JP4905787B2 - Antiglare film, antireflection film, polarizing plate, image display device, and production method of antiglare film - Google Patents

Description

  The present invention relates to an antiglare film having a specific antiglare layer on a specific cellulose ester film, an antireflection film using the same, a polarizing plate, a liquid crystal display device, and a method for producing the antiglare film.

  In recent years, liquid crystal display devices (LCD) have increased in screen size, and for example, liquid crystal display devices having an optical film such as an antiglare film, an antireflection film, and a light diffusion sheet are increasing. For example, antiglare films and antireflection films are used in various image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), and cathode ray tube display devices (CRT). In order to prevent a decrease in contrast due to reflection or reflection of external light, it is arranged on the surface of the display. The light diffusion sheet is used for a backlight of a liquid crystal display device.

  In general, the antiglare film is formed by directly applying an antiglare coating on a plastic substrate film or as a layer having a thickness of about 3 to 10 μm through a lower layer of about 0.1 to 1 μm. The installation method is often performed by a coating method with excellent productivity (Patent Document 1). Since the antiglare film is used on the outermost surface of the display, various film strengths such as scratch resistance against fine scratches and film hardness that can withstand pressure when written with a writing instrument are required. However, the conventional anti-glare film has insufficient hardness of the anti-glare layer, the deformation of the underlying plastic base film, the anti-glare layer is also deformed, and the overall hardness of the anti-glare film is low, It is not satisfactory enough. In an antiglare film in which an antiglare layer made of an ionizing radiation curable resin is coated on a cellulose ester film with the above thickness, a pencil hardness of about 2H is common, and a sufficient hardness of 4H or more is obtained. There wasn't.

  Moreover, the ultraviolet absorber is added to the cellulose-ester film in order to provide durability. Patent Document 2 shows an example in which an ultraviolet curable resin layer is provided on a cellulose ester film containing an ultraviolet absorber. However, the pencil hardness is only about 2H, which is not sufficient. Patent Document 3 describes an example in which an antiglare layer is formed on a cellulose triacetate film containing an ultraviolet absorber, but these are only about 2H in pencil hardness, and cannot be said to be a sufficient level.

When an ultraviolet curable resin layer is formed on a cellulose ester film substrate containing an ultraviolet absorber, there is a problem that the film itself generates heat due to the irradiated ultraviolet rays and the substrate is deformed. In particular, in order to provide the necessary ultraviolet absorptivity for a thin film, the content of the ultraviolet absorber has to be increased, and the effect is significant accordingly. For example, it is shown that the light scattering films described in Patent Documents 4, 5, and 6 can obtain a pencil hardness of 3H by irradiating strong ultraviolet rays of 300 mJ / cm ² to form a light diffusion layer. However, the film obtained by this method is inferior in planarity, and the planarity may be further deteriorated particularly in a thin film or a wide film. Furthermore, when the width of the base film is increased, it is difficult to irradiate ultraviolet rays uniformly in the width direction, and the base material may be deformed. If the amount of irradiation is reduced due to fear of deformation of the base material, sufficient light intensity may not be secured near the edge, and the required hardness cannot be obtained. There was a decline.

  On the other hand, in recent years, the use environment of the image display apparatus has been extended to the outdoors, and it is desired that the cellulose ester film having the antiglare layer be improved in durability that can be used outdoors. In particular, in the antiglare film used for the exterior of the display device, the adhesion between the cellulose ester film and the antiglare layer is lowered due to continuous use outdoors and exposed to ultraviolet rays, etc. In some cases, peeling scratches may occur due to the abrasion of the product, and the product may not be used.

  On the other hand, a method for improving the adhesion to the hard coat layer by using a compatible ketone solvent or the like on the surface of the triacetyl cellulose film has been proposed. However, in this method, the triacetyl cellulose film may be whitened to impair transparency. Patent Document 7 discloses a method for improving adhesion to a triacetyl cellulose film by blending a cellulose resin in a hard coat layer. However, in this method, the adhesion may be insufficient when exposed to light such as ultraviolet rays for a long time.

JP 59-50401 A JP 2001-183528 A JP 2001-91705 A JP 2003-57415 A JP 2003-114304 A JP 2003-121618 A JP-A-9-302144

  The object of the present invention is to provide an antiglare film having excellent hardness and scratch resistance, and excellent adhesion when exposed to light such as sunlight for a long period of time, and having excellent flatness even if it is wide. The object is to provide a method of manufacturing with high productivity. Furthermore, it is providing the antireflection film, polarizing plate, and liquid crystal display device using such an anti-glare film.

  As a result of intensive studies, the inventor contains at least two plasticizers selected from plasticizers other than ultraviolet absorbers and phosphate ester plasticizers (the phosphate ester plasticizer is substantially contained). No) A curable resin composition having a film thickness of 8 to 40 μm on a cellulose ester film, containing at least one light transmissive resin and at least one light diffusing particle having an average particle diameter of 5 to 15 μm ( A) is applied to form an antiglare layer having a surface haze of 15% or less, so that it has excellent hardness and scratch resistance, and also has excellent adhesion when exposed to light such as sunlight for a long time. The present inventors have found that an antiglare film and an antireflection film having excellent flatness can be produced even if they are wide, and have completed the present invention.

