ³ ) and the fresh air flow rate is FA (m ³ / hr), the atmosphere of the heat treatment chamber per unit time determined by the following formula is Fresh-air. Is the number of replacements by. “Fresh-air” means that the wind blown into the heat treatment chamber is not a wind that is recycled and reused, and it means a fresh wind that does not contain volatilized solvent or plasticizer or has been removed. Yes.

Atmosphere replacement rate = FA / V (times / hour)
An atmosphere substitution rate of 12 times / hour or more is preferable because the plasticizer concentration in the atmosphere due to the plasticizer volatilized from the film can be sufficiently reduced, and reattachment to the film can be reduced.

<Substantially vertically aligned polymerizable liquid crystal compound layer>
A substantially vertically aligned polymerizable liquid crystal compound layer (hereinafter referred to as an optically anisotropic layer) will be described. The polymerizable liquid crystal compound layer preferably has the following characteristics.

0 ≦ Ro ≦ 10
−500 ≦ Rt ≦ −100
The optically anisotropic layer of the present invention is a liquid crystal material or a liquid crystal solution coated directly or on an intermediate layer on a cellulose ester film having at least one repeating unit represented by the general formula (1) or (2). Then, drying and heat treatment (also referred to as alignment treatment) are performed, and the alignment of the liquid crystal alignment is fixed by ultraviolet curing or thermal polymerization. By providing the vertically aligned rod-like liquid crystal layer on the cellulose ester film, the elasticity of the optical compensation film is improved, and the object effect of the present invention is exhibited in combination with the above-described characteristics.

  Here, “orienting in the vertical direction” means that the rod-like liquid crystal is in the range of 70 to 90 ° (the vertical direction is 90 °) with respect to the film surface serving as the support.

  The rod-like liquid crystal may be oriented obliquely or the orientation angle may be gradually changed. Preferably it is the range of 80-90 degrees.

  The optically anisotropic layer is a layer of rod-like liquid crystal aligned in the vertical direction with Ro in the range of 0 to 10 nm and Rt in the range of −500 to −100 nm. Further, Ro is more preferably in the range of 0 to 5 nm. The phase difference of the phase difference of the layer on which the liquid crystal alignment is fixed on these supports can be measured using AxoScan manufactured by Opto Science Co., Ltd.

  When forming a retardation layer by aligning rod-shaped liquid crystals, an alignment film coated with a vertical alignment agent that aligns the so-called liquid crystal material in the vertical direction is used, and the liquid crystal material is vertically aligned and then fixed. be able to.

  When the liquid crystal material itself is aligned in the vertical direction at the air interface, the alignment regulating force extends to the interface opposite to the air interface, and the alignment film is not particularly necessary, and this is also preferable from the viewpoint of simplifying the configuration. preferable.

  As a specific method for vertically aligning the liquid crystal material, an alignment film composed of a cross-linked product of a block polymer composition containing a (meth) acrylic block polymer described in JP-A-2005-148473 and the like is used. Known methods such as a method of using, a method of using a vertical alignment film described in JP 2005-265889 A, and a method of using an air interface vertical alignment agent can be used. In order to align in the vertical direction as described above, it is preferable to perform alignment of the rod-like liquid crystal layer, film thickness control, temperature during UV curing, tilt angle control, and control of the pretilt angle at the support / air interface.

  The liquid crystal layer is formed by curing a liquid crystal material capable of forming a liquid crystal phase at a predetermined temperature with a predetermined liquid crystal regularity. The upper limit of the temperature showing the liquid crystal phase is not particularly limited as long as the cellulose ester film of the base material is not damaged.

  Specifically, a temperature of 120 ° C. or lower is preferable from the viewpoint of easy control of process temperature and maintenance of dimensional accuracy, and a liquid crystal material that becomes a liquid crystal phase at a temperature of 100 ° C. or lower is preferably used. On the other hand, the lower limit of the temperature showing the liquid crystal phase can be said to be a temperature at which the liquid crystal material can maintain the alignment state when used as a polarizing plate.

  As the liquid crystal material described above, a polymerizable liquid crystal material is preferably used. The polymerizable liquid crystal material can be used by being polymerized by irradiating with predetermined actinic radiation. In the polymerized state, the vertical alignment state is fixed.

  As the polymerizable liquid crystal material, any of a polymerizable liquid crystal monomer, a polymerizable liquid crystal oligomer, and a polymerizable liquid crystal polymer can be used, and they can also be mixed with each other.

  Of the above, a polymerizable liquid crystal monomer is preferably used as the polymerizable liquid crystal material because of its high sensitivity during alignment and easy vertical alignment.

  Specific examples of the polymerizable liquid crystal monomer include a rod-like liquid crystal compound (I) represented by the following general formula (7) and a rod-like liquid crystal compound (II) represented by the following general formula (8). be able to. As the compound (I), a mixture of two or more compounds included in the general formula (7) can be used. Similarly, the compound (II) is included in the general formula (8). Two or more kinds of compounds may be mixed and used. In addition, one or more compounds (I) and one or more compounds (II) may be mixed and used.

In the general formula (7) representing the compound (I), R ¹ and R ² each represent hydrogen or a methyl group, but R ¹ and R ² are both hydrogen due to the wide temperature range showing the liquid crystal phase. preferable. X may be hydrogen, chlorine, bromine, iodine, an alkyl group having 1 to 4 carbon atoms, a methoxy group, a cyano group, or a nitro group, but is preferably chlorine or a methyl group. Moreover, a and b which show the chain length of the alkylene group which is a spacer with the (meth) acryloyloxy group of both ends of the molecular chain of a compound (I), and an aromatic ring are respectively arbitrary integers in the range of 2-12. Although it can take, it is preferable that it is the range of 4-10, and it is more preferable that it is the range of 6-9. The compound of the general formula (7) in which a = b = 0 is poor in stability, is susceptible to hydrolysis, and has high crystallinity. In addition, the compound of the general formula (7) in which a and b are each 13 or more has a low isotropic transition temperature (TI). For this reason, both of these compounds are not preferred because the temperature range showing liquid crystallinity is narrow.

  Compound (I) can be synthesized by any method. For example, compound (I) in which X is a methyl group can be obtained by an esterification reaction of 1 equivalent of methylhydroquinone and 2 equivalents of 4- (m- (meth) acryloyloxyalkoxy) benzoic acid. In the esterification reaction, the benzoic acid is usually activated with an acid chloride or a sulfonic anhydride, and this is reacted with methylhydroquinone. Moreover, a carboxylic acid unit and methylhydroquinone can also be directly reacted using a condensing agent such as DCC (dicyclohexylcarbodiimide). As other methods, esterification of 1 equivalent of methylhydroquinone and 2 equivalents of 4- (m-benzyloxyalkoxy) benzoic acid is first performed, and then the resulting ester is debenzylated by hydrogenation reaction or the like. Then, compound (I) can also be synthesized by a method in which the molecular terminal is acryloylated. When performing esterification reaction of methylhydroquinone and 4- (m-benzyloxyalkoxy) benzoic acid, methylhydroquinone is introduced into diacetate and then reacted with the above benzoic acid in a molten state to obtain an ester directly. It is also possible. The compound (I) in the case where X in the general formula (7) is not a methyl group can also be obtained by performing the same reaction as above using hydroquinone having a corresponding substituent instead of methylhydroquinone.

In the general formula (8) representing the compound (II), R ³ represents hydrogen or a methyl group, but R ³ is preferably hydrogen because of the wide temperature range showing the liquid crystal phase. As for c indicating the chain length of the alkylene group, the compound (II) having this value of 2 to 12 does not exhibit liquid crystallinity. However, considering the compatibility with the compound (I) having liquid crystallinity, c is preferably in the range of 4 to 10, and more preferably in the range of 6 to 9. Compound (II) can also be synthesized by any method. For example, compound (II) can be synthesized by esterification reaction of 1 equivalent of 4-cyanophenol and 1 equivalent of 4- (n- (meth) acryloyloxyalkoxy) benzoic acid. II) can be synthesized. In the esterification reaction, the benzoic acid is generally activated with an acid chloride or a sulfonic acid anhydride and reacted with 4-cyanophenol, as in the case of synthesizing the compound (I). Moreover, you may make the said benzoic acid and 4-cyanophenol react using condensing agents, such as DCC (dicyclohexyl carbodiimide).

  In addition to the above, conventionally known materials can be appropriately selected and used as the polymerizable liquid crystal oligomer and the polymerizable liquid crystal polymer.

  For example, as a polymerizable rod-like liquid crystalline compound, Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. Nos. 4,683,327, 5,622,648 and 5,770,107, International Publication No. 95/22586. Pamphlet, 95/24455, 97/00600, 98/23580, 98/52905, JP-A-1-272551, 6-16616, 7-110469, 11 JP-A-80081, JP-A-2001-328773, JP-A-2004-240188, JP-A-2005-99236, JP-A-2005-99237, JP-A-2005-121827, JP-A-2002-30042. The compounds described in Japanese Patent Publication No. Gazette and the like can be used.

  As commercially available compounds, UCL-018 (Dainippon Ink Chemical Co., Ltd.), Palio Color LC242 (BASF Co., Ltd.), etc. can be used.

  In addition to the polymerizable liquid crystal material, a photopolymerization initiator is used as necessary. When polymerizing a polymerizable liquid crystal material by electron beam irradiation, a photopolymerization initiator may not be necessary. However, in the case of curing by, for example, ultraviolet (UV) irradiation, which is generally used, photopolymerization is usually performed. An initiator is used to promote polymerization.

  Photopolymerization initiators include benzyl (also called bibenzoyl), benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylamino Methylbenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 3,3′-dimethyl-4-methoxybenzophenone, methylobenzoylformate, 2-methyl-1- (4 -(Methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 1- (4-dodecylphenyl) -2- Droxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2- Examples include methylpropan-1-one, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, or 1-chloro-4-propoxythioxanthone. it can.

  The amount of photopolymerization initiator added is generally preferably 0.01% to 20%, more preferably 0.1% to 10%, and even more preferably in the range of 0.5% to 5%. Can be added to the polymerizable liquid crystal material. In addition to the photopolymerization initiator, a sensitizer can be added.

  The film thickness of the liquid crystal layer is preferably in the range of 0.1 μm to 10 μm, and more preferably in the range of 0.2 to 5 μm.

  A polymerizable liquid crystal material is prepared by using a composition for forming a liquid crystal layer by blending a photopolymerization initiator, a sensitizer, etc., if necessary, and coating on a substrate to form a liquid crystal layer forming layer. To do.

  As a method of forming a layer in which the orientation of liquid crystal is fixed, for example, a method in which a dry film or the like is formed in advance and a layer in which the orientation of liquid crystal is fixed is laminated on a substrate, or a liquid crystal composition is dissolved Alternatively, it is possible to take a method such as melting and coating on a substrate, but as a liquid crystal composition, a solvent is added and a coating composition in which other components are dissolved is used on the substrate. It is preferable to form a layer in which the orientation of the liquid crystal is fixed by coating and removing the solvent. This is simple in terms of process as compared with other methods.

  The solvent is not particularly limited as long as it is a solvent capable of dissolving the above-described polymerizable liquid crystal material and the like and does not deteriorate the properties of the base film. Specifically, benzene, Hydrocarbons such as toluene, xylene, n-butylbenzene, diethylbenzene, tetralin; ethers such as methoxybenzene, 1,2-dimethoxybenzene, diethylene glycol dimethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or 2,4- Ketones such as pentanedione; esters such as ethyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, or γ-butyrolactone An amide solvent such as 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide, or dimethylacetamide; chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, tritrichloroethylene, tetrachloroethylene, chlorobenzene, or orthodichlorobenzene, etc. Halogen-based solvents; alcohols such as t-butyl alcohol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, ethylene glycol monomethyl ether, ethyl cellosolve, or butyl cellosolve; phenol, parachloro One type or two or more types of phenols such as phenol can be used.

  If only a single type of solvent is used, the solubility of the polymerizable liquid crystal material or the like may be insufficient, or the substrate may be eroded as described above. However, this inconvenience can be avoided by using a mixture of two or more solvents.

  Of the above-mentioned solvents, preferred as a single solvent are a hydrocarbon solvent and a glycol monoether acetate solvent, and a preferred mixed solvent is a mixed system of ethers or ketones and glycols. It is.

  The concentration of the solution depends on the solubility of the polymerizable liquid crystal material or the like and the film thickness of the liquid crystal layer to be produced, but cannot be defined unconditionally, but is usually preferably 1% to 60%, more preferably 3% to It is adjusted within the range of 40%.

  Compounds other than those described above can be added to the composition for forming a liquid crystal layer.

  Examples of compounds that can be added include polyester (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing polyhydric alcohol and monobasic acid or polybasic acid; A polyurethane (meth) acrylate obtained by reacting a compound having two isocyanate groups with each other and then reacting the reaction product with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak Type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ether, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin and the like (meth) Ak A photopolymerizable compound such as epoxy (meth) acrylate obtained by reacting phosphoric acid, a photopolymerizable liquid crystal compound having an acrylic group or a methacryl group, an onium salt described in JP-A-2007-45993, and a fluorine compound. Acrylate polymers and the like.

  The amount of these compounds added to the liquid crystal layer forming composition is generally preferably 40% or less, more preferably 20% or less of the liquid crystal layer forming composition.

  Addition of these compounds improves the curability of the liquid crystal material, increases the mechanical strength of the resulting liquid crystal layer, and improves its stability.

  In addition, a surfactant or the like can be added to the composition for forming a liquid crystal layer containing a solvent in order to facilitate coating.

  Examples of surfactants that can be added include cationic surfactants such as imidazoline, quaternary ammonium salts, alkylamine oxides and polyamine derivatives; polyoxyethylene-polyoxypropylene condensates, primary or secondary Alcohol ethoxylates, alkylphenol ethoxylates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl sulfate amines, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, etc. Anionic surfactants; amphoteric surfactants such as laurylamidopropylbetaine and laurylaminoacetic acid betaine; nonionics such as polyethylene glycol fatty acid esters and polyoxyethylene alkylamine Surfactant: Perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trimethyl ammonium salt, perfluoroalkyl group / hydrophilic group-containing oligomer, perfluoroalkyl / lipophilic group Fluorosurfactants such as containing oligomer perfluoroalkyl group-containing urethanes.

  The amount of surfactant added depends on the type of surfactant, the type of liquid crystal material, the type of solvent, and the type of alignment film on which the solution is applied. 10 ppm to 10% is preferable, more preferably 100 ppm to 5%, and still more preferably 0.1 to 1%.

  As a method for coating the composition for forming a liquid crystal layer, a spin coating method, a roll coating method, a printing method, a dip pulling method, a die coating method, a casting method, a bar coating method, a blade coating method, a spray coating method, a gravure coating method , Reverse coating method or extrusion coating method.

  The method for removing the solvent after coating the composition for forming a liquid crystal layer is performed, for example, by air drying, heat removal, or removal under reduced pressure, or a combination thereof. By removing the solvent, a layer in which the alignment of the liquid crystal is fixed is formed.

  In the step of curing the polymerizable liquid crystal material, energy for curing the polymerizable liquid crystal material is given, and thermal energy may be used, but it is usually performed by irradiation with ionizing radiation capable of causing polymerization.

  If necessary, a polymerization initiator may be contained in the polymerizable liquid crystal material. The ionizing radiation is not particularly limited as long as it is a radiation capable of polymerizing the polymerizable liquid crystal material. Usually, ultraviolet light or visible light is used from the viewpoint of the ease of the apparatus, and the wavelength is The light of 150-500 nm is preferable, More preferably, it is 250-450 nm, More preferably, it is an ultraviolet-ray with a wavelength of 300-400 nm.

  In the present invention, a method of performing radical polymerization by irradiating ultraviolet rays (UV) as actinic radiation and generating radicals from the polymerization initiator with ultraviolet rays is preferable. Since the method using UV as the actinic radiation is an already established technique, it can be easily applied including the polymerization initiator used.

  As a light source for irradiating ultraviolet rays, a low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), a high-pressure discharge lamp (high-pressure mercury lamp, metal halide lamp), or a short arc discharge lamp (ultra-high-pressure mercury lamp, xenon) Lamp, mercury xenon lamp) and the like.

  In particular, the use of metal halide lamps, xenon lamps, high-pressure mercury lamps, etc. is recommended. The irradiation intensity may be appropriately adjusted depending on the composition of the polymerizable liquid crystal material used for forming the layer in which the alignment of the liquid crystal is fixed and the amount of the photopolymerization initiator.

  The alignment fixing step by irradiation with actinic radiation may be performed at the processing temperature in the step of forming the liquid crystal layer forming layer described above, that is, the temperature condition in which the polymerizable liquid crystal material becomes a liquid crystal phase, It may be performed at a lower temperature.

<Intermediate layer>
Between a transparent film containing a cellulose ester having at least one repeating unit represented by the general formula (1) or (2) and an optically anisotropic layer in which the alignment is fixed by vertically aligning rod-shaped liquid crystals An intermediate layer can be provided.

  The intermediate layer is made of a transparent resin. The transparent resin is preferably a binder polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a binder polymer having a saturated hydrocarbon chain as a main chain.

  Particularly preferred is a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams, or a mixed composition of a crosslinking agent and a resin having a reactive site.

  Examples of the curable resin include UV curable urethane acrylate resins, UV curable polyester acrylate resins, UV curable epoxy acrylate resins, UV curable polyol acrylate resins, and UV curable epoxy resins. A type acrylate resin is preferably used.

  The UV curable urethane acrylate resin generally includes a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter, acrylate includes methacrylate). It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate.

  For example, those described in JP 59-151110 A can be used. For example, a mixture of 100 parts of purple light UV-7510B (manufactured by Nippon Synthetic Chemical Co., Ltd.), Unidic 17-806 (manufactured by Dainippon Ink Co., Ltd.) and 1 part of coronate L (manufactured by Nippon Polyurethane Co., Ltd.) Preferably used.

  Examples of UV curable polyester acrylate resins include those which are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Those described in the publication can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photopolymerization initiator added thereto, and reacted to form an oligomer. Those described in Japanese Patent No. 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.

  Specific examples of photopolymerization initiators for these curable resins include benzoin and derivatives thereof, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer.

  In addition, when using an epoxy acrylate photopolymerization initiator, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used.

  The photopolymerization initiator or photosensitizer used in the curable resin composition is 0.1 to 25 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the composition.

  Examples of the mixed composition of the crosslinking agent and the resin having a reactive site include polyvinyl alcohol and glyoxal, gelatin and glyoxal, and the like.

  Further, the intermediate layer may contain a fluorine-acrylic copolymer resin. The fluorine-acrylic copolymer resin is a copolymer resin composed of a fluorine monomer and an acrylic monomer, and a block copolymer composed of a fluorine monomer segment and an acrylic monomer segment is particularly preferable. The intermediate layer may be two or more layers.

<Method for producing intermediate layer>
The intermediate layer is coated by using a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or an ink jet method, and a coating composition for forming an intermediate layer containing a retardation increasing agent. It is preferable to heat-dry and apply UV curing after the coating.

  The coating amount is suitably 0.1 to 40 μm, preferably 0.5 to 30 μm, as the wet film thickness.

  The dry film thickness is 0.01 to 5 μm, preferably 0.02 to 2 μm.

  As the light source for the UV curing treatment, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.

Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm ² , preferably 5 to 150 mJ / cm ² .

  Moreover, when irradiating actinic radiation, it is preferable to carry out while applying tension | tensile_strength in the conveyance direction of a film, More preferably, it is performing applying tension | tensile_strength also in the width direction. The tension to be applied is preferably 30 to 300 N / m.

  The method for applying tension is not particularly limited, and tension may be applied in the transport direction on the back roll, or tension may be applied in the width direction or biaxial direction by a tenter. This makes it possible to obtain a film having further excellent flatness.

  The coating composition for forming the intermediate layer may contain a solvent. Examples of the organic solvent contained in the coating composition include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone). , Esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents may be appropriately selected or mixed for use.

  As the organic solvent, propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate (1 to 4 carbon atoms of the alkyl group) is preferable. Moreover, as content of an organic solvent, 5-80 mass% is preferable in a coating composition.

<Hard coat layer>
Next, the hard coat layer of the present invention will be described.

(Radically polymerizable compound)
In the hard coat layer of the present invention, it is preferable to use a radical polymerizable compound as a binder from the viewpoint of obtaining high pencil hardness. Examples of the radical polymerizable group include ethylenically unsaturated groups such as a (meth) acryloyl group, a vinyloxy group, a styryl group, and an allyl group, and among them, a compound having a (meth) acryloyl group is preferable. Moreover, as a radically polymerizable compound, it is preferable to contain the polyfunctional monomer which contains a 2 or more radically polymerizable group in a molecule | numerator. The polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. Examples of the polyfunctional acrylate monomer include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate. , Tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerol triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Lithol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, Tetramethylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate Acrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate, isobornyl acrylate and the like preferably. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

  Commercially available polyfunctional acrylates include Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka Co., Ltd.); Hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8 MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP-10, DP-20 DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.); KRM7033, RM 7039, KRM 7130, KRM 7131, UVECRYL 29201, UVECRYL 29202 (manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC- 5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries); SP -1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.); B420 (manufactured by Shin-Nakamura Chemical Co., Ltd.) or the like can be appropriately selected and used.

  In the hard coat composition, the addition amount of the radical polymerizable compound is preferably 15% by mass or more and less than 70% by mass in the solid content from the viewpoint of the stability of the hard coat composition.

(Radical polymerization accelerator)
In order to accelerate the curing of the radical polymerizable compound, it is preferable to use a photopolymerization initiator in combination with the radical polymerizable compound. When the photopolymerization initiator and the radical polymerizable compound are used in combination, it is preferable to contain the photopolymerization initiator and the radical polymerizable compound in a mass ratio of 20: 100 to 0.01: 100.

  Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.

  Furthermore, the hard coat layer contains the following cationically polymerizable compound, and the polarizing plate of the present invention constitutes the objective effect of the present invention, as well as a durability test when used in a liquid crystal panel. This is preferable because it is excellent in preventing unevenness of light and light leakage from an oblique direction.

(Cationically polymerizable compound)
Any cationically polymerizable compound can be used as long as it undergoes cationic polymerization by irradiation with energy active rays or heat to form a resin. Specific examples include an epoxy group, a cyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester compound, and a vinyloxo group. Among them, a compound having a functional group such as an epoxy group or a vinyl ether group is preferably used in the present invention. Examples of the cationically polymerizable compound having an epoxy group or a vinyl ether group include phenyl glycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, vinylcyclohexene dioxide, limonene dioxide, 3,4-epoxycyclohexylmethyl-3 ′. , 4'-epoxycyclohexanecarboxylate, bis- (6-methyl-3,4-epoxycyclohexyl) adipate, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, 1 , 4-cyclohexanedimethanol divinyl ether and the like. Moreover, as an epoxy compound, a polymer compound can also be used, for example, it is compoundable by the method currently disclosed by Unexamined-Japanese-Patent No. 7-247313.

  Among them, it is preferable to use an oxetane compound as the cationic polymerizable compound. As the oxetane compound, any compound having at least one oxetane ring in the molecule may be used. As such an oxetane compound, various compounds can be used. As preferred compounds, the following general formula (I) These are compounds of general formula (II) and general formula (III).

(Wherein R ⁷ represents hydrogen, fluorine, an alkyl group, a fluoroalkyl group, an allyl group, an aryl group or a furyl group, m represents an integer of 1 to 4, Z represents oxygen or sulfur, and R ⁸ Represents a monovalent to tetravalent organic group depending on the value of m.)

(Wherein R ⁹ and R ¹⁰ each independently represent hydrogen, fluorine, an alkyl group, a fluoroalkyl group, an allyl group, an aryl group, or a furyl group.)

(In the formula, R ¹¹ represents hydrogen, fluorine, an alkyl group, a fluoroalkyl group, an allyl group, an aryl group or a furyl group, R ¹² represents hydrogen or an inert monovalent organic group, and R ¹³ represents water. Represents a decomposable functional group, n represents an integer of 1 to 5, and p represents an integer of 0 to 2.)
In the above general formulas (I) to (III), when R ⁷ , R ⁹ , R ¹⁰ and R ¹¹ are alkyl groups, the carbon number thereof can be about 1 to 6, specifically, methyl, Examples include ethyl, propyl, butyl and the like. The fluoroalkyl group can also have about 1 to 6 carbon atoms. Furthermore, the aryl group is typically phenyl or naphthyl, which may be substituted with other groups.

In addition, the organic group represented by R ⁸ in the general formula (I) is not particularly limited. For example, when m is 1, an alkyl group, a phenyl group, or the like, and when m is 2, the number of carbon atoms is In the case where 1 to 12 linear or branched alkylene groups, linear or branched poly (alkyleneoxy) groups, and the like is 3 or 4, a similar polyfunctional group is exemplified.

The inactive monovalent organic group represented by R ¹² in the general formula (II) typically includes an alkyl group having 1 to 4 carbon atoms, and is hydrolyzable represented by R ^13. Examples of the functional group include an alkoxy group having 1 to 5 carbon atoms including methoxy and ethoxy, and a halogen atom such as a chlorine atom and a bromine atom.

  Furthermore, if necessary, a (co) polymer containing a monomer having a hydrogen bond-forming group and a reactive polymer having an oxetanyl group in the main chain or side chain and having a number average molecular weight of 20,000 or more can also be used.

  Moreover, you may use the fluorine-containing vinyl ether compound as shown by the following general formula.

_{CH 2 = CH-O- (CH} 2) a-O- (CH 2) b-Rf- (CH 2) b-O- (CH 2) a-O-CH = CH 2
(In the formula, Rf represents a fluorine-containing alkyl group, a represents an integer of 1 to 2, and b represents an integer of 0 to 3. Rf may be a linear or branched alkyl group.)
Specific compounds are as follows.

_{CH 2 = CH-O-CH} 2 -O- (CF 2) k-O-CH 2 -O-CH = CH 2
_{CH 2 = CH-O-CH} 2 -O-CH 2 - (CF 2) k-CH 2 -O-CH 2 -O-CH = CH 2
_{CH 2 = CH-O-CH} 2 -O- (CH 2) 2 - (CF 2) k- (CH 2) 2 -O-CH 2 -O-CH = CH 2
_{CH 2 = CH-O-CH} 2 -O- (CH 2) 3 - (CF 2) k- (CH 2) 3 -O-CH 2 -O-CH = CH 2
_{CH 2 = CH-O- (CH} 2) 2 -O- (CF 2) k-O- (CH2) 2 -O-CH = CH 2
_{CH 2 = CH-O- (CH} 2) 2 -O-CH 2 - (CF 2) k-CH 2 -O- (CH 2) 2 -O-CH = CH 2
_{CH 2 = CH-O- (CH} 2) 2 -O- (CH 2) 2 - (CF 2) k- (CH 2) 2 -O- (CH 2) 2 -O-CH = CH 2
_{CH 2 = CH-O- (CH} 2) 2 -O- (CH 2) 3 - (CF 2) k- (CH 2) 3 -O- (CH 2) 2 -O-CH = CH 2
In the above, k is preferably an integer of 2 or more and 12 or less, and more preferably, k is 4 or more and 10 or less. The fluorine-containing vinyl ether compound can be produced by reacting a fluorine-containing dialcohol and a vinyl ether having a halogen group in the presence of an alkali catalyst. Moreover, you may contain a fluorine-containing epoxy compound, for example, the compound as described in General formula (1)-(4) of Unexamined-Japanese-Patent No. 11-309830 can be used. Specific examples thereof include, but are not limited to, the following fluorine-containing epoxy compounds 1 to 4.

  Fluorine-containing epoxy compound 1

  Fluorine-containing epoxy compound 2

  Fluorine-containing epoxy compound 3

  Fluorine-containing epoxy compound 4

  In addition, the compounds described in JP-A-2007-254650, paragraph numbers [116] to [126] can also be mentioned.

  From the viewpoint of stability of the hard coat composition, the above-mentioned cationically polymerizable compound is preferably 15% by mass or more and less than 70% by mass in the solid content in the hard coat composition.

(Cationic polymerization accelerator)
Examples of the compound that accelerates the polymerization of the cationic polymerizable compound include known acids and photoacid generators. Examples of the photoacid generator include a cationic polymerization photoinitiator, a dye photodecoloring agent, a photochromic agent, a known compound used in a microresist, and a mixture thereof. Specific examples include onium compounds, organic halogen compounds, and disulfone compounds, and onium compounds are preferable. As the onium compound, diazonium salts, sulfonium salts, iodonium salts and the like represented by the following formulas are preferably used.

ArN ₂ ⁺ Z ⁻ ,
(R) ₃ S ⁺ Z ⁻ ,
(R) ₂ I ⁺ Z ⁻
In the formula, Ar represents an aryl group, R represents an aryl group or an alkyl group having 1 to 20 carbon atoms, and when R appears multiple times in one molecule, they may be the same or different, and Z ⁻ Represents a non-basic and non-nucleophilic anion.

In each of the above formulas, the aryl group represented by Ar or R is also typically phenyl or naphthyl, and these may be substituted with an appropriate group. Specific examples of the anion represented by Z ⁻ include tetrafluoroborate ion (BF ₄ ⁻ ), tetrakis (pentafluorophenyl) borate ion (B (C ₆ F ₅ ) ₄ ⁻ ), and hexafluorophosphate ion. (PF ₆ ⁻ ), hexafluoroarsenate ion (AsF ₆ ⁻ ), hexafluoroantimonate ion (SbF ₆ ⁻ ), hexachloroantimonate ion (SbCl ₆ ⁻ ), hydrogen sulfate ion (HSO ₄ ⁻ ), perchloric acid Ion (ClO ₄ ⁻ ) and the like.

  Examples of other onium compounds include ammonium salts, iminium salts, phosphonium salts, arsonium salts, selenonium salts, boron salts, and the like. For example, compounds described in paragraph numbers [0058] to [0059] of JP-A-2002-29162 Etc.

  Of these, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of the material stability of the compound.

  Specific examples of onium salts that can be suitably used include, for example, an amylated sulfonium salt described in paragraph No. [0035] of JP-A No. 9-268205, and paragraph Nos. Of JP-A No. 2000-71366. Diaryl iodonium salts or triarylsulfonium salts described in [0010] to [0011], sulfonium salts of thiobenzoic acid S-phenyl ester described in paragraph [0017] of JP-A-2001-288205, JP-A-2001-133696 Onium salts and the like described in paragraph numbers [0030] to [0033] of the publication.

  Other examples of the acid generator include organometallic / organic halides described in JP-A-2002-29162, paragraphs [0059] to [0062], and a photoacid generator having an o-nitrobenzyl type protecting group. And compounds such as compounds that generate photosulfonic acid to generate sulfonic acid (iminosulfonate, etc.). Since many of these compounds are commercially available, such commercially available products can be used. Commercially available initiators include, for example, “Syracure UVI-6990” (trade name) sold by Dow Chemical Japan Co., Ltd., and “Adekaoptomer SP-150” (available from ADEKA Corporation) Product name), Adeka optomer SP-300 (product name), “RHODORSIL PHOTOINITIAOR 2074” (product name) sold by Rhodia Japan Co., Ltd., and the like.

  As the acid, Bronsted acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like, or organic acid such as acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, dibutyltin dilaurate, Examples thereof include Lewis acids such as dibutyltin diacetate, dibutyltin dioctate, triisopropoxyaluminum, tetrabutoxyzirconium, and tetrabutoxytitanate.

  Aromatic polycarboxylic acids such as pyromellitic acid, pyromellitic anhydride, trimellitic acid, trimellitic anhydride, phthalic acid, phthalic anhydride, or anhydrides thereof, maleic acid, maleic anhydride, succinic acid, succinic anhydride Aliphatic polyvalent carboxylic acid or anhydride thereof such as

  As an acid, only 1 type may be used and 2 or more types may be used together.

  These acids and photoacid generators are preferably added in a proportion of 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, with respect to 100 parts by mass of the cationic polymerizable compound. is there. When the addition amount is in the above range, it is preferable from the viewpoint of stability of the curable composition, polymerization reactivity, and the like.

(Silicon compound)
Further, the hard coat layer preferably contains an organosilicon compound represented by the following general formula (B), a hydrolyzate thereof, or a polycondensate thereof.

R2 _m SiX2 _4-m (B)
In the formula, R2 is an epoxy group, X2 is a hydroxyl group or a hydrolyzable substituent, and m is an integer of 0 to 3.

  R2 of the alkoxysilane compound having an epoxy group represented by the general formula (B) is not particularly limited, but examples thereof include 2-glycidoxyethyl group, 3-glycidoxypropyl group, 3-glycidoxybutyl group and the like. Glycidoxy C1-C4 alkyl group, preferably glycidoxy C1-C3 alkyl group, glycidyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, 2- (3 Oxiranes such as 4-epoxycycloheptyl) ethyl group, 2- (3,4-epoxycyclohexyl) propyl group, 2- (3,4-epoxycyclohexyl) butyl group, 2- (3,4-epoxycyclohexyl) pentyl group And a C1-C3 alkyl group substituted with a C5-C8 cycloalkyl group having a group. Among these, a 2-glycidoxyethyl group, a 3-glycidoxypropyl group, and a 2- (3,4-epoxycyclohexyl) ethyl group are preferable. Preferred specific examples of the compound that can be used as the compound of the general formula (1) having these substituents R2 include 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, and 3-glycidide. Xylpropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4) -epoxycyclohexylethyltriethoxysilane and the like. These may be used alone or in combination of two or more.

The alkoxysilane compound can be produced, for example, by the method described in JP-A-10-324749 and JP-A-6-298940. As described in JP-A-2006-348061, it can also be obtained by (co) condensation of an alkoxysilane compound of the general formula (1) under a base catalyst. In that case, water can be added as needed to promote (co) condensation. The amount of water added is usually 0.05 to 1.5 mol, preferably 0.1 to 1.2 mol, with respect to 1 mol of alkoxy groups in the entire reaction mixture. The catalyst used for the condensation reaction is not particularly limited as long as it is basic, but an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. Organic bases such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, an inorganic base or ammonia is preferable because the catalyst can be easily removed from the product. The addition amount of the catalyst is usually 5 × 10 ^{−4 to} 7.5 mass%, preferably 1 × 10 ^{−3 to} 5 mass%, based on the amount of the alkoxysilane compound. The condensation reaction can be carried out without a solvent or in a solvent. There is no restriction | limiting in particular as a solvent in the case of using a solvent, if it is a solvent which melt | dissolves an alkoxysilane compound. Examples of such solvents include nonpolar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, and methyl isobutyl ketone, and aromatic hydrocarbons such as toluene and xylene, preferably methyl ethyl ketone and methyl isobutyl ketone. .

  Furthermore, you may contain the fluorine substituted alkyl group containing silane compound represented by the following general formula (OSi-2).

  The fluorine-substituted alkyl group-containing silane compound represented by the general formula (OSi-2) will be described.

In the formula, R ^{1 to} R ⁶ are alkyl groups having 1 to 16 carbon atoms, preferably 1 to 4 carbon atoms, halogenated alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and 6 to 12 carbon atoms, preferably 6 carbon atoms. 10 to 10 aryl groups, 7 to 14 carbon atoms, preferably 7 to 12 alkylaryl groups, arylalkyl groups, 2 to 8 carbon atoms, preferably 2 to 6 alkenyl groups, or 1 to 6 carbon atoms, preferably 1 to 3 alkoxy groups, a hydrogen atom or a halogen atom.

Rf represents-(CaHbFc)-, a is an integer of 1 to 12, b + c is 2a, b is an integer of 0 to 24, and c is an integer of 0 to 24. Such Rf is preferably a group having a fluoroalkylene group and an alkylene group. Specifically, examples of such fluorine-containing silicone compounds include (MeO) ₃ SiC ₂ H ₄ C ₂ F ₄ C ₂ H ₄ Si (MeO) ₃ , (MeO) ₃ SiC ₂ H ₄ C ₄ F ₈ C _{2 H 4 Si (MeO) 3} , (MeO) 3 SiC 2 H 4 C 6 F 12 C 2 H 4 Si (MeO) 3, (H 5 C 2 O) 3 SiC 2 H 4 C 4 F 8 C 2 H _{4 Si (OC 2 H 5)} 3, include methoxy disilane compound or the like represented by _{(H 5 C 2 O) 3} SiC 2 H 4 C 6 F 12 C 2 H 4 Si (OC 2 H 5) 3.