That is, the above object can be achieved by using the following structures and compounds.
(1)
On a cellulose ester film containing at least two kinds of plasticizers selected from ultraviolet absorbers and plasticizers other than phosphoric ester plasticizers, at least one kind of translucent resin and at least one kind of light diffusibility An anti-glare film having an anti-glare layer formed by coating particles and a curable resin composition (A) containing at least one metal compound selected from the group consisting of titanium alkoxides, zirconium alkoxides and their chelate compounds The content of the phosphate ester plasticizer in the cellulose ester film is less than 1% by mass, and the average particle size of the light diffusing particles in the antiglare layer is 5 to 15 μm, An anti-glare film, wherein the film thickness of the anti-glare layer is 8 to 40 μm, and the surface haze on the anti-glare layer coating side is 15% or less.
( 2 )
The antiglare film according to (1 ), wherein the surface haze is 10% or less and the internal haze is 10 to 90%.
( 3 )
The anti-glare film as described in (1) or (2) , wherein the pencil hardness with a load of 4.9 N is 4H or more.
( 4 )
The cellulose ester film has a total acyl group substitution degree of 2.6 to 2.9, a number average molecular weight (Mn) of 80000 to 200000, and a mass average molecular weight (Mw) / number average molecular weight (Mn) of 1.4 to 3 0.0, the cellulose ester solution is cast and then biaxially stretched, and the translucent resin in the antiglare layer contains an ionizing radiation curable compound, and the antiglare layer is The curable resin composition (A) is coated on the cellulose ester film and then irradiated with ionizing radiation to cure the curable resin composition (A). The antiglare film according to any one of ( 3 ).
( 5 )
The translucent resin in the antiglare layer contains a compound containing at least two ethylenically unsaturated groups in one molecule, (1) to ( 4 ), The anti-glare film as described in 2.
( 6 )
The antiglare film according to any one of (1) to ( 5 ), wherein at least one plasticizer contained in the cellulose ester film is a polyhydric alcohol ester plasticizer.
( 7 )
At least one plasticizer contained in the cellulose ester film is selected from citrate ester plasticizers, glycolate plasticizers, phthalate ester plasticizers, and fatty acid ester plasticizers. The antiglare film according to any one of (1) to ( 6 ).
( 8 )
At least 1 sort (s) of the ultraviolet absorber which this cellulose ester film contains is a benzophenone type ultraviolet absorber or a triazine type ultraviolet absorber, The prevention as described in any one of (1)-( 7 ) characterized by the above-mentioned. Dazzle film.
( 9 )
An antireflection film comprising a low refractive index layer having a refractive index lower than that of the antiglare layer on the antiglare film according to any one of (1) to ( 8 ).
( 10 )
A polarizing plate comprising the antiglare film according to any one of (1) to ( 8 ) or the antireflection film according to ( 9 ) on at least one side.
(11)
At least one of the anti-glare film as described in any one of (1)-( 8 ), the antireflection film as described in ( 9 ), and the polarizing plate as described in ( 10 ) is arrange | positioned, It is characterized by the above-mentioned. An image display device.
( 12 )
On a cellulose ester film containing at least two kinds of plasticizers selected from ultraviolet absorbers and plasticizers other than phosphoric ester plasticizers, at least one kind of translucent resin and at least one kind of light diffusibility An anti-glare film having an anti-glare layer formed by coating particles and a curable resin composition (A) containing at least one metal compound selected from the group consisting of titanium alkoxides, zirconium alkoxides and their chelate compounds A manufacturing method of
Contains an ultraviolet absorber and at least two plasticizers, has a total acyl group substitution degree of 2.6 to 2.9, a number average molecular weight (Mn) of 80,000 to 200,000, and a weight average molecular weight (Mw). / A cellulose ester solution containing a cellulose ester having a number average molecular weight (Mn) value of 1.4 to 3.0 is cast on a support and dried until it can be peeled off. On a cellulose ester film having a phosphate ester plasticizer content of less than 1% by mass obtained by biaxial stretching and drying.
At least one kind of metal selected from the group consisting of at least one kind of translucent resin, at least one kind of light diffusing particles having an average particle diameter of 5 to 15 μm , titanium alkoxide, zirconium alkoxide and their chelate compounds. A curable resin composition (A) containing a compound is coated, irradiated with ionizing radiation, and the resin composition (A) is cured with an amount of ionizing radiation of 5 to 100 mJ / cm ^2. A method for producing an antiglare film.
( 13 )
The method for producing an antiglare film as described in ( 12 ), wherein the thickness of the layer obtained by curing the resin composition (A) is 8 to 40 μm.
( 14 )
The illuminance of the ionizing radiation irradiation part for curing the curable tree composition (A) is 50 to 150 mW / cm ² , The method for producing an antiglare film according to ( 12 ) or ( 13 ).
( 15 )
The stretching of the cellulose ester film is characterized in that after peeling from the support, the cellulose ester film is stretched in the longitudinal direction (conveying direction) while containing a solvent, and then stretched in the transverse direction by a tenter ( 12 )-( 14 ) The manufacturing method of the anti-glare film as described in any one of.
( 16 )
The method for producing an antiglare film according to any one of ( 12 ) to ( 15 ), wherein the curable resin composition (A) is cured while applying a tension.
In addition, although this invention is a manufacturing method of the anti-glare film, the antireflection film, the polarizing plate, the image display apparatus, and the anti-glare film which were described in said (1)-(16), it is in the specification for reference. Other items are also described in.

A feature of the antiglare film and the antireflection film of the present invention is that the cellulose ester film contains at least two kinds of plasticizers other than phosphate ester. When a phosphate ester plasticizer is contained, not only the plasticizer itself is easily eluted, but also other plasticizers are easily eluted, and the flatness deteriorates due to a large amount of the plasticizer being removed from the cellulose ester. The plasticizer deposited between the cellulose ester film / antiglare layer is considered to reduce the adhesion at the cellulose film / antiglare layer interface. This tendency is particularly prominent when exposed to light rays such as sunlight for a long time.
Another feature of the antiglare film and the antireflection film of the present invention is that the film thickness is 8 to 40 μm on the cellulose ester film containing at least two kinds of plasticizers other than the phosphate ester type, and at least one kind. The anti-glare layer is formed by coating a curable resin composition (A) containing a translucent resin and at least one kind of light diffusing particles. As compared with a normal antiglare film having a smaller film thickness of the antiglare layer and containing only light diffusing particles, the scratch resistance and antiglare property could be improved.

  The antiglare film and antireflection film of the present invention are excellent in hardness and scratch resistance, have excellent adhesion when exposed to light such as sunlight for a long time, and have excellent flatness even when wide. .

  The polarizing plate using the antiglare film and the antireflection film of the present invention as a surface protective film has excellent hardness and scratch resistance, and excellent adhesion when exposed to light such as sunlight for a long period of time. Even if it exists, it has excellent flatness.

  Further, the image display device of the present invention includes the antiglare film, the antireflection film and / or the polarizing plate, and has excellent hardness and scratch resistance, and when exposed to light rays such as sunlight for a long time. Excellent adhesion and excellent flatness even with a wide width.

  Furthermore, the method for producing an antiglare film of the present invention provides excellent hardness and scratch resistance, and excellent adhesion when exposed to light such as sunlight for a long period of time. It is possible to provide an antiglare film having a large amount at a low cost.

  Hereinafter, the antiglare film, the antireflection film, the polarizing plate, the image display device, and the production method thereof of the present invention will be described. In addition, in this specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” represents the meaning of “numerical value 1 or more and numerical value 2 or less”.

  The antiglare film of the present invention comprises at least one translucent resin on a cellulose ester film containing at least two or more plasticizers selected from a plasticizer other than an ultraviolet absorber and a phosphate ester plasticizer. And an antiglare film having an antiglare layer formed by coating the curable resin composition (A) containing at least one kind of light diffusing particles, and a phosphate ester plasticizer in the cellulose ester film Is less than 1% by mass, the average particle size of the light diffusing particles in the antiglare layer is 5 to 15 μm, the film thickness of the antiglare layer is 8 to 40 μm, and the antiglare layer The surface haze on the coating side is 15% or less.

  In the present invention, the plasticizer used for the cellulose ester film is not particularly limited, but it is necessary to contain at least two plasticizers. At that time, it is necessary that the phosphoric acid ester-based plasticizer that has been conventionally used is not substantially contained. “Substantially not contained” means that the content of the phosphate plasticizer is less than 1% by mass with respect to the total solid content in the cellulose ester film, preferably 0.1% by mass. % And preferably 0% by mass (below the detection limit).

  That is, to contain at least two kinds of plasticizers means to contain two or more kinds of plasticizers other than the phosphate ester type. It is considered that at least one of the plasticizers is a polyhydric alcohol ester plasticizer, which is considered to prevent the elution of other plasticizers, and is more effective than the case of using alone, and is particularly preferable. When a phosphate ester plasticizer is contained, not only the plasticizer itself is easily eluted, but also other plasticizers are easily eluted, and the flatness deteriorates due to a large amount of the plasticizer being removed from the cellulose ester. The plasticizer deposited between the cellulose ester film / antiglare layer is considered to reduce the adhesion at the cellulose film / antiglare layer interface.