  The hard coat layer may contain a silane coupling agent. Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane. Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltri Acetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltri Ethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- Acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N- Examples include β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane. Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxyp Particularly preferred are propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

In addition, the hard coat layer may contain a silicon compound represented by CF ₃ (CF ₂ ) nCH ₂ CH ₂ Si (OR ₁ ) ₃ . (In the formula, R1 represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 12.) Specific examples of the compound include trifluoropropyltrimethoxysilane and trifluoropropyl. Examples include triethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and these are used alone or in combination of two or more. Can be used. _{It may} also contain H 2 NCONH (CH) mSi ( OR2) silicon compound in the terminal position represented by ₃ having a ureido group _(H 2 NCONH-). (In the formula, R2 represents an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 to 5.) Specific compounds include γ-ureidopropyltrimethoxysilane and γ-ureido. Examples thereof include propyltriethoxysilane and γ-ureidopropyltripropoxysilane. Among these, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, and the like are particularly preferable.

  In addition, the hard coat layer can use, for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, fluoroacrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin, or the like as a binder. It is preferable that a hard-coat layer contains 5-95 mass% binder on the whole.

(Other)
Further, a binder such as a known thermoplastic resin, thermosetting resin or hydrophilic resin such as gelatin may be added to the hard coat layer. These resins preferably have a polar group in the molecule. Examples of the polar _{group, -COOM, -OH, -NR2, -NR3X} , -SO 3 M, -OSO 3 M, -PO 3 M2, -OPO 3 M ( wherein, M represents a hydrogen atom, an alkali metal or an ammonium group X represents an acid that forms an amine salt, and R represents a hydrogen atom or an alkyl group.

  Further, the hard coat layer may contain fine particles of an inorganic compound or an organic compound in order to adjust the scratch resistance, slipperiness and refractive index.

  Examples of inorganic fine particles used in the hard coat layer include silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, and calcined kaolin. And calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

  Organic particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder. An ultraviolet curable resin composition such as polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluoroethylene resin powder can be added. Particularly preferred are cross-linked polystyrene particles (for example, SX-130H, SX-200H, SX-350H, manufactured by Soken Chemical), polymethyl methacrylate-based particles (for example, MX150, MX300, manufactured by Soken Chemical), and fluorine-containing acrylic resin fine particles. . Examples of the fluorine-containing acrylic resin fine particles include commercial products such as FS-701 manufactured by Nippon Paint. Examples of the acrylic particles include Nippon Paint: S-4000, and examples of the acrylic-styrene particles include Nippon Paint: S-1200, MG-251.

  The average particle diameter of these fine particle powders is preferably 0.01 to 5 μm, more preferably 0.1 to 5.0 μm, and particularly preferably 0.1 to 4.0 μm. Moreover, it is preferable to contain 2 or more types of microparticles | fine-particles from which a particle size differs. The proportion of the ultraviolet curable resin composition and the fine particles is desirably blended so as to be 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin composition.

  In order to increase the heat resistance of the hard coat layer, an antioxidant that does not inhibit the photocuring reaction can be selected and used. Examples include hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives, and the like. Specifically, for example, 4,4′-thiobis (6-tert-3-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Examples thereof include hydroxy-3,5-di-tert-butylbenzyl phosphate.

  The hard coat layer coating solution may contain a solvent, or may be appropriately contained and diluted as necessary. Examples of the organic solvent contained in the coating solution include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), It can be appropriately selected from esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents, or a mixture thereof can be used. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%.

  Further, the hard coat layer preferably contains a silicone surfactant or a polyoxyether compound. As the silicone surfactant, polyether-modified silicone is preferable. Specifically, BYK-UV3500, BYK-UV3510, BYK-333, BYK-331, BYK-337 (manufactured by BYK-Chemical Japan), TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone), KF-351, KF-351A, KF-352, KF-353, KF-354, KF-355, KF-615, KF-618, KF-945, KF- 6004 (polyether-modified silicone oil; manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are exemplified, but not limited thereto.

  Of the polyoxyether compounds, the polyoxyethylene oleyl ether compound is preferable, which is a compound represented by the general formula (α).

Formula (α) C ₁₈ H ₃₅ —O (C ₂ H ₄ O) nH
In the formula, n represents 2 to 40.

  The average addition number (n) of ethylene oxide with respect to the oleyl part is 2 to 40, preferably 2 to 10, more preferably 2 to 9, and further preferably 2 to 8. The compound of the general formula (α) can be obtained by reacting ethylene oxide with oleyl alcohol.

  Specific products include Emulgen 404 (polyoxyethylene (4) oleyl ether), Emulgen 408 (polyoxyethylene (8) oleyl ether), Emulgen 409P (polyoxyethylene (9) oleyl ether), Emulgen 420 (polyoxy) Ethylene (13) oleyl ether), Emulgen 430 (polyoxyethylene (30) oleyl ether) or more, Kao Corporation, NOFBLEEAO-9905 (polyoxyethylene (5) oleyl ether) manufactured by NOF Corporation. Note that () represents the number n.

  Nonionic polyoxyether compounds may be used alone or in combination of two or more. These improve applicability | paintability and it is preferable to add these components in 0.01-3 mass% with respect to the solid content component in a coating liquid.

  Further, the hard coat layer may contain a fluorine-siloxane graft polymer.

  The fluorine-siloxane graft polymer refers to a copolymer polymer obtained by grafting polysiloxane containing siloxane and / or organosiloxane alone and / or organopolysiloxane to at least a fluorine-based resin. Examples of commercially available products include ZX-022H, ZX-007C, ZX-049, and ZX-047-D manufactured by Fuji Kasei Kogyo Co., Ltd. These compounds may be used as a mixture. Fluorine-siloxane graft polymer should be used in a coating solution that has a mass ratio of actinic ray curable resin to fluorine-siloxane graft polymer: energy-active radiation curable resin = 0.05: 100 to 5.00: 100. To preferred.

  The hard coat layer may have a multilayer structure of two or more layers. One or both of them may be a so-called conductive layer containing, for example, conductive fine particles, a π-conjugated conductive polymer, or an ionic polymer. Examples of the π-conjugated conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and poly (3-hexylthiophene). , Poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-bromothiophene), poly (3-chlorothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene) , Poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3 Octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3,4-dihydroxythiophene), poly (3,4-dimethoxythiophene), poly (3,4-di Ethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene), poly (3,4-dioctyloxythiophene), poly ( 3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4 4-butenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3-methyl-4 -Ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene) , Polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-N-propylpyrrole), poly (3-butylpyrrole), poly (3-octyl) Pyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3-carboxypyrrole), poly (3 -Methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl 4-carboxybutylpyrrole), poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxypyrrole), poly ( 3-methyl-4-hexyloxypyrrole), polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), poly (3-anilinesulfonic acid) and the like. . Each of these may be used alone or two types of copolymers can be suitably used.

  Further, as a color correction filter for various display elements, a color tone adjusting agent (dye or pigment, etc.) having a color tone adjusting function may be included, or an electromagnetic wave blocking agent or an infrared absorbing agent may be added to each function. It is preferable to have it.

  As the coating method of the hard coat layer coating solution, the above-described methods can be used. The coating amount is suitably 0.1 to 100 μm, preferably 0.5 to 70 μm, as the wet film thickness. Moreover, as a dry film thickness, it is an average film thickness of 0.1-50 micrometers, Preferably it is 1-35 micrometers. The hard coat layer may be a single layer or a multilayer structure of two or more layers.

  The hard coat layer has a center line average roughness (Ra) defined by JIS B 0601 of 0.001 to 0.1 μm, or a fine hard coat layer and Ra is adjusted to 0.1 to 1 μm. An antiglare hard coat layer may also be used. The center line average roughness (Ra) is preferably measured by an optical interference type surface roughness measuring instrument, and can be measured, for example, using a non-contact surface fine shape measuring device WYKO NT-2000 manufactured by WYKO.

(Coating process)
In the formation of the hard coat layer, the step of subjecting the hard coat layer to light irradiation and subsequent heat treatment after coating and drying is preferred from the viewpoint that the objective effect of the present invention is more easily exhibited.

  An example of the heat treatment step is as shown in FIG. In addition, the heat treatment step needs to be performed in a place where the temperature and humidity can be adjusted, and is preferably performed in a clean room without dust.

  A preferable temperature for the heat treatment is 80 ° C. or higher, more preferably 120 ° C. or higher, from the viewpoint that the target effect is better exhibited. Further, the heat treatment time is preferably 20 minutes or less. Even if the heat treatment is carried out for a time longer than 20 minutes, the objective effect obtained better is not changed, and the film tends to be deteriorated in appearance such as discoloration or deformation due to heat.

  The heat treatment time here refers to a time during which the temperature is kept constant at a desired temperature, and does not include the time when the temperature is raised and the time when the temperature is lowered.

  The temperature to be held is preferably in the range of ± 5 ° C. of the set temperature. There may be a plurality of heat treatment steps. In that case, it may be designed so that each temperature can be changed.

  FIG. 1 is a schematic view showing a step of performing heat treatment continuously after irradiation. The long film Y is fed out from the feed roll 1, transported by the transport roller 2, and a hard coat layer is applied by the extrusion coater 3. At this time, the hard coat layer may be a single layer structure or a plurality of layers. Next, the long film Y coated with the hard coat layer is dried in the drying zone 5. The temperature of the drying zone 5 is preferably 50 to 150 ° C. Drying is performed by blowing warm air whose temperature and humidity are controlled from the front surface, back surface, or both surfaces of the long film Y. After drying, the film is cured by irradiating actinic rays such as ultraviolet rays with an air-cooled actinic ray lamp 6 a in the light irradiation lamp unit 6. Alternatively, the half-cure state can be achieved by controlling the irradiation amount and irradiation conditions. Actinic ray irradiation can also be performed in a state in which the long film Y is wound around the opposing roll 4 whose temperature is controlled to 20 to 120 ° C. in advance.

At that time, it is also preferable to send cooling air from the air cooling air vent 6b to adjust the temperature of the actinic ray irradiating unit, and N ₂ gas is supplied from the N ₂ supply chamber to promote hardening of the hard coat layer. It is also preferable to do.

As examples of the light irradiation lamp, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. These light sources are preferably air-cooled or water-cooled. The irradiation conditions vary depending on individual lamps, the dose of active ray is preferably a ^{50mJ / cm 2 ~1J / cm 2} , particularly preferably 50 to 500 mJ / cm ^2. Further, it is preferable to reduce the oxygen concentration to 0.01% to 5% by nitrogen purge in the irradiated portion.

  Next, after the light irradiation, heat treatment is performed in the heating zone 7. In the heating zone 7, the long film Y is heated at a predetermined temperature for a predetermined time by the transport rollers 2 arranged above and below.

  In the heat treatment step, it is preferably performed while applying a tension in the film transport direction or the width direction, and the applied tension is preferably 50 to 500 N / m, and more preferably 250 to 500 N / m. At 250 to 500 N / m, the objective effect of the present invention is better exhibited after a more severe durability test. When it exceeds 500 N / m, it becomes difficult to maintain the flatness of the film. The width tension applying method is not particularly limited, and may be a free span, a back roll or the like. In addition, a method of applying tension using a width regulating device in the width direction is also effective, preferably stretching by 3.0% or less, more preferably by stretching by 0.05% to 1.0%. Is more effective. Thereby, a film excellent in blocking resistance can be obtained.

  The long film Y subjected to the heat treatment is taken up as a take-up roll 9 in the take-up chamber 8. In that case, it is also preferable to carry out while blowing hot air of a predetermined temperature from the hot air outlet 10. As a measure for preventing electrification and dust adhesion, the hot air is preferably adjusted to a relative humidity in the range of 10 to 70% RH, preferably 20 to 70% RH, particularly 40 to 60% RH. Moreover, it is preferable that warm air is an ion wind, and it is preferable to install a static elimination apparatus and an air cleaner in the vicinity of the winding part.

  As shown in FIG. 2, the heat treatment may be performed by applying a roll of the hard coat film wound on the movable carriage 12 after the application, drying, and light irradiation, and performing the heat treatment in the heat treatment chamber A.

  In the heat treatment A, it is preferable to gradually increase or decrease the temperature in order to prevent a temperature difference between the inside and outside of the roll of the film roll due to a rapid temperature increase and avoid wrinkles and the like near the winding core. . Specifically, the rate of temperature increase and the rate of temperature decrease are preferably 0.3 to 5 ° C./hour.

  Moreover, in order to prevent blocking and to keep a winding form favorable, it is preferable to give a knurling process. The knurling process should just be formed in the at least one surface of the film, and may be formed in both surfaces. The thickness of the knurling part is preferably larger than the film thickness of the hard coat layer, and the thickness of the knurling part is preferably in the range of 5 to 30 μm. Preferably it is the range of 10-25 micrometers.

  In addition, as the winding core when winding the hard coat film in a roll shape, any material may be used as long as it is a cylindrical core, preferably a hollow plastic core, and a plastic material As long as it is a heat-resistant plastic that can withstand the heat treatment temperature, any resin such as phenol resin, xylene resin, melamine resin, polyester resin, and epoxy resin can be used. A thermosetting resin reinforced with a filler such as glass fiber is preferred. The number of windings on these winding cores is preferably 100 windings or more, more preferably 500 windings or more, and the winding thickness is preferably 5 cm or more. Moreover, when performing the said heat processing in the state which wound the hard coat film wound up in roll shape, you may rotate this roll.

  The rotation is preferably performed at a speed of 1 rotation or less per minute, and may be continuous or intermittent. Moreover, it is also preferable to perform the roll rewinding once or more during the heating period.

  In order to rotate the long hard coat film wound around the core during the heat treatment, it is preferable to provide a dedicated turntable in the heat treatment chamber. More preferably, the hard coat film is set on a dedicated carriage having a heat-resistant rotation function and rotated during the heat treatment in the heating chamber.

  It is also preferable that the hard coat film roll after the heat treatment is carried, for example, to a rewinding step (not shown) and cooled to room temperature while the hard coat film is rewinded to obtain a rewind roll. Furthermore, in the rewinding step, it is preferable to pass an atmosphere having a relative humidity of 10 to 70% RH or to wind in the atmosphere. When the relative humidity is preferably 20 to 70% RH, particularly 40 to 60% RH, a good hard coat film roll can be obtained without static electricity failure or collapse of the winding shape. The film rewinding speed is in the range of 1 to 200 m / min, preferably 10 to 100 m / min. At the time of rewinding, it is preferable that the film is drawn out and brought into contact with at least one roller in order to lower the film temperature.

  When rotating or rewinding these rolls, there is a possibility that static electricity failure or scratches may occur on the film. It is preferable to install a static eliminator or in a clean room. The surface of the contact roller during rewinding is smooth. It is preferable to use one having a high value.

  As the heating means in the heat treatment step, hot air blowing, contact heat transfer using a heating roll, induction heating using a microwave, radiant heat heating using an infrared heater, or the like can be used. As the infrared heater, an electric, gas, oil or steam far infrared ceramic heater can be used. A commercially available infrared heater (for example, manufactured by Noritake Company Limited) may be used. An oil-type or steam-type infrared heater using oil or steam as the heat medium is preferable from the viewpoint of explosion prevention in an atmosphere in which an organic solvent coexists. Moreover, the film temperature and heating temperature at the time of a heating can be measured with the non-contact-type infrared thermometer generally marketed. Further, feedback control may be performed on the heating means in order to control the temperature range.

  As a coating method of these hard coat layers, it can be applied by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or an ink jet method.

Further, the hard coat layer of the present invention, (HMS) is 400 N / mm ² or more, and preferably 800 N / mm ² or less. By adjusting the Martens hardness within this range, the surface hardness is excellent, and the object effect of the present invention is exhibited better.

  Martens hardness (Vickers hardness) is a microhardness meter using a Vickers indenter and a triangular pyramid indenter whose angle between ridges is 115 degrees. The hard coat surface of the film is approximately 1 / th of the film thickness of the hard coat layer. In the load test force-indentation depth curve when the indenter is pushed down to a thickness of 10, the indentation from the 50% value to the 90% value of the maximum load test force (Fmax) obtained from the load test force-indentation depth curve From the slope (m) in which the depth is proportional to the square root of the load test force, it is a value defined by the following formula.

1HMs = 1 / (26.4m ² )
Since the first protective film having the hard coat layer and the polarizing plate of the present invention have a high pencil hardness, the effect of the present invention is easily exhibited, so the pencil hardness is preferably 3H or more, more preferably 4H. That's it. The pencil hardness is 3H or higher and high hardness characteristics are exhibited. The surface hardness in the present invention means pencil hardness.

  For the pencil hardness, the prepared hard coat film is conditioned at a temperature of 23 ° C. and a relative humidity of 55% for 2 hours or more, and then using a test pencil specified by JIS S 6006, the pencil hardness specified by JIS K 5400. It is the value measured according to the evaluation method.

  The hard coat layer may be subjected to the following surface treatment. Examples of the surface treatment method include a cleaning method, an alkali saponification treatment method, a plasma treatment method, an electron beam method, an ion beam method, a sputtering method, an acid treatment, a corona treatment method, and an atmospheric pressure glow discharge plasma method.

  The alkali saponification treatment is generally carried out in a cycle in which the film is immersed in an alkali solution, washed with water and dried. Further, after the alkali treatment, neutralization in an acidic water step may be performed, followed by washing with water and drying. Examples of the alkaline solution include potassium hydroxide solution and sodium hydroxide solution, and the prescribed concentration of hydroxide ions is preferably 0.1 to 3N, and more preferably 0.5N to 2N. Adhesiveness between the hard coat layer and the low refractive index layer can be obtained by setting the content in the above range. The temperature of the alkaline solution is preferably in the range of 25 to 90 ° C., more preferably 40 to 70 ° C., from the viewpoint of precipitation of the alkaline solution. The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes.

  Further, the alkali saponification treatment may be performed by applying an alkali solution to the hard coat layer surface. For example, the methods described in JP-A Nos. 2003-313326 and 2007-332253 may be used.

  Examples of the plasma treatment include flame plasma treatment, atmospheric pressure plasma treatment, and atmospheric pressure plasma treatment.

  As plasma treatment, plasma treatment techniques disclosed in Japanese Patent Application Laid-Open Nos. 2004-352777, 2004-352777, 2007-314707, and the like can also be referred to.

  Further, the pure water contact angle on the surface of the hard coat layer after the surface treatment is 60 ° or less because, for example, when a low refractive index layer is provided on the hard coat layer, the adhesion between the hard coat layer and the hard coat layer is improved. preferable. The contact angle can be measured based on JIS K 2396.

<Antireflection film>
The first protective film having a hard coat layer according to the present invention may have an antireflection function in which a low refractive index layer is laminated directly or via another layer on the hard coat layer. By having an antireflection function, an effect of improving the visibility when incorporated in an image display device can be obtained.

(Low refractive index layer)
A low refractive index layer means a layer lower than the refractive index of a film base material. A specific refractive index is preferably in the range of 1.20 to 1.45 at 23 ° C. and a wavelength of 550 nm. Further, the film thickness of the low refractive index layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and further preferably 30 nm to 0.2 μm, from the characteristics as an optical interference layer.

  Further, in addition to the low refractive index layer, an antireflection layer may be configured by further combining a high refractive index layer having a higher refractive index than the support. Further, a medium refractive index layer (a layer having a higher refractive index than the support and a lower refractive index than the high refractive index layer) may be laminated. Moreover, you may provide a backcoat layer in the film back surface.

  Specific examples of the layer structure of the antireflection film include the following, but are not limited thereto.

Transparent film / Hard coat layer / Medium refractive index layer / Low refractive index layer Transparent film / Hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Transparent film / Hard coat layer / Low refractive index layer Transparent film / Hard coat layer / conductive layer / low refractive index layer Transparent film / hard coat layer / high refractive index layer (conductive layer) / low refractive index layer Transparent film / hard coat layer / antiglare layer / low refractive index layer Back coat layer / transparent film / hard coat layer / low refractive index layer Back coat layer / transparent film / hard coat layer / medium refractive index layer / low refractive index layer Back coat layer / transparent film / hard coat layer / antiglare layer / Low refractive index layer Back coat layer / Transparent film / Hard coat layer / Conductive layer / Low refractive index layer Back coat layer / Transparent film / Hard coat layer / High refractive index layer (conductive layer) / Low refractive index layer Low The composition for forming a refractive layer may contain at least one kind of particles having an outer shell layer and porous or hollow inside as silica-based fine particles. The porous or hollow particles are preferably hollow silica-based fine particles.

(Hollow silica fine particles)
The hollow silica-based fine particles are (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having cavities inside, and the contents are solvent, gas or porous It is a hollow particle filled with a porous material. Note that the low refractive index layer only needs to contain either (I) composite particles or (II) hollow particles, or both.

  Note that the cavity particles are particles having a cavity inside, and the cavity is covered with a coating layer (also referred to as a particle wall). The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle size of such hollow fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The average particle diameter of the hollow fine particles to be used is desirably 3/2 to 1/10, preferably 2/3 to 1/10, of the average film thickness of the low refractive index layer to be formed. These hollow fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol) and ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), ketone alcohol (for example, diacetone alcohol), or a mixed solvent containing these is preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and it is easy to use a silicate monomer or oligomer having a low polymerization degree, which is a coating liquid component described later. In some cases, the refractive index of the particles is increased by entering the voids inside the composite particles, and the effect of low refractive index may not be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible. In the case of hollow particles, if the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. .

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. Moreover, components other than silica may be contained, and specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O _3. , MoO ₃ , ZnO ₂ , WO _{3 and the} like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF 6, MgF, and the like. Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ and WO _3. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MO _X / SiO ₂ when the silica is expressed by SiO ₂ and the inorganic compound other than silica is expressed in terms of oxide (MO _X ) is 0.0001 to 1.0, Preferably it is in the range of 0.001 to 0.3. It is difficult to obtain a porous particle having a molar ratio MO _X / SiO ₂ of less than 0.0001. Even if it is obtained, a pore volume is small and particles having a low refractive index cannot be obtained. In addition, when the molar ratio MO _X / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it is difficult to obtain a material having a lower refractive index. is there.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  In addition, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used when preparing the hollow particles, the catalyst used, and the like. Moreover, what consists of the compound illustrated by the said porous particle as a porous substance is mentioned. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such hollow fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, hollow fine particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared in advance. A mixed aqueous solution is prepared, and this aqueous solution is gradually added to an aqueous alkaline solution having a pH of 10 or more while stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.

  In addition, alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica. Specifically, an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium And salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Usually, these sols are used. Can do. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When using a seed particle dispersion, the pH of the seed particle dispersion is adjusted to 10 or higher, and then an aqueous solution of the compound is added to the above-mentioned alkaline aqueous solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion. When seed particles are used in this way, it is easy to control the particle size of the porous particles to be prepared, and particles with uniform particle sizes can be obtained.

  The silica raw material and the inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. It grows on the top and particle growth occurs. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

The composite ratio of silica and an inorganic compound other than silica in the first step is that the inorganic compound relative to silica is converted to an oxide (MO _X ), and the molar ratio of MO _X / SiO ₂ is 0.05 to 2.0, Preferably it is in the range of 0.2-2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing the hollow particles, the molar ratio of MO _X / SiO ₂ is preferably in the range of 0.25 to 2.0.

Second step: Removal of inorganic compound other than silica from porous particles In the second step, inorganic compounds other than silica (elements other than silicon and oxygen) are obtained from the porous particle precursor obtained in the first step. At least a portion is selectively removed. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded through oxygen. By removing the inorganic compound (elements other than silicon and oxygen) from the porous particle precursor in this way, porous particles having a larger porosity and a larger pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, fluorine-substituted, obtained by dealkalizing an alkali metal salt of silica into the porous particle precursor dispersion obtained in the first step. It is preferable to add a silicic acid solution containing an alkyl group-containing silane compound or a hydrolyzable organosilicon compound to form a silica protective film. The thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

  By forming such a silica protective film, inorganic compounds other than silica described above can be removed from the porous particle precursor while maintaining the particle shape. Further, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore the silica coating layer described later is formed without reducing the pore volume. Can do. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

  When preparing hollow particles, it is desirable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor composed of a silica protective film, a solvent in the silica protective film, and an undissolved porous solid content. When a coating layer to be described later is formed on the precursor, the formed coating layer becomes a particle wall to form hollow particles.

The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. The hydrolyzable organic silicon compound used for the silica protective film formed of the general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, such as acrylic group An alkoxysilane represented by a hydrocarbon group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as fluorine-substituted tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed. The produced silicic acid polymer is deposited on the surface of the inorganic oxide particles. At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, a silica protective film can be formed using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film together using a silicic acid liquid and the said alkoxysilane.

Third step: Formation of silica coating layer In the third step, the porous particle dispersion prepared in the second step (in the case of hollow particles, the hollow particle precursor dispersion) contains a fluorine-substituted alkyl group-containing silane compound. By adding a hydrolyzable organosilicon compound or silicic acid solution, the surface of the particles is coated with a polymer such as a hydrolyzable organosilicon compound or silicic acid solution to form a silica coating layer.

The hydrolyzable organic silicon compound used for the silica coating layer formed, the above-mentioned such general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, An alkoxysilane represented by a hydrocarbon group such as an acryl group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, a hollow particle precursor). In addition, the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors). At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of porous particles (in the case of hollow particles, the hollow particle precursor) is water alone or a mixed solvent with an organic solvent and the mixed solvent has a high ratio of water to the organic solvent, a silicate solution You may form a coating layer using. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The silicic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors). ) Deposit on the surface. In addition, you may use a silicic acid liquid for the coating layer formation in combination with the said alkoxysilane. The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the finally obtained silica coating layer has a thickness of 1 to 20 nm. In such an amount, it is added in a dispersion of porous particles (in the case of hollow particles, a hollow particle precursor). When the silica protective film is formed, the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 20 nm.

  Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of a hollow particle precursor, the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably in the range of 80 to 300 ° C. When the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. Further, when the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of low refractive index may not be obtained.

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.42. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow. As the hollow silica-based fine particles, those commercially available from Catalyst Kasei Co., Ltd. can be preferably used.

  The content of the hollow silica-based fine particles having an outer shell layer and porous or hollow inside is preferably 10 to 50% by mass. In order to obtain the effect of a low refractive index, the content is preferably 15% by mass or more. Most preferably, it is 20-50 mass%.

  As a method of adding to the low refractive index layer, for example, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of the tetraalkoxysilane, pure water, and alcohol is added to the dispersion of the hollow silica fine particles. The silicic acid polymer produced by hydrolyzing tetraalkoxysilane is deposited on the surface of the hollow silica fine particles. At this time, tetraalkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used. The silica-based fine particles may be those produced by the production method described in the pamphlet of WO2007 / 099814.

(binder)
Moreover, it is preferable that the low refractive index layer contains the above-described cationic polymerizable compound as a binder from the viewpoint that the objective effect can be better exhibited. As the cationic polymerizable compound, the compounds described in the hard coat layer described above can be used. In addition, it is also preferable to use the above acid or photoacid generator as a compound that accelerates the polymerization of the cationic polymerizable compound. These acids and photoacid generators are preferably added in a proportion of 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound. From the viewpoint of stability in the composition for forming a low refractive index layer, polymerization reactivity, and the like.

  Moreover, you may use a radically polymerizable compound as a binder. As the radical polymerizable compound, the compounds described in the hard coat layer described above can be used.

  In order to accelerate curing of the radical polymerizable compound, it is preferable to use a photopolymerization initiator, and it is preferable to contain the photopolymerization initiator and the radical polymerizable compound in a mass ratio of 20: 100 to 0.01: 100.

  Furthermore, the fluorine substituted alkyl group containing silane compound represented by the said general formula (OSi-2) can also be contained.

  If the fluorine-containing alkyl group-containing silane compound is included as a binder, the transparent film itself is hydrophobic, so the transparent film is not sufficiently densified and is porous or cracked. Even if it has a void or a void, entry into the transparent film by chemicals such as moisture, acid and alkali is suppressed. Furthermore, fine particles such as metals contained in the conductive layer which is the substrate surface or the lower layer do not react with chemicals such as moisture, acid and alkali. For this reason, such a transparent film has excellent chemical resistance.

  In addition, when a fluorine-substituted alkyl group-containing silane compound is included as a binder, not only the hydrophobic property but also the slipperiness (low contact resistance) is obtained, and thus a transparent film having excellent scratch strength can be obtained. Can do. Further, when the binder contains a fluorine-substituted alkyl group-containing silane compound having such a structural unit, when the conductive layer is formed in the lower layer, the shrinkage rate of the binder is equivalent to that of the conductive layer. Therefore, it is possible to form a transparent film having excellent adhesion to the conductive layer. Furthermore, when the transparent film is heat-treated, the conductive layer is not peeled off due to the difference in shrinkage rate, and a portion having no electrical contact is not generated in the transparent conductive layer. For this reason, sufficient electroconductivity can be maintained as a whole film.

  A transparent film containing a fluorine-substituted alkyl group-containing silane compound and hollow silica-based fine particles having the outer shell layer and being porous or hollow inside has high scratch strength and is evaluated by eraser strength or nail strength. The film strength is high, the pencil hardness is high, and a transparent film excellent in strength can be formed.

  The low refractive index layer may contain a silane coupling agent. Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane. Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltri Acetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltri Ethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- Acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N- Examples include β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxyp Particularly preferred are propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

The low refractive index layer may contain a silicon compound represented by CF ₃ (CF ₂ ) nCH ₂ CH ₂ Si (OR ₁ ) ₃ . (In the formula, R1 represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 12.) Specific examples of the compound include trifluoropropyltrimethoxysilane and trifluoropropyl. Examples include triethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and these are used alone or in combination of two or more. Can be used. _{It may} also contain H 2 NCONH (CH) mSi ( OR2) silicon compound in the terminal position represented by ₃ having a ureido group _(H 2 NCONH-). (In the formula, R2 represents an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 to 5.) Specific compounds include γ-ureidopropyltrimethoxysilane and γ-ureido. Examples thereof include propyltriethoxysilane and γ-ureidopropyltripropoxysilane. Among these, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, and the like are particularly preferable.

  In addition, the low refractive index layer can use, for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, fluoroacrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin, etc. as a binder. .

  In addition, examples of the binder include polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, fluoroacrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, and alkyd resin.

  The low refractive index layer preferably contains 5 to 80% by mass of binder as a whole. The binder has a function of maintaining the structure of the low refractive index layer including voids. The usage-amount of a binder is suitably adjusted so that the intensity | strength of a low refractive index layer can be maintained, without filling a space | gap.

(solvent)
The low refractive index layer preferably contains an organic solvent. Specific examples of organic solvents include alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The solid content concentration in the low refractive index layer coating composition is preferably 1 to 4% by mass. By making the solid content concentration 4% by mass or less, coating unevenness is less likely to occur, and the content is 1% by mass or more. By doing so, the drying load is reduced.

  The low refractive index layer is a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, a known method such as an inkjet method, and the above coating composition for forming the low refractive index layer is applied, and after coating, It is formed by heat drying and curing treatment as necessary.

  The coating amount is suitably 0.05 to 100 μm, preferably 0.1 to 50 μm, as the wet film thickness. Further, the solid content concentration of the coating composition is adjusted so that the dry film thickness becomes the above film thickness.

Moreover, after forming a low refractive index layer, you may include the process of heat-processing at the temperature of 50-160 degreeC. The period of the heat treatment may be appropriately determined depending on the set temperature. For example, if it is 50 ° C., it is preferably a period of 3 days or more and less than 30 days, and if it is 100 ° C., a range of 1 minute or more and 1 day or less is preferable. . Examples of the curing method include a method of thermosetting by heating, a method of curing by irradiation with light such as ultraviolet rays, and the like. In the case of thermosetting, the heating temperature is preferably 50 to 300 ° C, preferably 60 to 250 ° C, more preferably 80 to 150 ° C. When curing by light irradiation, exposure of the irradiation light is ^{preferably, 100mJ / cm 2 ~500mJ / cm} 2 and more preferably ^{10mJ / cm 2 ~10J / cm 2} .

Here, the wavelength range of the irradiated light is not particularly limited, but light having a wavelength in the ultraviolet region is preferably used. Specifically, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm ² , preferably 5 to 150 mJ / cm ² , and particularly preferably 20 to 100 mJ / cm ² .

(High refractive index layer)
The antireflection layer may have the following high refractive index layer in addition to the above-described low refractive index layer. The high refractive index layer preferably contains metal oxide fine particles. The kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S A metal oxide having at least one element selected from the group consisting of Al, In, Sn, Sb, Nb, a halogen element, Ta and the like is doped with a minute amount of atoms. May be. A mixture of these may also be used. Among them, at least one metal oxide fine particle selected from zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate is used as a main component. Is particularly preferred. In particular, it is preferable to contain zinc antimonate particles.

  The average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, particularly preferably 10 to 150 nm. The average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased. The shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.

  Specifically, the refractive index of the high refractive index layer is higher than the refractive index of the film as the support, and is preferably in the range of 1.5 to 2.2 when measured at 23 ° C. and a wavelength of 550 nm. The means for adjusting the refractive index of the high refractive index layer is that the kind and addition amount of the metal oxide fine particles are dominant, so that the refractive index of the metal oxide fine particles is preferably 1.80 to 2.60, More preferably, it is 1.85 to 2.50.

  The metal oxide fine particles may be surface-treated with an organic compound. By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. . For this reason, the surface modification amount with a preferable organic compound is 0.1 mass%-5 mass% with respect to metal oxide particle, More preferably, it is 0.5 mass%-3 mass%. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, silane coupling agents are preferred. Two or more kinds of surface treatments may be combined.

  The thickness of the high refractive index layer containing the metal oxide fine particles is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm.

  The ratio of the metal oxide fine particles to be used and a binder such as an actinic ray curable resin to be described later varies depending on the kind of metal oxide fine particles, the particle size, etc. The latter one is preferable. The amount of the metal oxide fine particles used is preferably 5% by mass to 85% by mass, more preferably 10% by mass to 80% by mass, and most preferably 20% by mass to 75% by mass in the high refractive index layer. If the amount used is small, the desired refractive index and the effect of the present invention cannot be obtained, and if it is too large, the film strength deteriorates.

  The metal oxide fine particles are supplied to a coating solution for forming a high refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ketone alcohol (eg, diacetone alcohol). , Esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene) Chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, Tiger hydrofuran), ether alcohols (e.g., 1-methoxy-2-propanol), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate. Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide fine particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder. It is also preferable to contain a dispersant.

  Furthermore, metal oxide fine particles having a core / shell structure may be contained. One layer of the shell may be formed around the core, or a plurality of layers may be formed in order to further improve the light resistance. The core is preferably completely covered by the shell.

  For the core, titanium oxide (rutile type, anatase type, amorphous type, etc.), zirconium oxide, zinc oxide, cerium oxide, indium oxide doped with tin, tin oxide doped with antimony, etc. can be used. Titanium may be the main component.

  The shell is preferably formed of a metal oxide or sulfide containing an inorganic compound other than titanium oxide as a main component. For example, an inorganic compound mainly composed of silicon dioxide (silica), aluminum oxide (alumina) zirconium oxide, zinc oxide, tin oxide, antimony oxide, indium oxide, iron oxide, zinc sulfide, or the like is used. Of these, alumina, silica, and zirconia (zirconium oxide) are preferable. A mixture of these may also be used.

  The coating amount of the shell with respect to the core is 2 to 50% by mass as an average coating amount. Preferably it is 3-40 mass%, More preferably, it is 4-25 mass%. When the coating amount of the shell is large, the refractive index of the fine particles is lowered, and when the coating amount is too small, the light resistance is deteriorated. Two or more inorganic fine particles may be used in combination.