  The value of Mw / Mn of the cellulose ester is preferably 1.4 to 3.0. In addition, in this invention, although the cellulose ester film should just contain the cellulose ester whose value of Mw / Mn is 1.4-3.0 as a material, the cellulose ester ( The value of Mw / Mn of the whole (preferably cellulose triacetate or cellulose acetate propionate) is more preferably in the range of 1.4 to 3.0. In the synthesis process of cellulose ester, it is difficult to make it less than 1.4, and cellulose ester having a uniform molecular weight can be obtained by fractionation by gel filtration or the like. On the other hand, if it exceeds 3.0, the flatness maintaining effect is lowered, which is not preferable. More preferably, it is 1.7 to 2.2.

  Moreover, it is preferable that the number average molecular weight (Mn) of a cellulose ester is 80,000-200,000. If the molecular weight of the cellulose ester is large and the distribution of the molecular weight is small, it is presumed that the plasticizer and ultraviolet absorber added are difficult to elute when the antiglare layer is applied. This effect is presumed to become more remarkable when the cellulose ester molecules are oriented in the transverse direction by biaxial stretching. It is also preferable that the total acyl group substitution degree of the cellulose ester is in the range of 2.6 to 2.9, and that an unsubstituted hydroxyl group remains in the cellulose main chain at an appropriate ratio. It is thought that it contributes to preventing the elution of the absorbent.

  The antiglare layer in the present invention is formed by coating a curable resin composition (A) containing at least one light transmissive resin and at least one light diffusing particle on a cellulose ester film. The film thickness of the antiglare layer needs to be 8 to 40 μm, more preferably 12 to 35 μm, and particularly preferably 18 to 30 μm. If it is too thin, the hard property will be insufficient, and if it is too thick, the curling and brittleness may deteriorate and the workability may be reduced, the cost may increase, and unevenness may occur. If the film thickness of the antiglare layer is lower than this range, sufficient pencil hardness cannot be obtained, and if the film thickness of the antiglare layer is higher than this range, the flatness tends to be lowered, and a thin display device can be obtained. There is a possibility that the thinning for use is impaired. The average particle size of the light diffusing particles in the antiglare layer needs to be 5 to 15 μm, preferably 6 to 12 μm, more preferably 7 to 10 μm. If the average particle size is less than 5 μm, the light scattering angle distribution spreads to a wide angle, which causes blurring of characters on the display, which is not preferable. On the other hand, if it exceeds 15 μm, it is necessary to increase the thickness of the antiglare layer, resulting in an increase in curl and an increase in material cost.

In the antiglare film of the present invention, the surface haze on the antiglare layer coating side is 15% or less, preferably 10% or less, more preferably 5% or less, and further preferably 3% or less. Particularly preferred. It is considered that by suppressing the surface haze and suppressing the surface roughness, it contributes to scratch resistance against fine scratches.
In addition, the antiglare film of the present invention uses the internal scattering of the hard coat layer to make it difficult to see the pattern, color unevenness, luminance unevenness, and glare of the liquid crystal panel, and to enlarge the viewing angle by scattering. Can be granted. The internal haze is preferably 10 to 90%, more preferably 15 to 80%, and most preferably 20 to 70%.

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

The surface haze and internal haze can be measured by the following procedure.
(1) The total haze value (H) of the film is measured according to JIS-K7136.
(2) A few drops of silicone oil are added to the front and back surfaces of the low refractive index layer side of the film, and sandwiched from the front and back using two 1 mm thick glass plates (micro slide glass product number S 9111, manufactured by MATSANAMI), Two glass plates and a film are optically closely adhered to each other, and the haze is measured in a state where surface haze is removed, and only the silicone oil is sandwiched between two separately measured glass plates to subtract the measured haze. The calculated value is calculated as the internal haze (Hi) of the film.
(3) A value obtained by subtracting the internal haze (Hi) calculated in (2) from the total haze (H) measured in (1) above is calculated as the surface haze (Hs) of the film.

One feature of the antiglare layer of the present invention is that it has a pencil hardness of 4H or more and is excellent in flatness. Moreover, surprisingly, with the configuration of the present invention, it was possible to obtain a hardness higher than that of the prior art even when the amount of ultraviolet irradiation when curing the antiglare layer was low. Sufficient hardness can be obtained even if the amount of UV irradiation is reduced, so that heat generation of the UV absorber and antiglare layer in the cellulose ester film due to UV irradiation is suppressed, and an antiglare film with excellent flatness is obtained. It was confirmed that productivity was improved dramatically. In particular, an antiglare film having a pencil hardness of 4H or more was obtained at an irradiation dose of 100 mJ / cm ² or less.

The present invention is described in further detail below.
[Cellulose ester film]
The manufacturing method of the cellulose-ester film of the anti-glare film of this invention is described.
<Cellulose ester>
As the molecular weight of the cellulose ester used in the present invention, those having a number average molecular weight (Mn) of 80,000 to 200,000 are used. 100,000 to 200,000 are more preferable, and 150,000 to 200,000 are particularly preferable.

  The cellulose ester used in the present invention has a mass average molecular weight (Mw) to number average molecular weight (Mn) ratio, Mw / Mn of 1.4 to 3.0 as described above, but preferably 1.7. It is the range of -2.2.

  The average molecular weight and molecular weight distribution of the cellulose ester can be measured by a known method using high performance liquid chromatography. Using this, the number average molecular weight and the mass average molecular weight can be calculated, and the ratio (Mw / Mn) 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 Corp.) Mw = 100000 to 500 samples were used. It is preferable to obtain 13 samples at approximately equal intervals.

  The cellulose ester used in the present invention is a carboxylic acid ester having about 2 to 22 carbon atoms, and is particularly preferably a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. For example, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate phthalate and the like, JP-A-10-45804, Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in JP-A-8-231761, U.S. Pat. No. 2,319,052 can be used. Among the above descriptions, the lower fatty acid esters of cellulose particularly preferably used are cellulose triacetate and cellulose acetate propionate. These cellulose esters can be used as a mixture.

  In the case of cellulose triacetate, those having a total acyl group substitution degree (acetyl group substitution degree) of 2.6 to 2.9 are preferably used.

  Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 4 carbon atoms as a substituent, the substitution degree of acetyl group is X, and the substitution degree of propionyl group is Y, the following formula (I) And (II) at the same time.

Formula (I) 2.6 ≦ X + Y ≦ 2.9
Formula (II) 0 ≦ X ≦ 2.5
Among them, cellulose acetate propionate (total acyl group substitution degree = X + Y) satisfying 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 0.9 is preferable. The portion not substituted with an acyl group usually exists as a hydroxyl group. These can be synthesized by known methods.

  These acyl group substitution degrees can be measured according to the method prescribed in ASTM-D817-96.

  As the cellulose ester, cellulose ester synthesized from 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 cotton linter (hereinafter sometimes simply referred to as a linter) or a cellulose ester synthesized from wood pulp alone or in combination.

  Moreover, the cellulose ester obtained from these can be mixed and used in arbitrary ratios, respectively. These cellulose esters are prepared by using an organic acid such as acetic acid or an organic solvent such as methylene chloride when sulfuric acid is used as the acylating agent (acetic anhydride, propionic anhydride, butyric anhydride). It can obtain by making it react by a conventional method using a protic catalyst like.