  The titanium oxide used as a core can use what was produced by the liquid phase method or the gaseous-phase method. As a method for forming the shell around the core, for example, U.S. Pat. No. 3,410,708, JP-B-58-47061, U.S. Pat. No. 2,885,366, and U.S. Pat. No. 1, British Patent No. 1,134,249, US Pat. No. 3,383,231, British Patent No. 2,629,953, No. 1,365,999, etc. Can do.

  The high refractive index layer or the low refractive index layer described above can contain a compound represented by the following general formula (CL1) or a chelate compound thereof, and can improve physical properties such as hardness.

Formula (CL1) _An MB _x-n
In the formula, M represents a metal atom, A represents a hydrolyzable functional group or a hydrocarbon group having a hydrolyzable functional group, and B represents an atomic group covalently or ionically bonded to the metal atom M. x represents the valence of the metal atom M, and n represents an integer of 2 or more and x or less.

  Examples of the hydrolyzable functional group A include halogens such as alkoxyl groups and chloro atoms, ester groups and amide groups. The metal compound belonging to the general formula (CL1) includes an alkoxide having two or more alkoxyl groups directly bonded to a metal atom, or a chelate compound thereof. Preferable metal compounds include titanium alkoxide, zirconium alkoxide, or chelate compounds thereof. Titanium alkoxide has a high reaction rate and a high refractive index and is easy to handle. However, since it has a photocatalytic action, its light resistance deteriorates when added in a large amount. Zirconium alkoxide has a high refractive index but tends to become cloudy, so care must be taken in dew point management during coating. Moreover, since titanium alkoxide has the effect of promoting the reaction of the ultraviolet curable resin and metal alkoxide, the physical properties of the coating film can be improved by adding a small amount.

  Examples of the titanium alkoxide include tetramethoxy titanium, tetraethoxy titanium, tetra-iso-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, and the like. Is mentioned.

  Examples of the zirconium alkoxide include tetramethoxy zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert-butoxy zirconium and the like. Is mentioned.

  Preferred chelating agents for forming a chelate compound by coordination with a free metal compound include alkanolamines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, acetylacetone and acetoacetic acid. Examples thereof include ethyl and the like having a molecular weight of 10,000 or less. By using these chelating agents, it is possible to form a chelate compound that is stable against water mixing and is excellent in the effect of reinforcing the coating film.

  The addition amount of the metal compound is preferably adjusted so that the content of the metal oxide derived from the metal compound contained in the high refractive index layer is 0.3 to 5% by mass. If it is less than 0.3% by mass, the scratch resistance is insufficient, and if it exceeds 5% by mass, the light resistance tends to deteriorate.

  The high refractive index layer preferably contains a radical polymerizable compound as a binder for the metal oxide fine particles in order to improve the film forming property and physical properties of the coating film. As the radically polymerizable compound, a monomer or oligomer having two or more functional groups that cause a polymerization reaction directly by irradiation with actinic rays such as ultraviolet rays or electron beams or indirectly by the action of a photopolymerization initiator is used. Specifically, polyol acrylate, epoxy acrylate, urethane acrylate, polyester acrylate or a mixture thereof is preferable. For example, the polyfunctional acrylate compound described in the hard coat layer described above is preferable.

  The addition amount of the radical polymerizable compound is preferably 15% by mass or more and less than 50% by mass in the solid content in the high refractive index composition.

  In order to accelerate curing of the radically polymerizable compound, it is preferable to contain a photopolymerization initiator. The addition amount of the photopolymerization initiator is preferably contained in a mass ratio of photopolymerization initiator: radically polymerizable compound = 3: 7 to 1: 9.

  As the photopolymerization initiator, specifically, the compounds described in the hard coat layer described above can be used.

  Examples of the organic solvent used for coating the high refractive index layer include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol). , Benzyl alcohol, etc.), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thio Diglycol, etc.), polyhydric alcohol ethers (eg, ethylene glycol monomethyl ether, Lenglycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ether) Range amine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.) ), Heterocyclic rings (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone), sulfoxides (for example, dimethyl sulfoxide) , Sulfones (e.g., sulfolane), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable.

  The high refractive index layer is obtained by applying the above composition to a transparent resin film or hard coat layer surface using a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like. It is applied by 1 to 100 μm, and after application, it is dried by heating, and is cured as necessary. The content described in the low refractive index layer can be used in the curing step. The dry film thickness is adjusted to the above film thickness by adjusting the solid content concentration of the coating composition.

(Conductive layer)
The conductive layer can be provided on the base film, for example, applied between the hard coat layer and the antireflection layer or on the transparent film on the side opposite to the side on which the antireflection layer is provided. be able to.

  The conductive layer imparts a function of preventing the first protective film from being charged during handling. Specifically, the π-conjugated conductive polymer and ionic polymer compound described above are applied to the hard coat layer. A metal oxide or the like is preferably used.

The surface specific resistance of the conductive layer is preferably adjusted to 10 ¹¹ Ω / □ (25 ° C., 55% RH) or less, more preferably 10 ¹⁰ Ω / □ (25 ° C., 55% RH) or less. Particularly preferably, it is 10 ⁹ Ω / □ (25 ° C., 55% RH) or less.

  Here, although details of the measurement of the surface specific resistance value are described in the Examples, the sample was conditioned for 24 hours under the conditions of 25 ° C. and 55% RH, and a terraohm meter model VE-30 manufactured by Kawaguchi Electric Co., Ltd. was used. Use to measure.

  An overcoat layer may be further provided on the conductive layer as the outermost surface layer, but the surface specific resistance value is measured by measuring the surface specific resistance value on the outermost surface layer on the side where the conductive layer is provided. It is defined as the surface specific resistance value of the conductive layer.

  Furthermore, examples of the ionic polymer compound include anionic polymer compounds such as those described in JP-B-49-23828, JP-A-49-23827, and JP-A-47-28937; JP-B-55-734, JP-A-50 Ionene type polymers having a dissociation group in the main chain as seen in JP-B-54672, JP-B-59-14735, JP-A-57-18175, JP-A-57-18176, JP-A-57-56059, etc .; No. -13223, No. 57-15376, No. 53-45231, No. 55-145578, No. 55-65950, No. 55-67746, No. 57-11342, No. 57-19735, No. 58 Cationic pendant having a cationic dissociation group in the side chain as seen in JP-A-56858, JP-A-61-27853, and 62-9346 Polymers; and the like. Among them, a quaternary ammonium cationic polymer having molecular crosslinking is particularly preferable, and a quaternary ammonium cationic polymer not containing chlorine ions and having molecular crosslinking is particularly preferably used from the viewpoint of environmental safety such as prevention of dioxin generation.

The ionic polymer compound may be used alone, or several types of ionic polymer compounds may be used in combination. The content of the resin film of the ionic polymer compound is preferably 0.02g~1.0g / ^{m 2,} particularly preferably from 0.02g~0.5g / ^{m 2.}

  Further, fine particles may be added to the conductive layer. Examples thereof include fine particles containing silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate and the like as constituent components.

  The average particle diameter of the fine particles described above is preferably 0.01 μm to 10 μm, more preferably 0.01 μm to 5 μm, and the addition amount is 0.05 part to 10 parts by mass with respect to the solid content in the coating agent. Parts are preferred, with 0.1 to 5 parts being particularly preferred.

  Moreover, in order for a conductive layer to show sufficient antistatic effect and to maintain easy adhesion with an overcoat layer, it is preferable to contain a cellulose ester resin or an acrylic resin.

  Examples of the cellulose ester resin include cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose nitrate.

  Examples of acrylic resins include Acrypet MD, VH, MF, V (manufactured by Mitsubishi Rayon Co., Ltd.), Hyperl M4003, M-4005, M-4006, M-4202, M-5000, M -5001, M-4501 (manufactured by Negami Kogyo Co., Ltd.), Dialnal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR- 79, BR-80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105, BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (manufactured by Mitsubishi Rayon Co., Ltd.) Various homopolymers and copolymers to produce Le and methacrylic monomer as a raw material is preferably used.

  The resin used here is preferably 60% by mass or more, more preferably 80% by mass or more of the total resin used in the conductive layer, and an actinic ray curable resin or thermosetting resin is added as necessary. You can also These resins are coated as a binder in a state dissolved in the following solvent.

  For the coating composition for coating the conductive layer, the following solvents are preferably used. As the solvent, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents (methylene chloride) can be appropriately mixed and used, but are not particularly limited thereto.

  Examples of the hydrocarbons include benzene, toluene, xylene, hexane, cyclohexane and the like, and examples of alcohols include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, tert- Examples include butanol, pentanol, 2-methyl-2-butanol, and cyclohexanol. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of esters include methyl formate, ethyl formate, Examples thereof include methyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, ethyl lactate, and methyl lactate. Examples of glycol ethers (C1 to C4) include methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ester. As terrestrial (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, or propylene glycol mono (C1-C4) alkyl ether esters, propylene glycol monomethyl Examples of ether acetate, propylene glycol monoethyl ether acetate, and other solvents include methylene chloride and N-methylpyrrolidone. Although not particularly limited to these, a solvent in which these are appropriately mixed is also preferably used.

  As a coating method of the conductive layer coating composition, using a gravure coater, dip coater, wire bar coater, reverse coater, extrusion coater, etc., the coating solution film thickness (sometimes referred to as wet film thickness) is 1 to 100 μm. In particular, 5 to 30 μm is preferable.

(Back coat layer)
It is preferable to provide a backcoat layer on the surface opposite to the side on which the hardcoat layer is provided. The back coat layer is provided in order to correct curling caused by providing a hard coat layer or other layers. That is, the degree of curling can be balanced by imparting the property of being rounded with the surface on which the backcoat layer is provided facing inward. The back coat layer is preferably applied also as an anti-blocking layer. In this case, it is preferable that fine particles are added to the back coat layer coating composition in order to provide an anti-blocking function.

  As fine particles added to the back coat layer, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, and oxidation. Mention may be made of indium, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate.

  These fine particles are commercially available under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, and TT600 (manufactured by Nippon Aerosil Co., Ltd.). . Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used. Examples of the polymer include silicone resin, fluororesin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.

  Among these, Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large anti-blocking effect while keeping haze low. In the hard coat film of the present invention, the dynamic friction coefficient on the back side of the actinic ray curable resin layer is preferably 0.9 or less, particularly preferably 0.1 to 0.9.

  The fine particles contained in the backcoat layer are preferably contained in an amount of 0.1 to 50% by mass, more preferably 0.1 to 10% by mass with respect to the binder. The increase in haze when a backcoat layer is provided is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.0 to 0.1%.

  Examples of the solvent used for coating the backcoat layer include dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, ethylene chloride, tetrachloroethane, trichloroethane, Chloroform, water, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, cyclohexanone, cyclohexanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, or hydrocarbons (toluene, xylene) Are used in appropriate combinations.

  It is preferable to apply these coating compositions on the surface of the hard coat film with a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like with a wet film thickness of 1 to 100 μm. Is particularly preferably 5 to 30 μm.

  Examples of the resin used as the binder of the backcoat layer include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate-vinyl alcohol copolymer, partially hydrolyzed vinyl chloride-vinyl acetate copolymer. Polymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. Vinyl polymer or copolymer, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8-2.3, propionyl group substitution degree 0.1-1.0), diacetyl cellulose, cellulose Cellulose derivatives such as acetate butyrate resin, maleic acid and / or Or acrylic acid copolymer, acrylic ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin , Polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, urethane resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butadiene resin, butadiene-acrylonitrile Examples thereof include, but are not limited to, rubber resins such as resins, silicone resins, fluorine resins, and the like. As the acrylic resin, the above-described compounds can be used for the conductive layer.

  As the resin used as the binder, it is preferable to use a blend of acetylated cellulose and acrylic resin such as cellulose diacetate and cellulose acetate prothionate, and the refractive index difference between the fine particles and the binder using fine particles made of acrylic resin. By setting the value to less than 0 to 0.02, a highly transparent back coat layer can be obtained.

  The order in which the backcoat layer is applied may be before or after the hardcoat layer is applied, but when the backcoat layer also serves as an anti-blocking layer, it is preferably applied first. Alternatively, the backcoat layer can be applied in two or more steps. Moreover, it is also preferable that the backcoat layer also serves as an easy-adhesion layer for improving the adhesion with the polarizer.

(Reflectivity of antireflection layer)
The reflectance of the antireflection layer can be measured with a spectrophotometer or a spectrocolorimeter. At that time, after the surface on the measurement side of the sample is roughened, the light absorption treatment is performed by attaching a black spray, a black acrylic plate, etc., and then the reflected light in the visible light region (400 to 700 nm) is measured. To do.

  The lower the reflectivity, the better. However, the average value in the visible light region wavelength is 2.0% or less, and an external light antireflection function when used on the outermost surface of an image display device such as an LCD is suitably obtained. It is preferable from the point which is made. The minimum reflectance is preferably 0.8% or less.

  Moreover, it is preferable to have a flat reflection spectrum in the wavelength region of visible light. In addition, the reflection hue on the surface of the display device that has been subjected to the antireflection treatment is often colored red or blue because the reflectance in the short wavelength region and the long wavelength region is high in the visible light region due to the design of the antireflection film. The color tone of the reflected light varies depending on the application, and when used on the outermost surface of a flat-screen television or the like, a neutral color tone is preferred. In this case, generally preferred reflection hue ranges are 0.17 ≦ x ≦ 0.27 and 0.07 ≦ y ≦ 0.17 on the XYZ color system (CIE1931 color system). Further, the range in which the distance Δxy of (x, y) = (0.31, 0.31) on the xy plane is 0.05 or less is preferable because it is closer to neutral with no color, and 0.03 or less is preferable. Further preferred. The color tone can be calculated from the refractive index of each layer in accordance with a conventional method in consideration of the reflectance and the color of reflected light.

(Base film)
The base film of the first protective film having a hard coat layer will be described. As the base film, a cellulose ester film having at least one repeating unit represented by the general formula (1) or (2) described above can be used, and the base film described below can be used.

  The base film is preferably easy to manufacture, easy to adhere to the hard coat layer, and optically isotropic. Any of these may be used, for example, cellulose ester films such as triacetyl cellulose film, cellulose acetate propionate ionate film, cellulose diacetate film, cellulose acetate butyrate film, polyethylene terephthalate, polyethylene naphthalate. Polyester film such as phthalate, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, Shinji Otectic polystyrene film, norbornene resin film, polymethylpentene Examples include, but are not limited to, film, polyether ketone film, polyether ketone imide film, polyamide film, fluororesin film, nylon film, cycloolefin polymer film, polymethyl methacrylate film or acrylic film. Absent. Among these, cellulose ester films (for example, Konica Minoltak KC8UX2M, KC4UX2M, KC4UY, KC8UT, KC5UN, KC12UR, KC8UCR-3, KC8UCR-4 (above, manufactured by Konica Minolta Opto), polycarbonate film, cycloolefin A polymer film and a polyester film are preferred, and a cellulose ester film is particularly preferred from the viewpoint of production, cost, isotropy, adhesiveness, and the object effects of the present invention.

  The molecular weight of the cellulose ester is preferably a number average molecular weight (Mn) of 60,000 to 300,000, more preferably 70,000 to 200,000, particularly preferably 100,000 to 200,000. The cellulose ester preferably has a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 4.0 or less, more preferably 1.4 to 2.3.

  Since the average molecular weight and molecular weight distribution of the cellulose ester can be measured using high performance liquid chromatography, the number average molecular weight (Mn) and the weight average molecular weight (Mw) can be calculated using this, and the ratio can be calculated.

  The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (GL Science Co., Ltd.)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation)
A calibration curve with 13 samples from Mw = 100000 to 500 was used. The 13 samples are preferably used at approximately equal intervals.

  As the cellulose ester, a cellulose ester synthesized using cotton linter, wood pulp, kenaf or the like as a raw material can be used alone or in combination. In particular, it is preferable to use a cellulose ester synthesized from cotton linter (hereinafter sometimes simply referred to as linter) alone or in combination.

  The cellulose ester film is preferably a transparent support having a light transmittance of 90% or more, more preferably 93% or more. Cellulose ester resin has a total acyl group substitution degree (T) of 2.00 to 3.00, an acetyl group substitution degree (ac) of 0 to 1.89, and an acyl group other than the acetyl group having 3 to 7 carbon atoms. And the weight average molecular weight (Mw) is preferably 75,000 to 280000.

  Moreover, the cellulose ester film can contain the acrylic polymer described in the cellulose ester film having the repeating unit represented by the general formula (1) or (2), and acrylic polymer: cellulose ester resin = 95. : It is preferable to contain by mass ratio of 5-30: 70. The cellulose ester film may contain acrylic particles, and commercially available products may be used as the acrylic particles. For example, metabrene W-341 (C2) (manufactured by Mitsubishi Rayon Co., Ltd.), Chemisnow MR-2G (C3), MS-300X (C4) (manufactured by Soken Chemical Co., Ltd.) and the like can be mentioned. The acrylic particles are preferably contained at 0.5 to 45 mass% with respect to the total mass of the cellulose ester resin and the acrylic polymer.

  You may make a base film contain additives, such as a plasticizer described in the cellulose-ester film which has a repeating unit represented by General formula (1) or (2), and an ultraviolet absorber. Moreover, you may give an internal haze.

(particle)
Internal haze, for example, by adding particles with a refractive index different from that of the base film to the base film and controlling the addition amount, particle size, etc., generating haze due to internal scattering, and adjusting this Can be achieved. The particles are classified into inorganic particles and organic particles. The inorganic particles are not particularly limited, and examples thereof include silicon oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate. The organic particles are not particularly limited. For example, fluorinated acrylic resin powder, polystyrene resin powder, polymethacrylic acid methyl acrylate resin powder, silicone resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin Examples thereof include powder, melamine resin powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, and polyfluoroethylene resin powder. These inorganic particles and organic particles may be used in combination of two or more different types and average particle diameters, and those obtained by surface-treating the surface of the particles with an organic substance are also preferably used.