  In the case of acetyl cellulose, it is necessary to extend the time for the acetylation reaction in order to increase the acetylation rate. However, if the reaction time is too long, the decomposition proceeds at the same time, and the polymer chain is broken and the acetyl group is decomposed, resulting in undesirable results. Therefore, it is necessary to set the reaction time within a certain range in order to increase the degree of acetylation and suppress decomposition to some extent. It is not appropriate to define the reaction time because the reaction conditions are various and greatly change depending on the reaction apparatus, equipment and other conditions. As the decomposition of the polymer progresses, the molecular weight distribution becomes wider. Therefore, in the case of cellulose ester as well, the degree of decomposition can be defined by the commonly used value of mass average molecular weight (Mw) / number average molecular weight (Mn). That is, in the process of acetylation of cellulose triacetate, the mass average molecular weight is used as one index of the degree of reaction for allowing the acetylation reaction to take place for a sufficient period of time without causing excessive decomposition due to being too long. The value of (Mw) / number average molecular weight (Mn) can be used.

  An example of a method for producing a cellulose ester is shown below: 100 parts by mass of a flocculent linter was crushed as a cellulose raw material, 40 parts by mass of acetic acid was added, and pretreatment activation was performed at 36 ° C. for 20 minutes. Thereafter, 8 parts by mass of sulfuric acid, 260 parts by mass of acetic anhydride and 350 parts by mass of acetic acid were added, and esterification was performed at 36 ° C. for 120 minutes. After neutralization with 11 parts by mass of a 24% magnesium acetate aqueous solution, saponification aging was carried out at 63 ° C. for 35 minutes to obtain acetylcellulose. This was stirred for 160 minutes at room temperature using a 10-fold acetic acid aqueous solution (acetic acid: water = 1: 1 (mass ratio)), then filtered and dried to obtain purified acetylcellulose having an acetyl substitution degree of 2.75. . This acetylcellulose had Mn of 92,000, Mw of 156,000, and Mw / Mn of 1.7. Similarly, cellulose esters having different degrees of substitution and Mw / Mn ratios can be synthesized by adjusting the esterification conditions (temperature, time, stirring) and hydrolysis conditions of the cellulose ester.

  The synthesized cellulose ester is preferably purified to remove low molecular weight components or to remove unacetylated components by filtration.

  In the case of a mixed acid cellulose ester, it can be obtained by a reaction described in JP-A-10-45804. The measuring method of the substitution degree of an acyl group can be measured according to the provisions of ASTM-D817-96.

  Cellulose esters are also affected by trace metal components in cellulose esters. These are considered to be related to water used in the production process, but it is preferable that there are few components that can become insoluble nuclei, and metal ions such as iron, calcium, and magnesium contain organic acidic groups. Insoluble matter may be formed by salt formation with a polymer degradation product or the like that may be present, and it is preferable that the amount is small. The iron (Fe) component is preferably 1 ppm or less. About calcium (Ca) component, it is contained in a lot of ground water and river water, etc., and it becomes hard water, and it is unsuitable as drinking water. Ligand and coordination compounds, that is, complexes are easily formed, and scum (insoluble starch, turbidity) derived from many insoluble calcium is formed.

  The calcium (Ca) component is 60 ppm or less, preferably 0 to 30 ppm. The magnesium (Mg) component is preferably in the range of 0 to 70 ppm, and more preferably 0 to 20 ppm, because too much will cause insoluble matter. Metal components such as iron (Fe) content, calcium (Ca) content, magnesium (Mg) content, etc. are pre-processed by completely digesting cellulose ester with micro digest wet cracking equipment (sulfuric acid decomposition) and alkali melting. After performing, it can obtain | require by performing an analysis using ICP-AES (inductively coupled plasma emission spectroscopy analyzer).

<Plasticizer>
The cellulose ester film used in the present invention contains at least two kinds of plasticizers. Further, it does not substantially contain a phosphate ester plasticizer such as triphenyl phosphate. “Substantially not containing” means that the content of the phosphoric ester plasticizer is less than 1% by mass, preferably 0.1% by mass, particularly preferably not added.

  By containing two or more kinds of plasticizers, the elution of the plasticizer can be reduced. The reason is not clear, but it seems that elution is suppressed by the ability to reduce the amount added per type and the interaction between the two plasticizers and the cellulose ester.

  The two plasticizers are not particularly limited, but are preferably selected from the polyhydric alcohol ester plasticizer, phthalate ester, citrate ester, fatty acid ester, glycolate plasticizer, and the like. Of these, at least one is preferably a polyhydric alcohol ester plasticizer.

  The polyhydric alcohol ester plasticizer is a plasticizer comprising an ester of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. Preferably it is a 2-20 valent aliphatic polyhydric alcohol ester.

The polyhydric alcohol used in the present invention is represented by the following general formula.
R _1- (OH) _n
However, R ₁ represents an n-valent organic group, n represents a positive integer of 2 or more, and the OH group represents an alcoholic and / or phenolic hydroxyl group.

  Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane- Examples include 1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, and xylitol. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.

  There is no restriction | limiting in particular as monocarboxylic acid used for the polyhydric alcohol ester of this invention, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention.

  Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.

  As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. The number of carbon atoms is more preferably 1-20, and particularly preferably 1-10. When acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.

  Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.

  Examples of preferable alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.

  Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid. The aromatic monocarboxylic acid which has, or those derivatives can be mentioned. Benzoic acid is particularly preferable.

  The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferred because it is less likely to volatilize, and a smaller one is preferred in terms of moisture permeability and compatibility with cellulose ester.

  The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.

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

  The glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used. Examples of alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl methyl glycolate, octyl phthalate Ethyl glycolate, and the like.

  Examples of the phthalate ester plasticizer include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.

  Examples of the citrate plasticizer include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.

  Examples of fatty acid ester plasticizers include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.

  Examples of the phosphate ester plasticizer include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like. The agent is not substantially contained in the cellulose ester film constituting the present invention. As described above, “not containing substantially” means that the content is less than 1% by mass, preferably less than 0.1% by mass, and particularly preferably not contained at all.

  As described above, when a phosphate ester plasticizer is included, the base material is likely to be deformed when the antiglare layer is formed, which is not preferable.

  The total content of the plasticizer in the cellulose ester film is preferably 5 to 20% by mass, more preferably 6 to 16% by mass, and particularly preferably 8 to 13% by mass with respect to the total solid content. The contents of the two kinds of plasticizers are each at least 1% by mass, preferably 2% by mass or more.

  The polyhydric alcohol ester plasticizer is preferably contained in an amount of 1 to 12% by mass, particularly preferably 3 to 11% by mass. If the amount is too small, deterioration of flatness is recognized, and if it is too large, bleeding out tends to occur. The ratio of the polyhydric alcohol ester plasticizer to the other plasticizer is preferably in the range of 1: 4 to 4: 1, more preferably 1: 3 to 3: 1. If the amount of the plasticizer added is too large or too small, the film is liable to be deformed, which is not preferable.

<Ultraviolet absorber>
The cellulose ester film according to the present invention contains an ultraviolet absorber. The ultraviolet absorber is intended to improve durability by absorbing ultraviolet rays of 400 nm or less, and in particular, the transmittance at a wavelength of 370 nm is preferably 10% or less, more preferably 5% or less, and further Preferably it is 2% or less.