  Particularly preferred inorganic particles are silicon dioxide. Specific examples of silicon dioxide include Aerosil 200V, Aerosil R972V, Aerosil R972, R974, R812, 200, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.), Sea Hoster KEP-10, Sea Hoster KEP-30, Commercial products having trade names such as Seahoster KEP-50 (above, made by Nippon Shokubai Co., Ltd.), Silo Hovic 100 (made by Fuji Silysia), Nip Seal E220A (made by Nippon Silica Kogyo), Admafine SO (made by Admatechs), etc. Can be preferably used. The shape of the particles can be used without any particular limitation, such as indefinite shape, needle shape, flat shape, and spherical shape. However, the use of spherical particles is particularly preferable because it is easy to adjust the haze. As the organic particles, fluorine-containing acrylic resin particles are particularly suitable.

  The average particle size of the particles added to the base film is preferably 0.3 to 1 μm, more preferably 0.4 to 0.7 μm. The average particle size can be determined by visual observation from an image photograph of secondary electron emission obtained by scanning electron microscope (SEM) or the like of 500 particles or by image processing, or by dynamic light scattering, static It can be measured by a particle size distribution meter using an automatic light scattering method or the like. The average particle diameter here refers to the number average particle diameter. In addition, an average particle diameter means the average particle diameter of an aggregate, when particle | grains are the aggregates of a primary particle. Moreover, when a particle is not spherical, it means the diameter of a circle corresponding to the projected area.

  The refractive index of the particles is preferably 1.45 to 1.70, more preferably 1.45 to 1.65. In addition, the refractive index of the particles is measured by measuring the turbidity by dispersing the same amount of particles in the solvent in which the refractive index is changed by changing the mixing ratio of two kinds of solvents having different refractive indexes. The refractive index of the solvent can be measured by measuring with an Abbe refractometer.

  Further, the difference in refractive index between the resin used for the support and the particles is preferably 0.02 or more and 0.20 or less in order to increase the internal haze using the light scattering effect. A more preferable range of the refractive index difference is 0.05 or more and 0.15 or less.

  The content of the inorganic or organic particles is preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin for producing the film base material, and more preferably 5 parts by mass to 25 parts by mass for obtaining internal haze. Part.

  The particles may be dispersed together with cellulose ester, other additives and an organic solvent when preparing the composition (dope) for producing the base film, or may be dispersed alone in the solution. . As a method for dispersing the particles, it is preferable that the particles are preliminarily dispersed in an organic solvent and then finely dispersed by a disperser (high pressure disperser) having a high shearing force.

(Organic solvent)
The dope for producing the base film preferably contains an organic solvent from the viewpoint of film forming property and productivity. Any organic solvent can be used without limitation as long as it dissolves cellulose ester and other additives simultaneously. For example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3 , 3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3 , 3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane and the like. Among these organic solvents, methylene chloride, methyl acetate, ethyl acetate, and acetone are preferably used.

  The dope preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms in addition to the organic solvent. When the proportion of alcohol in the dope increases, the web gels, facilitating peeling from the metal support, and when the proportion of alcohol is small, the role of promoting dissolution of cellulose esters in non-chlorine organic solvents There is also. Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability of these dopes, the boiling point being relatively low, good drying properties, and no toxicity. The concentration of the cellulose ester in the dope is preferably adjusted to 15 to 40% by mass, and the dope viscosity is preferably adjusted to a range of 10 to 50 Pa · s in order to obtain good film surface quality.

  The substrate film may be either produced by the solution casting method or produced by the melt casting method, but is preferably at least stretched in the width direction, and in particular, the residue remaining in the solution casting step. When the dissolution amount is 3 to 40% by mass, it is preferably stretched 1.01 to 1.5 times in the width direction. More preferably, it is biaxially stretched in the width direction and the lengthwise direction, and when the amount of residual dissolution is 3 to 40% by mass, it is stretched by 1.01 to 1.5 times in the width direction and the lengthwise direction, respectively. It is desirable that The draw ratio at this time is particularly preferably 1.03 to 1.45.

  The base film has a length of 100 m to 9000 m, more preferably 1000 m to 7000 m, and a width of preferably 1.2 m or more, and more preferably 1.4 to 4 m. By making the length and width of the base film within the above ranges, the handleability and productivity are excellent. The base film is preferably in a roll shape.

(Film forming method)
The base film can be formed by the above-described solution casting method or melt casting method.

<Polarizing plate>
The polarizing plate using the first protective film and the second protective film of the present invention will be described. The polarizing plate can be produced by a general method. The first and second protective films of the present invention are subjected to alkali saponification treatment on the back side, and the treated protective film is immersed and stretched in an iodine solution on at least one surface of the polarizing film, and completely saponified polyvinyl It is preferable to bond using an aqueous alcohol solution. At that time, in the first protective film, the hard coat layer is preferably bonded to the side far from the polarizing film, and in the second protective film, the optically anisotropic layer is preferably bonded to the side far from the polarizing film.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are ones in which iodine is dyed on a system film and ones in which a dichroic dye is dyed, but it is not limited to this.

  As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound.

  A polarizing film having a thickness of 5 to 30 μm, preferably 8 to 15 μm, is preferably used. On the surface of the polarizing film, one surface of the protective film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

  In addition, the polarizing plate has a length of 100 m or more, and a productive effect is obtained. The longer the length is 1500 m, 2500 m, and 5000 m, the higher the productivity effect of manufacturing the polarizing plate. Moreover, since the polarizing plate of this invention is excellent in rework property, the effect that a polarizing plate yield improves can also be acquired.

<Liquid crystal display device>
Incorporation of the polarizing plate of the present invention on the viewing surface side of the liquid crystal display device makes it possible to produce the liquid crystal display device of the present invention that is excellent in various visibility in addition to being excellent in flat characteristics.

  As the liquid crystal display device, a reflective type, a transmissive type, a transflective type LCD, or a TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), or IPS type LCD is preferable. Although it is used, it is particularly preferably used in an IPS liquid crystal ideographic apparatus.

  FIG. 3 is a schematic view of an IPS mode liquid crystal display device according to the present invention.

  A light guide plate, a prism sheet (not shown), and a backlight side polarizing plate L-12 are arranged adjacent to the backlight L-13 from below. The polarizing film L-8 of the backlight side polarizing plate L-12 is sandwiched between the polarizing plate protective film L-7 and the polarizing plate protective film L-9. Next, there is an IPS liquid crystal cell L-6 having a configuration of an electrode side cell glass substrate L-6-2, an IPS type liquid crystal cell L-6-3, and a non-electrode type cell glass substrate L-6-1. There is a polarizing film L-2 constituting the plate L-10, a first protective film L-1 of the present invention, and a second protective film L-11.

  Other polarizing plate protective films L-7 and L-9 are not particularly limited. For example, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyethylene films, polypropylene films, polycycloolefin films, cellophane, and cellulose. Acetate film, cellulose acetate butyrate film, cellulose acetate phthalate film, cellulose acetate propionate film, cellulose triacetate, film made of cellulose esters such as cellulose nitrate or derivatives thereof, polyvinylidene chloride film, polyvinyl alcohol film, ethylene Vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film , Cycloolefin polymer film (eg, ARTON (manufactured by JSR), ZEONEX, ZEONOR (manufactured by ZEON)), polymethylpentene film, polyetherketone film, polyethersulfone film, polysulfone film, polyetherketoneimide Examples thereof include a film, a polyamide film, an acrylic film, and a polyacrylate film.

  Cellulose ester films such as cellulose acetate propionate film and cellulose triacetate film (TAC film) are commercially available films, such as Konica Minolta Op KONICA MINOLTATAC KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY KC4UY, KC12UR, KC16UR, KC4UE, KC8UE, KC4FR-1, KC4FR-2, etc. are preferably used. In addition, a cycloolefin polymer film, a polycarbonate film, a polyester film, or a polyacrylic film can also be preferably used in terms of transparency, mechanical properties, and lack of optical anisotropy. These resin films may be films formed by a melt casting method or a solution casting method.

  In the case of an IPS mode type liquid crystal display device, the polarizing plate protective films L-7 and L-9 have a retardation value Rt value in the range of -20 to 20 nm, more preferably -10 to 10 nm, and a Ro value. It is also preferable to use a film in the range of 0 to 10 nm.

<IPS horizontal electric field switching mode type liquid crystal display device>
By incorporating a polarizing plate using the polarizing plate protective film of the present invention into a commercially available IPS (In Plane Switching) mode type liquid crystal display device, it has excellent visibility, excellent color shift, corner unevenness, and front contrast characteristics. The liquid crystal display device of the present invention can be manufactured.

  The IPS mode of the present invention includes a fringe-field switching (FFS) mode in the present invention, and the polarizing plate of the present invention can be incorporated in the same manner as the IPS mode. A liquid crystal display device can be manufactured.

(IPS mode liquid crystal cell)
The liquid crystal layer of the liquid crystal panel in the IPS mode type liquid crystal display device is homogeneously aligned parallel to the substrate surface in the initial state, and the director of the liquid crystal layer is parallel to the electrode wiring direction when no voltage is applied. The direction of the director of the liquid crystal layer shifts to a direction perpendicular to the electrode wiring direction when a voltage is applied, and the director direction of the liquid crystal layer is the direction of the director when no voltage is applied. When tilted in the direction of the electrode wiring by 45 ° compared to the liquid crystal layer when the voltage is applied, the azimuth angle of the polarization is rotated by 90 ° like a half-wave plate, and the transmission axis and polarization of the output side polarizing plate are rotated. The azimuth angles of the two coincide with each other to display white.

  In general, the thickness of the liquid crystal layer is constant, but since it is driven by a lateral electric field, it is considered that a slight unevenness in the thickness of the liquid crystal layer can increase the response speed to switching. Even if the thickness of the layer is not constant, the effect can be maximized. In this invention, there is little influence with respect to the change of the thickness of a liquid crystal layer. The thickness of the liquid crystal layer is 2 to 6 μm, and preferably 3 to 5.5 μm.

  The liquid crystal display device of the present invention is used for a large liquid crystal television. As a screen size, it can be used for 17 or more types, preferably 26 to 100 types.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1
<Preparation of Cellulose Triacetate Film 1 which is a Base Film of First Protective Film>
(Preparation of dope solution A)
The following materials were sequentially put into a sealed container, the temperature in the container was raised from 20 ° C. to 80 ° C., and then stirred for 3 hours while maintaining the temperature at 80 ° C. to completely dissolve the cellulose triacetate. . The silicon oxide fine particles were dispersed and added in a solution of a solvent to be added in advance and a small amount of cellulose triacetate. This dope was filtered using a filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope solution A.

(Dope solution A)
Cellulose triacetate (acetyl group substitution degree 2.9) 100 parts by mass Trimethylolpropane tribenzoate 5 parts by mass Ethylphthalylethyl glycolate 5 parts by mass Fine particles of silicon oxide 0.1 parts by mass (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.)
Tinuvin 109 (manufactured by Ciba Japan) 1 part by weight Tinuvin 171 (manufactured by Ciba Japan) 1 part by weight Methylene chloride 400 parts by weight Ethanol 40 parts by weight Butanol 5 parts by weight The above materials are mixed to prepare a dope solution A The obtained dope liquid A was passed through a casting die kept at a temperature of 35 ° C. and cast on a support of 35 ° C. made of a stainless steel endless belt to form a web. Next, the web was dried on the support, and the web was peeled from the support with a peeling roll when the residual solvent amount of the web reached 100% by mass.

  Next, the web is transported while being dried with a drying air of 90 ° C. in a drying process of transporting by a plurality of rolls arranged on the top and bottom, and subsequently grips both ends of the web with a tenter, and then in the width direction (TD) at 130 ° C. It extended | stretched so that it might be 1.2 times before extending | stretching. After stretching with a tenter, the web was dried with a drying air of 140 ° C. in a conveying and drying process using a plurality of rolls arranged vertically. After heat-treating for 15 minutes in an atmosphere with an atmosphere substitution rate of 15 (times / hour) in the drying step, the sample was cooled to room temperature and subjected to knurling with a width of 1 cm and an average height of 25 μm at both ends. A cellulose triacetate film 1 having a refractive index of 1.49 having a thickness of 5 m, a thickness of 60 μm, and a length of 5000 m was produced.

<Atmosphere replacement rate>
The atmosphere replacement rate is defined as the atmosphere of the heat treatment chamber per unit time determined by the following formula when the atmosphere capacity of the heat treatment chamber is V (m ³ ) and the fresh air flow rate is FA (m ³ / hr). The number of replacements with -air. “Fresh-air” means that the wind blown into the heat treatment chamber is not a wind that is recycled and reused, and it means a fresh wind that does not contain volatilized solvent or plasticizer or has been removed. Yes.

Atmosphere replacement rate = FA / V (times / hour)
<Preparation of hard coat film 1>
A hard coat film 1 was produced on the produced cellulose triacetate film 1 by the following procedure.

On the cellulose triacetate film 1 produced above, the following hard coat layer coating composition 1 is filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a hard coat layer coating solution, which is coated using a micro gravure coater. Then, after drying at 80 ° C., while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less, the illuminance of the irradiation part is 200 mW / cm ² and the irradiation amount is 0.3 J / kg using an ultraviolet lamp. After the coating layer is cured as cm ^{2 and} a hard coat layer having a dry film thickness of 25 μm is formed, the back coat layer coating composition 1 described below is opposite to the surface coated with the hard coat layer so as to have a wet film thickness of 18 μm. The hard coat film 1 was prepared by coating the surface of the film with an extrusion coater and drying at 80 ° C.

(Hard coat layer composition 1)
<Preparation of fluorine-siloxane graft polymer I>
Hereinafter, commercial product names of materials used for the preparation of the fluorine-siloxane graft polymer I are shown.

Radical polymerizable fluororesin (A): Cefalcoat CF-803 (hydroxyl value 60, number average molecular weight 15,000; manufactured by Central Glass Co., Ltd.)
One-end radical polymerizable polysiloxane (B): Silaplane FM-0721 (number average molecular weight 5,000; manufactured by Chisso Corporation)
Radical polymerization initiator: Perbutyl O (t-butylperoxy-2-ethylhexanoate; manufactured by NOF Corporation)
Curing agent: Sumidur N3200 (biuret type prepolymer of hexamethylene diisocyanate; manufactured by Sumika Bayer Urethane Co., Ltd.)
(Synthesis of radical polymerizable fluororesin (A))
In a glass reactor equipped with a mechanical stirrer, thermometer, condenser and dry nitrogen gas inlet, cefal coat CF-803 (1554 parts by mass), xylene (233 parts by mass), and 2-isocyanatoethyl methacrylate (6 3 parts by mass) and heated to 80 ° C. in a dry nitrogen atmosphere. After reacting at 80 ° C. for 2 hours and confirming that the absorption of isocyanate disappeared by the infrared absorption spectrum of the sample, the reaction mixture was taken out and 50% by mass of radically polymerizable fluororesin (A) via a urethane bond. Got.

(Preparation of fluorine-siloxane graft polymer I)
In a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser and a dry nitrogen gas inlet, the synthesized radical polymerizable fluororesin (A) (26.1 parts by mass), xylene (19.5 parts by mass) ), N-butyl acetate (16.3 parts by mass), methyl methacrylate (2.4 parts by mass), n-butyl methacrylate (1.8 parts by mass), lauryl methacrylate (1.8 parts by mass), 2-hydroxyethyl Add methacrylate (1.8 parts by mass), FM-0721 (5.2 parts by mass), and perbutyl O (0.1 parts by mass), heat to 90 ° C. in a nitrogen atmosphere, and hold at 90 ° C. for 2 hours. did. Perbutyl O (0.1 part) was added, and the solution was further maintained at 90 ° C. for 5 hours to obtain a 35 mass% fluorine-siloxane graft polymer I solution having a weight average molecular weight of 171,000.

  The weight average molecular weight was determined by GPC. Moreover, the mass% of the fluorine-siloxane graft polymer I was calculated | required by HPLC (liquid chromatography).

(Hardcoat layer coating composition 1)
The following materials were stirred and mixed to obtain hard coat layer coating composition 1.

Pentaerythritol triacrylate 20.0 parts by mass Pentaerythritol tetraacrylate 50.0 parts by mass Dipentaerythritol hexaacrylate 30.0 parts by mass Dipentaerythritol pentaacrylate 30.0 parts by mass Irgacure 184 (manufactured by Ciba Japan) 8.0 Parts by mass The above-prepared fluorine-siloxane graft polymer I (35% by mass) 5.0 parts by mass Seahoster KEP-50 (silica particles having an average particle size of 0.47 to 0.61 μm, manufactured by Nippon Shokubai Co., Ltd.) 50 parts by mass propylene Glycol monomethyl ether 20 parts by weight Methyl acetate 40 parts by weight Methyl ethyl ketone 60 parts by weight (Backcoat layer coating composition 1)
Diacetylcellulose 0.6 parts by mass Methyl acetate 75 parts by mass Methanol 25 parts by mass 2% methanol dispersion of silica particles 16 parts by mass (KE-P30, manufactured by Nippon Shokubai Co., Ltd.)
(Measurement of Martens hardness)
The Martens hardness (HMs) of the hard coat layer surface of the hard coat film 1 was measured using a micro hardness meter. That is, using a microhardness meter (trade name, DUH-212, manufactured by Shimadzu Corporation) using a Vickers indenter and a triangular pyramid indenter having an angle of 115 degrees, first, a hard coat layer on the surface of the hard coat film The indenter was pushed to a thickness of about 1/10 of the film thickness, and a load test force-indentation depth curve when the indenter was pushed in was created. Next, from the created load test force-indentation depth curve, the indentation depth from the 50% value to the 90% value of the maximum load test force (Fmax) is as follows from the slope (m) proportional to the square root of the load test force. The Martens hardness (Hms) value of the hard coat layer surface defined by the formula was calculated.

1HMs = 1 / (26.4m ² )
As a result, the Martens hardness (HMs) of the hard coat layer surface of the hard coat film 1 was 452 N / mm ² .

<Preparation of hard coat films 2-4>
Hard coat films 2 to 4 were prepared by appropriately adjusting the hard coat film thickness and curing conditions so that the Martens hardness (HMs) of the hard coat layer surface of the hard coat film was the value described in Table 1.

<Preparation of retardation film 1>
<Production of Cellulose Ester Film A (Production of Cellulose Ester-Containing Transparent Film Having at least one Repeating Unit Represented by General Formula (1) or (2))>
(Synthesis of cellulose ester X)
To the reactor, 80 parts of cellulose acetate (Daicel Chemical Industries, Ltd., L-20, substitution degree 2.41) was added and dried under reduced pressure at 110 ° C. for 4 hours, 4 Torr (1 Torr is 133.322 Pa). . Thereafter, purging was performed with dry nitrogen, a reflux condenser was attached, 20 parts of ε-caprolactone and 67 parts of cyclohexanone that had been dried and distilled in advance were added, and the mixture was heated to 160 ° C. and stirred to dissolve cellulose acetate uniformly. To this reaction solution, 0.25 part of monobutyltin trioctylate was added and heated at 160 ° C. with stirring for 2 hours. Thereafter, the reaction solution was cooled to room temperature to terminate the reaction and obtain a reaction product. Furthermore, 10 parts of the reaction product was dissolved in 90 parts of chloroform, and then slowly dropped into 900 parts of a large excess of methanol, and the precipitated precipitate was filtered to remove the homopolymer of ε-caprolactone. . Furthermore, it heat-dried at 60 degreeC for 5 hours or more, and obtained the cellulose ester X which (epsilon) -caprolactone reacted with the cellulose acetate. And the primary structure of the cellulose ester obtained by < ¹ > H-NMR was analyzed. As a result, the average number of moles of ε-caprolactone reacted per mole of glucose unit was 0.43, the average degree of substitution was 0.08, and the average degree of polymerization was 5.1.

(Preparation of dope solution B)
The following materials were sequentially put into a sealed container, the temperature in the container was raised from 20 ° C. to 80 ° C., and the mixture was stirred for 3 hours while maintaining the temperature at 80 ° C. to completely dissolve the cellulose ester. The silicon oxide fine particles were added dispersed in a solution of a solvent to be added in advance and a small amount of cellulose ester. This dope was filtered using a filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope solution B.

(Dope solution B)
Cellulose ester X 100 parts by mass Monopet SB (sugar ester compound) 9 parts by mass Silicon oxide fine particles 0.1 parts by mass (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.)
Methylene chloride 400 parts by weight Ethanol 40 parts by weight Butanol 5 parts by weight The above materials are mixed to prepare a dope solution B, and the obtained dope solution B is made of stainless steel endless from a casting die kept at a temperature of 35 ° C. The web was formed by casting on a support composed of a belt and having a temperature of 35 ° C. Next, the web was dried on the support, and the web was peeled from the support with a peeling roll when the residual solvent amount of the web reached 100% by mass.

  Next, the web is transported while being dried with a drying air of 100 ° C. in a transport drying process using a plurality of rolls arranged on the upper and lower sides. Subsequently, both ends of the web are gripped by a tenter and then stretched in the width direction (TD) at 130 ° C. It extended | stretched so that it might become 1.2 times before. After stretching with a tenter, the web was dried with a drying air of 140 ° C. in a conveying and drying process using a plurality of rolls arranged vertically. The film was cooled to room temperature and subjected to a knurling process having a width of 10 mm and an average height of 10 μm at both ends of the film and wound up to prepare a cellulose ester film A having a width of 1.5 m, a film thickness of 80 μm, a length of 5000 m, and a length. The draw ratio of the web conveyance direction (MD) immediately after peeling calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times.

  The retardation of the cellulose ester film A was Ro = 80 nm and Rt = 170 nm. The retardation is a value measured at a wavelength of 590 nm using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments) after humidity adjustment to 23 ° C. and 55% RH.

(Preparation of retardation film 1)
On the cellulose ester film A prepared above, the following intermediate layer coating solution was coated by die coating, after 30 seconds drying at 80 ° C., the UV 80 mJ / cm ^2, was cured by irradiation illuminance 150 mW / cm ^2. The film thickness of the intermediate layer after curing was 1.5 μm. Next, a coating liquid of a rod-like liquid crystal compound, which is the following polymerizable liquid crystal compound, was applied on the intermediate layer by die coating. After coating, heating at 100 ° C. for 2 minutes and then cooling at 28 ° C. for 1 minute to align the rod-like liquid crystal compound, provide a polymerizable liquid crystal compound layer (optically anisotropic layer 1), and further optically anisotropic layer 1 Was cured by irradiation at an oxygen concentration of 0.2%, a temperature of 28 ° C. at 200 mJ / cm ² and an illuminance of 200 mW / cm ² to obtain a retardation film 1. The thickness of the optically anisotropic layer 1 was 1.4 μm. The retardation of the retardation film 1 as a whole was 80 nm for Ro and −14 nm for Rt. The retardation is a value measured at a wavelength of 590 nm using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments) after humidity adjustment to 23 ° C. and 55% RH.

(Interlayer coating solution)
25 parts by mass of polyester acrylate (Laromar LR8800 manufactured by BASF Japan Ltd.)
Propylene glycol monomethyl ether 290 parts by mass Isopropyl alcohol 685 parts by mass Photopolymerization initiator (Irgacure 184, manufactured by Ciba Japan Co., Ltd.) 0.05 parts by mass (rod-like liquid crystal compound coating solution)
UV-polymerizable liquid crystal material 20 parts by mass (UCL-018 manufactured by Dainippon Ink & Chemicals, Inc.)
Propylene glycol monomethyl ether 80 parts by mass Hindered amine (LS-765 Sankyo Lifetech Co., Ltd.) 0.02 parts by mass Sensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) 0.10 parts by mass The following air interface side vertical alignment Agent 1 0.01 parts by weight

(Preparation of retardation film 2)
A retardation film 2 was produced in the same manner as the retardation film 1 except that the cellulose ester film A was changed to the following cellulose ester film B and the thickness of the optically anisotropic layer 1 was changed to 1.55 μm. The retardation of the entire retardation film 2 was Ro of 81 nm and Rt of −13 nm. The retardation is a value measured at a wavelength of 590 nm using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments) after humidity adjustment to 23 ° C. and 55% RH.

<Preparation of cellulose ester film B>
(Synthesis of cellulose ester Y)
To the reactor, 80 parts of cellulose acetate (Daicel Chemical Industries, Ltd., L-20, substitution degree 2.41) was added and dried under reduced pressure at 110 ° C. for 4 hours, 4 Torr (1 Torr is 133.322 Pa). . Then, purging with dry nitrogen, attaching a reflux condenser, adding 80 parts of L-lactide (manufactured by Musashino Chemical Laboratories) and 67 parts of cyclohexanone that were dried and distilled in advance, and heating and stirring to 160 ° C. The cellulose acetate was uniformly dissolved. To this reaction solution, 0.25 part of monobutyltin trioctylate was added and heated at 160 ° C. with stirring for 2 hours. Thereafter, the reaction solution was cooled to room temperature to terminate the reaction and obtain a reaction product. Furthermore, 10 parts of the reaction product was dissolved in 90 parts of chloroform, and then slowly dropped into 900 parts of a large excess of methanol, and the precipitated precipitate was filtered off to remove the L-lactide homopolymer. . Furthermore, it heat-dried at 60 degreeC for 5 hours or more, and obtained the cellulose ester Y which L-lactide reacted with the cellulose acetate. And the primary structure of the cellulose ester obtained by < ¹ > H-NMR was analyzed. As a result, the primary structure of the graft obtained by ¹ H-NMR was analyzed. As a result, the average number of moles of L-lactide reacted per mole of glucose unit was 1.80, the average degree of substitution was 0.33, and the average degree of polymerization was 7.1.

(Preparation of dope solution C)
The following materials were sequentially put into a sealed container, the temperature in the container was raised from 20 ° C. to 80 ° C., and the mixture was stirred for 3 hours while maintaining the temperature at 80 ° C. to completely dissolve the cellulose ester. . The silicon oxide fine particles were added dispersed in a solution of a solvent to be added in advance and a small amount of cellulose ester. This dope was filtered using a filter paper (Azumi filter paper No. 244 manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope solution C.

(Dope solution C)
Cellulose ester Y 100 parts by mass Monopet SB (sugar ester compound) 9 parts by mass Silicon oxide fine particles 0.1 parts by mass (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.)
Methylene chloride 400 parts by weight Ethanol 40 parts by weight Butanol 5 parts by weight The above materials are mixed to prepare a dope solution C, and the obtained dope solution C is made of stainless steel endless from a casting die kept at a temperature of 35 ° C. The web was formed by casting on a support composed of a belt and having a temperature of 35 ° C. Next, the web was dried on the support, and the web was peeled from the support with a peeling roll when the residual solvent amount of the web reached 100% by mass.

  Next, the web is transported while being dried with a drying air of 100 ° C. in a transport drying process using a plurality of rolls arranged on the upper and lower sides. Subsequently, both ends of the web are gripped by a tenter and then stretched in the width direction (TD) at 130 ° C. It extended | stretched so that it might become 1.2 times before. After stretching with a tenter, the web was dried with a drying air of 140 ° C. in a conveying and drying process using a plurality of rolls arranged vertically. The film was cooled to room temperature and subjected to a knurling process having a width of 10 mm and an average height of 10 μm at both ends of the film and wound up to prepare a long cellulose ester film B having a width of 1.5 m, a film thickness of 100 μm, a length of 5000 m. The draw ratio of the web conveyance direction (MD) immediately after peeling calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times.

  The retardation of the cellulose ester film B was Ro = 81 nm and Rt = 190 nm. The retardation is a value measured at a wavelength of 590 nm using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments) after humidity adjustment to 23 ° C. and 55% RH.

(Production of retardation film 3)
The cellulose ester film B was used as the retardation film 3 as it was without providing an optically anisotropic layer.

(Production of retardation film 4)
A norbornene-based polymer film 1 (NB1) was prepared by synthesizing a norbornene-based polymer from the cellulose ester film A with reference to Synthesis Example 8 of JP-A-2008-31304. A phase difference film 4 was produced in the same manner except that the surface of the combined film 1 was subjected to a surface treatment by an atmospheric pressure plasma treatment and then the optically anisotropic layer 1 was coated with a thickness of 1.9 μm. The retardation of the retardation film 4 as a whole was 75 nm for Ro and −16 nm for Rt. The retardation is a value measured at a wavelength of 590 nm using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments) after humidity adjustment to 23 ° C. and 55% RH.

<Preparation of norbornene polymer film 1 (NB1)>
(Synthesis of norbornene polymer 1)
NBOAc: 5-norbornen-2-yl acetate (bicyclo [2.2.1] hept-5-en-2-yl acetate)
Norbornene (NB): norbornylene or bicyclo [2.2.1] hept-5-ene) was purchased from Aldrich.

  150 parts by mass of toluene and 152 parts by mass of NBOAc were placed in a reaction vessel. Next, 0.018 parts by mass of allyl palladium chloride dimer (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 10 parts by mass of toluene, 0.028 parts by mass of tricyclohexylphosphine (manufactured by Strem Co.), and dimethylaniline dissolved in 5 parts by mass of methylene chloride. A reaction vessel was charged with 0.12 parts by mass of nium tetrakispentafluorophenylborate (manufactured by Strem) and 0.33 parts by mass of allyltributyltin (manufactured by Aldrich) dissolved in 10 parts by mass of toluene. When heating was started and the temperature reached 90 ° C., 130 parts by mass of NB dissolved in 20 parts by mass of toluene was added dropwise over 1 hour. The mixture was reacted at 90-100 ° C. for 6 hours. During this time, toluene was added as appropriate with an increase in the viscosity of the reaction solution. 10 parts by mass of 1-hexene (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and further reacted for 1 hour. The obtained reaction solution was put into excess methanol to precipitate a polymer. The precipitate was collected, washed with methanol, and vacuum dried at 110 ° C. for 6 hours. The obtained polymer (norbornene polymer 1) was dissolved in tetrahydrofuran, and the molecular weight was measured by gel permeation chromatography. When the mass average molecular weight (Mw) was measured, the number average molecular weight (Mn) was 100200, the mass average molecular weight (Mw) was 256300, and the molecular weight distribution (Mw / Mn) was 2.56.

(Preparation of dope solution D)
The following materials were sequentially put into a sealed container, the temperature in the container was raised from 20 ° C. to 80 ° C., and the mixture was stirred for 3 hours while maintaining the temperature at 80 ° C. to completely remove the norbornene polymer 1 Dissolved in. The silicon oxide fine particles were added dispersed in a solution of a solvent to be added in advance and a small amount of cellulose ester. This dope was filtered using filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope solution D.

(Dope solution D)
Norbornene-based polymer 1 100 parts by mass Silicon oxide fine particles 0.1 part by mass (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.)
Methylene chloride 400 parts by weight Ethanol 40 parts by weight Butanol 5 parts by weight The above materials are mixed to prepare a dope solution D, and a stainless steel endless belt is prepared from a casting die in which the obtained dope solution D is kept at 35 ° C. A web was formed by casting on a support having a temperature of 35 ° C. Next, the web was dried on the support, and the web was peeled from the support with a peeling roll when the residual solvent amount of the web reached 100% by mass.

  Next, the web is transported while being dried with a drying air of 110 ° C. in a drying process of transport by a plurality of rolls arranged on the top and bottom, and subsequently grips both ends of the web with a tenter, and then in the width direction (TD) at 150 ° C. It extended | stretched so that it might become 1.3 time before extending | stretching. After stretching with a tenter, the web was dried with a drying air of 155 ° C. in a transport drying process using a plurality of rolls arranged vertically. After heat-treating for 15 minutes in an atmosphere with an atmosphere substitution rate of 15 (times / hour) in the drying step, it was cooled to room temperature and subjected to a knurling process with a width of 10 mm and an average height of 10 μm at both ends. A norbornene polymer film 1 (NB1) having a thickness of 5 m, a thickness of 82 μm, and a length of 5000 m was produced. The retardation of the norbornene polymer film 1 (NB1) was Ro = 75 nm and Rt = 225 nm. The retardation is a value measured at a wavelength of 590 nm using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments) after humidity adjustment to 23 ° C. and 55% RH.

(Production of retardation film 5)
A retardation film 5 was produced in the same manner as the retardation film 1 except that the cellulose ester film A was changed to the following cellulose triacetate film 2 and the thickness of the optically anisotropic layer 1 was changed to 1.4 μm. The retardation of the retardation film 5 as a whole was 76 nm for Ro and −12 nm for Rt. The retardation is a value measured at a wavelength of 590 nm using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments) after humidity adjustment to 23 ° C. and 55% RH.

<Preparation of cellulose triacetate film 2>
(Preparation of dope solution E)
The following materials are sequentially put into a sealed container, the temperature in the container is raised from 20 ° C. to 80 ° C., and the mixture is stirred for 3 hours while maintaining the temperature at 80 ° C. to completely dissolve the triacetyl cellulose. did. In another sealed container, 7 parts by mass of the following retardation developer A, 10 parts by mass of retardation developer B, 0.28 parts by mass of silicon dioxide fine particles (average particle size: 0.1 μm), 80 parts by mass of methylene chloride And 20 parts by mass of methanol were added and stirred while heating to prepare a solution. 40 parts by mass of the solution was mixed with 474 parts by mass of the triacetyl cellulose solution, and the dope was prepared by sufficiently stirring. This dope was filtered using a filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope solution E.

(Dope solution E)
Triacetyl cellulose (acetylation degree 61.0%) Substitution degree 2.9 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride 300 parts by weight Methanol 54 parts by mass 1-butanol 11 parts by mass Retardation developer A 7 parts by mass

  Retardation developer B 10 parts by mass

  The above-mentioned materials are mixed to prepare a dope liquid E, and the obtained dope liquid E is passed through a casting die kept at a temperature of 35 ° C., and then on a support having a temperature of 35 ° C. made of a stainless steel endless belt. Cast to form a web. Next, the web was dried on the support, and the web was peeled from the support with a peeling roll when the residual solvent amount of the web reached 110% by mass.

  Next, the web is transported while being dried with a drying air of 100 ° C. in a transport drying process using a plurality of rolls arranged at the top and bottom, and subsequently gripped at both ends of the web with a tenter and then stretched in the width direction (TD) at 135 ° C. It extended | stretched so that it might become 1.35 times before. After stretching with a tenter, the web was dried with a drying air of 140 ° C. in a conveying and drying process using a plurality of rolls arranged vertically. The film was cooled to room temperature, and subjected to a knurling process having a width of 10 mm and an average height of 10 μm at both ends of the film and wound up to prepare a cellulose triacetate film 2 having a width of 1.5 m, a film thickness of 85 μm, a length of 5000 m, and a length. The draw ratio of the web conveyance direction (MD) immediately after peeling calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times.

  The retardation of the cellulose triacetate film 2 was Ro = 76 nm and Rt = 178 nm. The retardation is a value measured at a wavelength of 590 nm using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments) after humidity adjustment to 23 ° C. and 55% RH.

<Preparation of cellulose triacetate film 3>
(Preparation of dope solution F)
Sealed container The composition of the following dope solution F was charged, heated to 70 ° C., and cellulose triacetate (TAC) was completely dissolved while stirring.

(Dope F)
Triacetylcellulose (acetylation degree 61.0%) 85 parts by mass 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) bezotriazole
1.5 parts by mass Methyl methacrylate-2-hydroxyethyl acrylate copolymer 8 parts by mass (80/20 (mass ratio)) Mw; 8000
Methyl acrylate polymer (*) Mw; 1000 5 parts by mass Methylene chloride 475 parts by mass Ethanol 50 parts by mass (*) The methyl acrylate monomer was polymerized by the polymerization method described in Example 3 of JP 2000-128911 A, and Mw 1000, A polymer of Mn700 was obtained. The reaction product had a hydroxyl value (OHV; mg / g KOH) of 50.

(Preparation of matting agent solution)
A matting agent solution was obtained by thoroughly stirring and mixing 20 parts by mass of silica particles (AEROSIL R972, Nippon Aerosil Co., Ltd.) having an average particle diameter of 16 nm and 80 parts by mass of methanol for 30 minutes.

(Matting agent solution composition)
Silica particle dispersion liquid having an average particle diameter of 16 nm 11.0 parts by mass Methylene chloride (first solvent) 76.1 parts by mass Ethanol (second solvent) 3.5 parts by mass Acetylpropionylcellulose (acetyl substitution degree 2.06, propionyl substitution) Degree 0.79) 1.9 parts by mass After the dope solution F was filtered using a filter paper (Azumi Filter Paper Co., Ltd., Azumi Filter Paper No. 244), 6.5 parts by mass of the matting agent solution was mixed and mixed. The liquid was cast from a casting die kept at a temperature of 35 ° C. onto a support at a temperature of 35 ° C. made of a stainless steel endless belt to form a web. Next, the web was dried on the support, and the web was peeled from the support with a peeling roll when the residual solvent amount of the web reached 100% by mass.