  Although the ultraviolet absorber used in the present invention is not particularly limited, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders Examples include the body.

  For example, 5-chloro-2- (3,5-di-sec-butyl-2-hydroxylphenyl) -2H-benzotriazole, (2-2H-benzotriazol-2-yl) -6- (linear and side Chain dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, etc., and tinuvin 109, tinuvin 171, tinuvin 234, tinuvin 326, tinuvin 327, tinuvin 328, etc. These are commercially available products manufactured by Ciba Specialty Chemicals and can be preferably used.

  For example, as the benzotriazole ultraviolet absorber, a compound represented by the following general formula (A) can be used.

In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, and are a hydrogen atom, halogen atom, nitro group, hydroxyl group, alkyl group, alkenyl group, aryl group, alkoxyl group, acyloxy Represents a group, aryloxy group, alkylthio group, arylthio group, mono- or dialkylamino group, acylamino group or 5- to 6-membered heterocyclic group, and R ₄ and R ₅ are closed to form a 5- to 6-membered carbocyclic ring May be.

Moreover, these groups described above may have an arbitrary substituent.
Although the specific example of the ultraviolet absorber which concerns on this invention is given to the following, this invention is not limited to these.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- 4-Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba)
Furthermore, the ultraviolet absorber preferably used in the present invention is a benzophenone ultraviolet absorber or a triazine ultraviolet absorber, and particularly preferably a triazine ultraviolet absorber. It is preferable that the ultraviolet absorber does not contain a halogen atom in the molecule.

  As the benzophenone-based ultraviolet absorber, a compound represented by the following general formula (B) is preferably used.

In the formula, Y represents a hydrogen atom, a halogen atom or an alkyl group, an alkenyl group, an alkoxyl group, and a phenyl group, and these alkyl group, alkenyl group, and phenyl group may have a substituent. A represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group or a —CO (NH) _n-1 —D group, and D represents an alkyl group, an alkenyl group or a substituent. Represents a phenyl group which may have m and n represent 1 or 2.

  In the above, the alkyl group represents, for example, a linear or branched aliphatic group having up to 24 carbon atoms, the alkoxyl group represents, for example, an alkoxyl group having up to 18 carbon atoms, and the alkenyl group has, for example, carbon number An alkenyl group up to 16 represents an allyl group, a 2-butenyl group, or the like. In addition, as substituents to alkyl groups, alkenyl groups, and phenyl groups, halogen atoms such as chlorine atoms, bromine atoms, fluorine atoms, etc., hydroxyl groups, phenyl groups (this phenyl group is substituted with alkyl groups or halogen atoms, etc.) May be used).

  Specific examples of the benzophenone compound represented by the general formula (B) are shown below, but the present invention is not limited thereto.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)

Moreover, the compound which has a 1,3,5-triazine ring can be used preferably as a ultraviolet absorber of the optical film of this invention.
Among them, the compound having a 1,3,5-triazine ring is preferably a compound represented by the following general formula (I).

In the general formula (I), X ¹ is a single bond, —NR ⁴ —, —O— or —S—; X ² is a single bond, —NR ⁵ —, —O— or —S—; X ³ is a single bond, —NR ⁶ —, —O— or —S—; R ¹ , R ² and R ³ are an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; and R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. The compound represented by the general formula (I) is particularly preferably a melamine compound.

In the melamine compound, in the general formula (I), X ¹ , X ² and X ³ are —NR ⁴ —, —NR ⁵ — and —NR ⁶ —, respectively, or X ¹ , X ² and X 3 ³ is a single bond, and R ¹ , R ² and R ³ are heterocyclic groups having a free valence on the nitrogen atom. ^{-X 1 -R 1, -X 2 -R} 2 and -X ³ -R ³ are preferably the same substituents. R ¹ , R ² and R ³ are particularly preferably aryl groups. R ⁴ , R ⁵ and R ⁶ are particularly preferably a hydrogen atom.

  The alkyl group is preferably a chain alkyl group rather than a cyclic alkyl group. A linear alkyl group is preferred to a branched alkyl group.

  The number of carbon atoms of the alkyl group is preferably 1-30, more preferably 1-20, still more preferably 1-10, still more preferably 1-8, 6 is most preferred. The alkyl group may have a substituent.

  Specific examples of the substituent include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) and an acyloxy group (for example, acryloyloxy, methacryloyloxy). The alkenyl group is preferably a chain alkenyl group rather than a cyclic alkenyl group. A linear alkenyl group is preferable to a branched chain alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 10, still more preferably 2 to 8, 6 is most preferred. The alkenyl group may have a substituent.

  Specific examples of the substituent include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) or an acyloxy group (for example, each group such as acryloyloxy and methacryloyloxy).

  The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have a substituent.

  Specific examples of the substituent include, for example, a halogen atom, hydroxyl, cyano, nitro, carboxyl, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, alkoxycarbonyl group, alkenyloxy Carbonyl group, aryloxycarbonyl group, sulfamoyl, alkyl-substituted sulfamoyl group, alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group, sulfonamido group, carbamoyl, alkyl-substituted carmoyl group, alkenyl-substituted carbamoyl group, aryl-substituted carbamoyl group, amide group, alkylthio Groups, alkenylthio groups, arylthio groups and acyl groups are included. The said alkyl group is synonymous with the alkyl group mentioned above.

  The alkyl group of the alkoxy group, acyloxy group, alkoxycarbonyl group, alkyl-substituted sulfamoyl group, sulfonamido group, alkyl-substituted carbamoyl group, amide group, alkylthio group and acyl group is also synonymous with the alkyl group described above.

The said alkenyl group is synonymous with the alkenyl group mentioned above.
The alkenyl part of the alkenyloxy group, acyloxy group, alkenyloxycarbonyl group, alkenyl-substituted sulfamoyl group, sulfonamide group, alkenyl-substituted carbamoyl group, amide group, alkenylthio group and acyl group is also synonymous with the alkenyl group described above.

  Specific examples of the aryl group include phenyl, α-naphthyl, β-naphthyl, 4-methoxyphenyl, 3,4-diethoxyphenyl, 4-octyloxyphenyl, and 4-dodecyloxyphenyl. Can be mentioned.

  Examples of the aryloxy group, acyloxy group, aryloxycarbonyl group, aryl-substituted sulfamoyl group, sulfonamido group, aryl-substituted carbamoyl group, amide group, arylthio group, and acyl group are the same as the above aryl group.

When X ¹ , X ² or X ³ is —NR—, —O— or —S—, the heterocyclic group preferably has aromaticity.

  The heterocyclic ring in the heterocyclic group having aromaticity is generally an unsaturated heterocyclic ring, preferably a heterocyclic ring having the largest number of double bonds. The heterocyclic ring is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring.

  The hetero atom in the heterocyclic ring is preferably each atom such as N, S or O, and particularly preferably an N atom.

  As the heterocyclic ring having aromaticity, a pyridine ring (as the heterocyclic group, for example, each group such as 2-pyridyl or 4-pyridyl) is particularly preferable. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the aryl moiety.

When X ¹ , X ² or X ³ is a single bond, the heterocyclic group is preferably a heterocyclic group having a free valence on the nitrogen atom. The heterocyclic group having a free valence on the nitrogen atom is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and a 5-membered ring. Is most preferred. The heterocyclic group may have a plurality of nitrogen atoms.