  Next, the web is transported while being dried with a drying air of 100 ° C. in a transport drying process using a plurality of rolls arranged on the upper and lower sides. Subsequently, both ends of the web are gripped by a tenter and then stretched in the width direction (TD) at 130 ° C. The film was stretched to 1.1 times the previous size. After stretching with a tenter, the web was dried with a drying air of 140 ° C. in a conveying and drying process using a plurality of rolls arranged vertically. After cooling to room temperature, the film was subjected to a knurling process with a width of 10 mm and an average height of 10 μm at both ends of the film, and wound to prepare a long cellulose triacetate film 3 having a width of 1.5 m, a film thickness of 60 μm, a length of 5000 m. The retardation was Ro = 0.5 nm and Rt = −1 nm. The retardation is a value measured at a wavelength of 590 nm using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments) after humidity adjustment to 23 ° C. and 55% RH.

<Preparation of Polarizing Plate 101>
(Alkaline saponification treatment)
Conditions described below for the retardation film 1 having a peelable protective film (PET) attached to the optically anisotropic layer 1 and the hard coat film 1 having a peelable protective film (PET) attached to the hard coat layer The alkali saponification treatment was carried out. In addition, after the alkali saponification treatment, the protective film of the hard coat film 1 and the retardation film 1 was peeled off and bonded to the polarizing film as described below to prepare the polarizing plate 101.

Saponification step 2.5M-NaOH 50 ° C. 90 seconds Water washing step Water 30 ° C. 45 seconds Neutralization step 10 parts HCl 30 ° C. 45 seconds Water washing step Water 30 ° C. 45 seconds Water treatment, neutralization, water washing in this order And then dried at 80 ° C.

<Preparation and bonding of polarizing film>
A 120 μm-thick long roll polyvinyl alcohol film is immersed in 100 parts by mass of an aqueous solution containing 1 part by mass of iodine and 4 parts by mass of boric acid, and stretched 6 times at 50 ° C. in the film forming direction to form the polarizing film L-2. Produced.

  Next, using a polyvinyl alcohol adhesive, the hard coat film 1 saponified on one side L-1 of the polarizing film so that the transmission axis of the polarizing film L-2 and the in-plane slow axis of the film are parallel to each other A long polarizing plate was prepared such that the opposite side of the hard coat layer and the retardation film 1 were combined as shown in FIG. Next, as shown in FIG. 4, it was cut (punched) into a size of 576 × 324 mm to produce a polarizing plate 101.

<Preparation of polarizing plates 102 to 108>
In the production of the polarizing plate 101, a long polarizing plate was produced in the same manner except that the hard coat film of the first protective film and the retardation film of the second protective film were used in combination as described in Table 1. Polarizing plates 102 to 108 were produced by punching. The retardation film 4 was saponified without attaching a peelable protective film (PET).

<Evaluation>
The following evaluation was performed about the produced deflection plates 101-108.

(Surface hardness: pencil hardness)
The surface hardness of the deflection plates 101 to 108 was evaluated by a pencil hardness test.

  Using the test pencil specified by JIS-S6006, according to the pencil hardness evaluation method specified by JIS-K5400, the hard coat layer surface of the deflecting plates 101 to 108 is repeated five times with a pencil of each hardness using a 500 g weight. The hardness of scratches and scratches was measured. The higher the number, the higher the hardness, and the higher the pencil hardness 3H, the higher the hardness characteristics.

(Evaluation of cracks and cracks)
About the edge part of the punched polarizing plates 101-108, the state of the edge part was observed using a 10 times loupe, and the crack and the crack were evaluated according to the following criteria.

◎: Level at which no cracking / crushing occurs ○: Cracking / crushing is slightly observed but there is no practical problem △: Cracking / crushing is slightly observed ×: Cracking・ The level at which the occurrence of sawdust is seen (overall evaluation)
From the evaluation results of the surface hardness and cracking / crusting, it was shown in Table 1 as a comprehensive evaluation based on the following criteria.

◎: Hardness is 4H or more, cracks and crusts are ◎
○: Hardness is 3H or more and cracks and cracks are ◎
Δ: Hardness is 3H or more, and cracks and cracks are ○
X: Hardness is 3H or more, and cracks and crusts are △ or less (practical problem level)
XX: The hardness was less than 3H, and cracks and crusts were Δ or less. The results obtained are shown in Table 1.

<Production of Liquid Crystal Display Device 501>
The polarizing plate of Panasonic 26-inch liquid crystal television, TH-26LX60 liquid crystal panel is peeled off, and the polarizing plate 101 prepared above is applied to the polarizing plate on the viewing side (L-10) with an optical anisotropic layer and a thickness of 5 μm as shown in FIG. The liquid crystal cell glass L-6-1 was pasted using an adhesive. Further, on the backlight side, cellulose triacetate film 3 (L-7) and cellulose triacetate film 1 (L-9), which were subjected to alkali saponification treatment in the same manner as described above, and a polarizer were bonded in a configuration as shown in FIG. The polarizing plate 201 was bonded to the liquid crystal cell glass L-6-2 using an adhesive having a thickness of 5 μm, so that a liquid crystal panel 401 was produced. Next, the liquid crystal panel 401 was set on a liquid crystal television, and a liquid crystal display device 501 was manufactured.

<Production of liquid crystal display devices 502 to 508>
Liquid crystal panels 402 to 407 are produced in the same manner except that the polarizing plate (L-10) on the viewing side of the liquid crystal display device 501 is changed to 102 to 108, set in a liquid crystal television, and the liquid crystal display devices 502 to 508 are attached. Produced.

<Evaluation>
The liquid crystal display devices 501 to 508 produced above were evaluated as follows.

(Smoothness (flatness) evaluation)
The liquid crystal display devices 501 to 508 produced above are placed on a desk 80 cm high from the floor, and a daylight direct fluorescent lamp (FLR40S • D / MX Panasonic Corporation is placed on the ceiling 3 m high from the floor. 10 sets of 40W × 2 pieces were arranged at 1.5 m intervals. In this case, when the evaluator is in front of the display surface of the liquid crystal display panel, the fluorescent lamp is arranged so that the fluorescent lamp comes to the ceiling portion from the evaluator's overhead to the rear.

  Next, the smoothness (flatness) of the liquid crystal panels 401 to 408 of the liquid crystal display devices 501 to 508 was evaluated according to the following criteria.

◎: Fluorescent lamp looks straight ○: Fluorescent lamp appears to be slightly bent △: Fluorescent lamp appears to be bent ×: Fluorescent lamp appears to be greatly bent Table 2 shows the results obtained above. .

  From the results of Table 1 and Table 2, a transparent film containing a cellulose ester having at least one repeating unit represented by the general formula (1) or (2) is used for the base film of the second protective film, In addition, the polarizing plate of the present invention in which an optically anisotropic layer is provided on the transparent film is excellent in both high hardness and prevention of occurrence of cracks and crushing failures, and also has excellent flatness when used in an image display device. Have

Among them Martens hardness of the hard coat layer, 400 N / mm ² or more, the polarizing plate of the present invention having a 800 N / mm ² or less hard coat layer has high hardness and crack-splinter pencil hardness and excellent more particularly 4H It is excellent for both failure control.

Example 2
(Preparation of hard coat film 5)
In producing the hard coat film 1, a hard coat film 5 was produced in the same manner except that the hard coat layer composition 1 was changed to the hard coat layer composition 2.

  The following materials were stirred and mixed to obtain hard coat layer composition 2.

(Hard coat layer composition 2)
Cationic polymerizable compound: [1- (3-ethyl-3-oxetanyl) methyl] ether
130 parts by mass 4-methylphenyl [4- (1-methylethyl) phenyl] iodonium tetrakis (pentafluorophenyl) borate 5 parts by mass (Lordsil 2074, produced by Rhodia Japan)
Seahoster KEP-50 (silica particles having an average particle size of 0.47 to 0.61 μm, manufactured by Nippon Shokubai Co., Ltd.)
The adjusted fluorine-siloxane graft polymer I (35% by mass) 5.0 parts by mass Propylene glycol monomethyl ether 20 parts by mass Ethyl acetate 40 parts by mass Methyl ethyl ketone 60 parts by mass (Preparation of polarizing plate 109)
A polarizing plate 109 was produced in the same manner except that the hard coat film 5 was used in the production of the polarizing plate 101. As a result of testing the pencil hardness of this polarizing plate 109 in the same manner as in Example 1 and observing the end portion after punching, the cracks and the cracks were also ◎.

<Production of Liquid Crystal Display Device 509>
A liquid crystal panel 409 and a liquid crystal display device 509 were produced in the same manner except that the polarizing plate (L-10) on the viewing side was changed to the polarizing plate 109 in the production of the liquid crystal display device 501. Next, the backlights of the liquid crystal display device 501 and the liquid crystal display device 509 are turned on and left in a black display state for 2000 hours. The smoothness (flatness) after the standing and the intensity of occurrence of unevenness based on the following criteria, light The leak was evaluated.

(Evaluation of unevenness)
The intensity of unevenness was visually observed and evaluated according to the following criteria.

Situation evaluation No occurrence of unevenness ◎
Slightly weak cloudy unevenness occurs ○
Weak cloudy unevenness occurs △
Strong unevenness occurs at the four corners ×
(Light leakage evaluation)
Light leakage was evaluated by observing from an oblique direction of 70 °.

Situation evaluation There was very little light leakage.
Although there is a slight light leak, there is no problem in terms of actual damage ○
Some light leakage is observed △
Light leakage is observed on the entire surface ×
The obtained results are shown in Table 3.

  From the results shown in Table 3, under the conditions assuming long-term use, an excellent effect is exhibited when the hard coat layer coating composition is made into a cationically polymerizable compound and used in an image display device.

Reference example 1
Using the hard coat film 1 produced in Example 1, an antireflection film 1 was produced.

(Atmospheric pressure plasma treatment)
In the production of the hard coat film 1 of Example 1, the hard coat film 6 was produced in the same manner except that the nitrogen purge was not performed during the ultraviolet irradiation. Next, an atmospheric pressure plasma treatment apparatus is used on the surface of the hard coat layer of the hard coat film 6, the electrode gap is set to 0.5 mm, the following discharge gas is supplied to the discharge space, and discharge is performed at 100 kHz. Surface treatment by plasma treatment was performed.

(Discharge gas)
Nitrogen gas 80.0% by volume
Oxygen gas 20.0% by volume
(Formation of a low refractive index layer)
The following coating composition for a low refractive index layer is die coated on the hard coat layer of the hard coat film 6 that has been subjected to the atmospheric pressure plasma treatment, dried at a temperature of 80 ° C., and then in an atmosphere having an oxygen concentration of 1.0 vol% or less. The antireflective film 1 was produced by irradiating ultraviolet rays of 0.3 J / cm ² with a high pressure mercury lamp while purging with nitrogen so as to provide a low refractive index layer so that the film thickness after curing was 85 nm. The refractive index of the low refractive index layer was 1.38.

(Coating composition for low refractive index layer)
An isopropyl alcohol dispersion of hollow silica fine particles 1 and a tetraethoxysilane hydrolyzate A were prepared, and then a coating composition 1 for a low refractive index layer was prepared.

(Preparation of isopropyl alcohol dispersion of hollow silica fine particles 1)
Step (a): A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of 0.98 mass% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02 mass% sodium aluminate aqueous solution as Al ₂ O ₃ were added to the mother liquor. Added simultaneously. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ core particle dispersion having a solid content concentration of 20% by mass.

Step (b): Obtained by adding 1700 g of pure water to 500 g of this core particle dispersion and heating to 98 ° C., and maintaining the temperature while dealkalizing the sodium silicate aqueous solution with a cation exchange resin. Further, 3000 g of a silicic acid solution (SiO ₂ concentration: 3.5% by mass) was added to obtain a dispersion of core particles in which a first silica coating layer was formed.

Step (c): Next, 1125 g of pure water was added to 500 g of the core particle dispersion formed with the first silica coating layer washed with an ultrafiltration membrane to a solid content concentration of 13% by mass, and concentrated hydrochloric acid (35. 5%) was added dropwise to adjust the pH to 1.0, and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and SiO ₂ · Al from which some of the constituent components of the core particles forming the first silica coating layer were removed. A dispersion of ₂ O ₃ porous particles was prepared.

Step (d): A mixture of 1500 g of the above porous particle dispersion, 500 g of pure water, 1,750 g of ethanol, and 626 g of 28% ammonia water was heated to a temperature of 35 ° C., and then ethyl silicate ( SiO _{2 (} 28% by mass) 104 g was added, and the surface of the porous particles on which the first silica coating layer was formed was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer. Next, a dispersion of hollow silica fine particles 1 having a solid content concentration of 20% by mass was prepared by replacing the solvent with isopropyl alcohol using an ultrafiltration membrane. The thickness of the first silica coating layer of the hollow silica fine particles, 3 nm, the average particle size is _45nm, MO X / SiO ₂ (molar ratio) is 0.0017, the refractive index was 1.28. Here, the average particle diameter and the coefficient of variation of the particle diameter were measured by a dynamic light scattering method.

(Preparation of tetraethoxysilane hydrolyzate A)
After mixing 230 g of tetraethoxysilane (trade name: KBE04, manufactured by Shin-Etsu Chemical Co., Ltd.) and 440 g of ethanol and adding 120 g of a 2% aqueous acetic acid solution thereto, the mixture is stirred for 28 hours at room temperature (25 ° C.). Silane hydrolyzate A was prepared.

(Coating composition 1 for low refractive index layer)
Propylene glycol monomethyl ether 430 parts by mass Isopropyl alcohol 430 parts by mass Tetraethoxysilane hydrolyzate A (solid content 21% conversion) 120 parts by mass γ-methacryloxypropyltrimethoxysilane 3.0 parts by mass (trade name: KBM503, Shin-Etsu) (Made by Chemical Industries)
60 parts by mass of isopropyl alcohol dispersion of hollow silica fine particles 1 (average particle size 45 nm, particle size variation coefficient 30%)
Aluminum ethyl acetoacetate / diisopropylate 3.0 parts by mass (manufactured by Kawaken Fine Chemical Co., Ltd.)
3.0 parts by mass of FZ-2207 (10% propylene glycol monomethyl ether solution, manufactured by Nihon Unicar Company)
(Measurement of reflectance)
As a result of measuring the reflectance of the produced antireflection film 1 using CM-3700d (manufactured by Konica Minolta Sensing Co., Ltd.), it was 1.4% and had good performance.

<Preparation of Polarizing Plate 110>
(Alkaline saponification treatment)
In the production of the polarizing plate 101, the retardation film 1 and the antireflection film 1 were subjected to an alkali saponification treatment in the same manner except that a peelable protective film (made of PET) was bonded to the low refractive index layer of the antireflection film 1. After the saponification treatment, the protective film was peeled off and bonded to the polarizing film to produce a long polarizing plate. Next, the polarizing plate 110 was produced by punching. As a result of testing the pencil hardness of the polarizing plate 110 in the same manner as in Example 1, it was 4H.

<Production of Liquid Crystal Display Device 510>
A liquid crystal panel 410 and a liquid crystal display device 510 were produced in the same manner except that the polarizing plate (L-10) on the viewing side was changed to the polarizing plate 110 in the production of the liquid crystal display device 501. As a result of evaluating smoothness (flatness) in the same manner as in Example 1, it was evaluated as ◎ and excellent in visibility.

It is the schematic which showed the process of heat-processing continuously after actinic light irradiation. It is the schematic which heat-processes the hard coat film roll or antireflection film after winding in the heat processing chamber A. 1 is a schematic view of a liquid crystal display device according to a preferred embodiment of the present invention. It is a figure which shows punching of a polarizing plate.

Explanation of symbols

Y Long film 1 Feeding roll 2 Conveying roller 3 Extrusion coater 4 Opposing roll 5 Drying zone 6 Actinic ray irradiation lamp unit 6a Air-cooled actinic ray lamp 6b Air cooling air vent 6c N2 supply chamber 7 Heating zone 8 Winding chamber 9 Winding Take-up roll 10 Warm air outlet 12 Movable carriage 15 Winding core A Heat treatment chamber L-1 Polarizing plate protective film L-2, L-8 Polarizing film L-3 Transparent film L-4 Intermediate layer L-5 Bar shape Optically anisotropic layer in which the liquid crystal is vertically aligned and fixed in alignment L-6 IPS liquid crystal cell L-6-1 Non-electrode side cell glass substrate L-6-2 Electrode side cell glass substrate L-6-3 IPS type liquid crystal cell L-7 Polarizing plate protective film L-9 Polarizing plate protective film L-10 Viewing side polarizing plate (viewing side polarizing plate)
L-11 Optical compensation film of the present invention L-12 Backlight side polarizing plate L-13 Backlight 81 Absorption axis (stretching axis)
82 Longitudinal direction

Claims (5)

In the polarizing plate in which the first protective film, the polarizing film, and the second protective film are laminated in this order, the polymerizable liquid crystal compound layer in which the second protective film is substantially vertically aligned, and the following general formula (1) Or a transparent film containing a cellulose ester having at least one repeating unit represented by (2), and the first protective film has at least a hard coat layer on the side far from the polarizing film. A polarizing plate characterized by having.

[In formula, A and B represent a C1-C12 bivalent hydrocarbon group or a C1-C12 bivalent hydrocarbon group substituted by the hydroxyl group. However, A and B may be the same or different. ] The Martens hardness of the hard coat layer (HMS) is, 400 N / mm ² or more, polarizing plate according to claim 1, characterized in that 800 N / mm ² or less. The polarizing plate according to claim 1, wherein the hard coat layer contains a cationic polymerizable compound. A liquid crystal display device using the polarizing plate according to claim 1 on at least one side of a liquid crystal cell. An IPS liquid crystal display device comprising the polarizing plate according to claim 1 on at least one side of an in-plane switching mode (IPS) liquid crystal cell.

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