  Moreover, the hetero atom in a heterocyclic group may have hetero atoms other than a nitrogen atom (for example, O atom, S atom). The heterocyclic group may have a substituent. Specific examples of the substituent of the heterocyclic group are the same as the specific examples of the substituent of the aryl moiety.

  Specific examples of the heterocyclic group having a free valence on the nitrogen atom are shown below.

  The molecular weight of the compound having a 1,3,5-triazine ring is preferably 300 to 2,000. The boiling point of the compound is preferably 260 ° C. or higher. The boiling point can be measured using a commercially available measuring device (for example, TG / DTA100, manufactured by Seiko Electronics Industry Co., Ltd.).

Specific examples of the compound having a 1,3,5-triazine ring are shown below.
A plurality of R shown below represent the same group.

(1) Butyl (2) 2-methoxy-2-ethoxyethyl (3) 5-undecenyl (4) phenyl (5) 4-ethoxycarbonylphenyl (6) 4-butoxyphenyl (7) p-biphenylyl (8) 4 -Pyridyl (9) 2-naphthyl (10) 2-methylphenyl (11) 3,4-dimethoxyphenyl (12) 2-furyl

(14) Phenyl (15) 3-ethoxycarbonylphenyl (16) 3-butoxyphenyl (17) m-biphenylyl (18) 3-phenylthiophenyl (19) 3-chlorophenyl (20) 3-benzoylphenyl (21) 3 Acetoxyphenyl (22) 3-benzoyloxyphenyl (23) 3-phenoxycarbonylphenyl (24) 3-methoxyphenyl (25) 3-anilinophenyl (26) 3-isobutyrylaminophenyl (27) 3-phenoxy Carbonylaminophenyl (28) 3- (3-ethylureido) phenyl (29) 3- (3,3-diethylureido) phenyl (30) 3-methylphenyl (31) 3-phenoxyphenyl (32) 3-hydroxyphenyl (33) 4-Ethoxycarbonylphenyl (34) 4- Toxiphenyl (35) p-biphenylyl (36) 4-phenylthiophenyl (37) 4-chlorophenyl (38) 4-benzoylphenyl (39) 4-acetoxyphenyl (40) 4-benzoyloxyphenyl (41) 4-phenoxy Carbonylphenyl (42) 4-methoxyphenyl (43) 4-anilinophenyl (44) 4-isobutyrylaminophenyl (45) 4-phenoxycarbonylaminophenyl (46) 4- (3-ethylureido) phenyl (47 ) 4- (3,3-diethylureido) phenyl (48) 4-methylphenyl (49) 4-phenoxyphenyl (50) 4-hydroxyphenyl (51) 3,4-diethoxycarbonylphenyl (52) 3,4 -Dibutoxyphenyl (53) 3,4-diphenylphenyl (5 ) 3,4-diphenylthiophenyl (55) 3,4-dichlorophenyl (56) 3,4-dibenzoylphenyl (57) 3,4-diacetoxyphenyl (58) 3,4-dibenzoyloxyphenyl (59) 3,4-diphenoxycarbonylphenyl (60) 3,4-dimethoxyphenyl (61) 3,4-dianilinophenyl (62) 3,4-dimethylphenyl (63) 3,4-diphenoxyphenyl (64) 3 , 4-Dihydroxyphenyl (65) 2-naphthyl (66) 3,4,5-triethoxycarbonylphenyl (67) 3,4,5-tributoxyphenyl (68) 3,4,5-triphenylphenyl (69 ) 3,4,5-triphenylthiophenyl (70) 3,4,5-trichlorophenyl (71) 3,4,5-tribenzoylphenol Nyl (72) 3,4,5-triacetoxyphenyl (73) 3,4,5-tribenzoyloxyphenyl (74) 3,4,5-triphenoxycarbonylphenyl (75) 3,4,5-trimethoxy Phenyl (76) 3,4,5-trianilinophenyl (77) 3,4,5-trimethylphenyl (78) 3,4,5-triphenoxyphenyl (79) 3,4,5-trihydroxyphenyl

(80) Phenyl (81) 3-ethoxycarbonylphenyl (82) 3-butoxyphenyl (83) m-biphenylyl (84) 3-phenylthiophenyl (85) 3-chlorophenyl (86) 3-benzoylphenyl (87) 3 Acetoxyphenyl (88) 3-benzoyloxyphenyl (89) 3-phenoxycarbonylphenyl (90) 3-methoxyphenyl (91) 3-anilinophenyl (92) 3-isobutyrylaminophenyl (93) 3-phenoxy Carbonylaminophenyl (94) 3- (3-ethylureido) phenyl (95) 3- (3,3-diethylureido) phenyl (96) 3-methylphenyl (97) 3-phenoxyphenyl (98) 3-hydroxyphenyl (99) 4-Ethoxycarbonylphenyl (100) 4 Butoxyphenyl (101) p-biphenylyl (102) 4-phenylthiophenyl (103) 4-chlorophenyl (104) 4-benzoylphenyl (105) 4-acetoxyphenyl (106) 4-benzoyloxyphenyl (107) 4-phenoxy Carbonylphenyl (108) 4-methoxyphenyl (109) 4-anilinophenyl (110) 4-isobutyrylaminophenyl (111) 4-phenoxycarbonylaminophenyl (112) 4- (3-ethylureido) phenyl (113 ) 4- (3,3-diethylureido) phenyl (114) 4-methylphenyl (115) 4-phenoxyphenyl (116) 4-hydroxyphenyl (117) 3,4-diethoxycarbonylphenyl (118) 3,4 -Dibutoxyphenyl 119) 3,4-diphenylphenyl (120) 3,4-diphenylthiophenyl (121) 3,4-dichlorophenyl (122) 3,4-dibenzoylphenyl (123) 3,4-diacetoxyphenyl (124) 3 , 4-Dibenzoyloxyphenyl (125) 3,4-diphenoxycarbonylphenyl (126) 3,4-dimethoxyphenyl (127) 3,4-dianilinophenyl (128) 3,4-dimethylphenyl (129) 3 , 4-Diphenoxyphenyl (130) 3,4-dihydroxyphenyl (131) 2-naphthyl (132) 3,4,5-triethoxycarbonylphenyl (133) 3,4,5-tributoxyphenyl (134) 3 , 4,5-triphenylphenyl (135) 3,4,5-triphenylthiophenyl (1 36) 3,4,5-trichlorophenyl (137) 3,4,5-tribenzoylphenyl (138) 3,4,5-triacetoxyphenyl (139) 3,4,5-tribenzoyloxyphenyl (140) 3,4,5-triphenoxycarbonylphenyl (141) 3,4,5-trimethoxyphenyl (142) 3,4,5-trianilinophenyl (143) 3,4,5-trimethylphenyl (144) 3 , 4,5-Triphenoxyphenyl (145) 3,4,5-trihydroxyphenyl

(146) phenyl (147) 4-ethoxycarbonylphenyl (148) 4-butoxyphenyl (149) p-biphenylyl (150) 4-phenylthiophenyl (151) 4-chlorophenyl (152) 4-benzoylphenyl (153) 4 Acetoxyphenyl (154) 4-benzoyloxyphenyl (155) 4-phenoxycarbonylphenyl (156) 4-methoxyphenyl (157) 4-anilinophenyl (158) 4-isobutyrylaminophenyl (159) 4-phenoxy Carbonylaminophenyl (160) 4- (3-ethylureido) phenyl (161) 4- (3,3-diethylureido) phenyl (162) 4-methylphenyl (163) 4-phenoxyphenyl (164) 4-hydroxyphenyl

(165) phenyl (166) 4-ethoxycarbonylphenyl (167) 4-butoxyphenyl (168) p-biphenylyl (169) 4-phenylthiophenyl (170) 4-chlorophenyl (171) 4-benzoylphenyl (172) 4 Acetoxyphenyl (173) 4-benzoyloxyphenyl (174) 4-phenoxycarbonylphenyl (175) 4-methoxyphenyl (176) 4-anilinophenyl (177) 4-isobutyrylaminophenyl (178) 4-phenoxy Carbonylaminophenyl (179) 4- (3-ethylureido) phenyl (180) 4- (3,3-diethylureido) phenyl (181) 4-methylphenyl (182) 4-phenoxyphenyl (183) 4-hydroxyphenyl

(184) phenyl (185) 4-ethoxycarbonylphenyl (186) 4-butoxyphenyl (187) p-biphenylyl (188) 4-phenylthiophenyl (189) 4-chlorophenyl (190) 4-benzoylphenyl (191) 4 Acetoxyphenyl (192) 4-benzoyloxyphenyl (193) 4-phenoxycarbonylphenyl (194) 4-methoxyphenyl (195) 4-anilinophenyl (196) 4-isobutyrylaminophenyl (197) 4-phenoxy Carbonylaminophenyl (198) 4- (3-ethylureido) phenyl (199) 4- (3,3-diethylureido) phenyl (200) 4-methylphenyl (201) 4-phenoxyphenyl (202) 4-hydroxyphenyl

(203) phenyl (204) 4-ethoxycarbonylphenyl (205) 4-butoxyphenyl (206) p-biphenylyl (207) 4-phenylthiophenyl (208) 4-chlorophenyl (209) 4-benzoylphenyl (210) 4 Acetoxyphenyl (211) 4-benzoyloxyphenyl (212) 4-phenoxycarbonylphenyl (213) 4-methoxyphenyl (214) 4-anilinophenyl (215) 4-isobutyrylaminophenyl (216) 4-phenoxy Carbonylaminophenyl (217) 4- (3-ethylureido) phenyl (218) 4- (3,3-diethylureido) phenyl (219) 4-methylphenyl (220) 4-phenoxyphenyl (221) 4-hydroxyphenyl

(222) phenyl (223) 4-butylphenyl (224) 4- (2-methoxy-2-ethoxyethyl) phenyl (225) 4- (5-nonenyl) phenyl (226) p-biphenylyl (227) 4-ethoxy Carbonylphenyl (228) 4-butoxyphenyl (229) 4-methylphenyl (230) 4-chlorophenyl (231) 4-phenylthiophenyl (232) 4-benzoylphenyl (233) 4-acetoxyphenyl (234) 4-benzoyl Oxyphenyl (235) 4-phenoxycarbonylphenyl (236) 4-methoxyphenyl (237) 4-anilinophenyl (238) 4-isobutyrylaminophenyl (239) 4-phenoxycarbonylaminophenyl (240) 4- ( 3-ethylureido) phenyl ( 41) 4- (3,3-Diethylureido) phenyl (242) 4-phenoxyphenyl (243) 4-hydroxyphenyl (244) 3-butylphenyl (245) 3- (2-methoxy-2-ethoxyethyl) phenyl (246) 3- (5-Nonenyl) phenyl (247) m-biphenylyl (248) 3-ethoxycarbonylphenyl (249) 3-butoxyphenyl (250) 3-methylphenyl (251) 3-chlorophenyl (252) 3- Phenylthiophenyl (253) 3-benzoylphenyl (254) 3-acetoxyphenyl (255) 3-benzoyloxyphenyl (256) 3-phenoxycarbonylphenyl (257) 3-methoxyphenyl (258) 3-anilinophenyl (259) ) 3-Isobutyrylaminophenyl 260) 3-phenoxycarbonylaminophenyl (261) 3- (3-ethylureido) phenyl (262) 3- (3,3-diethylureido) phenyl (263) 3-phenoxyphenyl (264) 3-hydroxyphenyl (265) ) 2-Butylphenyl (266) 2- (2-methoxy-2-ethoxyethyl) phenyl (267) 2- (5-nonenyl) phenyl (268) o-biphenylyl (269) 2-ethoxycarbonylphenyl (270) 2 -Butoxyphenyl (271) 2-methylphenyl (272) 2-chlorophenyl (273) 2-phenylthiophenyl (274) 2-benzoylphenyl (275) 2-acetoxyphenyl (276) 2-benzoyloxyphenyl (277) 2 -Phenoxycarbonylphenyl (278 ) 2-methoxyphenyl (279) 2-anilinophenyl (280) 2-isobutyrylaminophenyl (281) 2-phenoxycarbonylaminophenyl (282) 2- (3-ethylureido) phenyl (283) 2- ( 3,3-diethylureido) phenyl (284) 2-phenoxyphenyl (285) 2-hydroxyphenyl (286) 3,4-dibutylphenyl (287) 3,4-di (2-methoxy-2-ethoxyethyl) phenyl (288) 3,4-diphenylphenyl (289) 3,4-diethoxycarbonylphenyl (290) 3,4-didodecyloxyphenyl (291) 3,4-dimethylphenyl (292) 3,4-dichlorophenyl (293 ) 3,4-Dibenzoylphenyl (294) 3,4-diacetoxyphenyl ( 95) 3,4-dimethoxyphenyl (296) 3,4-di-N-methylaminophenyl (297) 3,4-diisobutyrylaminophenyl (298) 3,4-diphenoxyphenyl (299) 3,4 -Dihydroxyphenyl (300) 3,5-dibutylphenyl (301) 3,5-di (2-methoxy-2-ethoxyethyl) phenyl (302) 3,5-diphenylphenyl (303) 3,5-diethoxycarbonyl Phenyl (304) 3,5-didodecyloxyphenyl (305) 3,5-dimethylphenyl (306) 3,5-dichlorophenyl (307) 3,5-dibenzoylphenyl (308) 3,5-diacetoxyphenyl ( 309) 3,5-dimethoxyphenyl (310) 3,5-di-N-methylaminophenyl (311) 3,5 Diisobutyrylaminophenyl (312) 3,5-diphenoxyphenyl (313) 3,5-dihydroxyphenyl (314) 2,4-dibutylphenyl (315) 2,4-di (2-methoxy-2-ethoxyethyl) ) Phenyl (316) 2,4-diphenylphenyl (317) 2,4-diethoxycarbonylphenyl (318) 2,4-didodecyloxyphenyl (319) 2,4-dimethylphenyl (320) 2,4-dichlorophenyl (321) 2,4-Dibenzoylphenyl (322) 2,4-diacetoxyphenyl (323) 2,4-dimethoxyphenyl (324) 2,4-di-N-methylaminophenyl (325) 2,4- Diisobutyrylaminophenyl (326) 2,4-diphenoxyphenyl (327) 2,4-dihydroxy Phenyl (328) 2,3-dibutylphenyl (329) 2,3-di (2-methoxy-2-ethoxyethyl) phenyl (330) 2,3-diphenylphenyl (331) 2,3-diethoxycarbonylphenyl ( 332) 2,3-didodecyloxyphenyl (333) 2,3-dimethylphenyl (334) 2,3-dichlorophenyl (335) 2,3-dibenzoylphenyl (336) 2,3-diacetoxyphenyl (337) 2,3-dimethoxyphenyl (338) 2,3-di-N-methylaminophenyl (339) 2,3-diisobutyrylaminophenyl (340) 2,3-diphenoxyphenyl (341) 2,3-dihydroxy Phenyl (342) 2,6-dibutylphenyl (343) 2,6-di (2-methoxy-2-ethoxyethyl) Phenyl (344) 2,6-diphenylphenyl (345) 2,6-diethoxycarbonylphenyl (346) 2,6-didodecyloxyphenyl (347) 2,6-dimethylphenyl (348) 2,6-dichlorophenyl ( 349) 2,6-dibenzoylphenyl (350) 2,6-diacetoxyphenyl (351) 2,6-dimethoxyphenyl (352) 2,6-di-N-methylaminophenyl (353) 2,6-diisobu Tyrylaminophenyl (354) 2,6-diphenoxyphenyl (355) 2,6-dihydroxyphenyl (356) 3,4,5-tributylphenyl (357) 3,4,5-tri (2-methoxy-2) -Ethoxyethyl) phenyl (358) 3,4,5-triphenylphenyl (359) 3,4,5-triethoxy Carbonylphenyl (360) 3,4,5-tridodecyloxyphenyl (361) 3,4,5-trimethylphenyl (362) 3,4,5-trichlorophenyl (363) 3,4,5-tribenzoylphenyl ( 364) 3,4,5-triacetoxyphenyl (365) 3,4,5-trimethoxyphenyl (366) 3,4,5-tri-N-methylaminophenyl (367) 3,4,5-triiso Butyrylaminophenyl (368) 3,4,5-triphenoxyphenyl (369) 3,4,5-trihydroxyphenyl (370) 2,4,6-tributylphenyl (371) 2,4,6-tri ( 2-methoxy-2-ethoxyethyl) phenyl (372) 2,4,6-triphenylphenyl (373) 2,4,6-triethoxycarbonyl Enyl (374) 2,4,6-tridodecyloxyphenyl (375) 2,4,6-trimethylphenyl (376) 2,4,6-trichlorophenyl (377) 2,4,6-tribenzoylphenyl (378) ) 2,4,6-triacetoxyphenyl (379) 2,4,6-trimethoxyphenyl (380) 2,4,6-tri-N-methylaminophenyl (381) 2,4,6-triisobuty Rylaminophenyl (382) 2,4,6-triphenoxyphenyl (383) 2,4,6-trihydroxyphenyl (384) pentafluorophenyl (385) pentachlorophenyl (386) pentamethoxyphenyl (387) 6-N -Methylsulfamoyl-8-methoxy-2-naphthyl (388) 5-N-methylsulfamoyl-2-naphthy (389) 6-N-phenylsulfamoyl-2-naphthyl (390) 5-ethoxy-7-N-methylsulfamoyl-2-naphthyl (391) 3-methoxy-2-naphthyl (392) 1-ethoxy 2-naphthyl (393) 6-N-phenylsulfamoyl-8-methoxy-2-naphthyl (394) 5-methoxy-7-N-phenylsulfamoyl-2-naphthyl (395) 1- (4- Methylphenyl) -2-naphthyl (396) 6,8-di-N-methylsulfamoyl-2-naphthyl (397) 6-N-2-acetoxyethylsulfamoyl-8-methoxy-2-naphthyl (398) ) 5-Acetoxy-7-N-phenylsulfamoyl-2-naphthyl (399) 3-benzoyloxy-2-naphthyl (400) 5-acetylamino-1 Naphthyl (401) 2-methoxy-1-naphthyl (402) 4-phenoxy-1-naphthyl (403) 5-N-methylsulfamoyl-1-naphthyl (404) 3-N-methylcarbamoyl-4-hydroxy- 1-naphthyl (405) 5-methoxy-6-N-ethylsulfamoyl-1-naphthyl (406) 7-tetradecyloxy-1-naphthyl (407) 4- (4-methylphenoxy) -1-naphthyl ( 408) 6-N-methylsulfamoyl-1-naphthyl (409) 3-N, N-dimethylcarbamoyl-4-methoxy-1-naphthyl (410) 5-methoxy-6-N-benzylsulfamoyl-1 -Naphtyl (411) 3,6-di-N-phenylsulfamoyl-1-naphthyl (412) methyl (413) ethyl (414) butyl ( 415) Octyl (416) dodecyl (417) 2-butoxy-2-ethoxyethyl (418) benzyl (419) 4-methoxybenzyl

(424) methyl (425) phenyl (426) butyl

(430) methyl (431) ethyl (432) butyl (433) octyl (434) dodecyl (435) 2-butoxy 2-ethoxyethyl (436) benzyl (437) 4-methoxybenzyl

  In the present invention, a melamine polymer may be used as the compound having a 1,3,5-triazine ring. The melamine polymer is preferably synthesized by a polymerization reaction between a melamine compound represented by the following general formula (II) and a carbonyl compound.

In the above synthetic reaction scheme, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

  The alkyl group, alkenyl group, aryl group, heterocyclic group, and substituents thereof have the same meanings as the groups and substituents described in the general formula (I).

  The polymerization reaction between the melamine compound and the carbonyl compound is the same as the method for synthesizing a normal melamine resin (for example, melamine formaldehyde resin). Moreover, you may use a commercially available melamine polymer (melamine resin).

  The molecular weight of the melamine polymer is preferably 2,000 to 400,000. Specific examples of the repeating unit of the melamine polymer are shown below.

MP-1: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OH
^{MP-2: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-3: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-4: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-5: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-6: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-7: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-8: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-9: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-10: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-11: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-12: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-13: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-14: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-15: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-16: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-17: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-18: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-19: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-20: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
MP-21: R ¹³ , R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH _{2 On} -C ₄ H ₉
^{MP-22: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-23: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-24: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-25: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2O -n-C 4 H 9
^{MP-26: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
^{MP-27: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-28: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-29: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-30: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-31: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-32: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-33: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-34: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-35: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-36: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-37: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-38: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-39: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-40: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-41: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-42: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-43: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-44: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-45: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-46: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-47: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-48: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-49: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-50: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

^{MP-51: R 13, R} 14, R 15, R 16: CH 2 OH
^{MP-52: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-53: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-54: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-55: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-56: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-57: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-58: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-59: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-60: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-61: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-62: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-63: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-64: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-65: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-66: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-67: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-68: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-69: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-70: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-71: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-72: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-73: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-74: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-75: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-76: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
^{MP-77: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-78: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-79: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-80: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-81: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-82: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-83: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-84: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-85: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-86: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-87: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-88: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-89: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-90: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-91: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-92: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-93: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-94: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-95: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-96: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-97: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-98: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-99: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-100: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

^{MP-101: R 13, R} 14, R 15, R 16: CH 2 OH
^{MP-102: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-103: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-104: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-105: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-106: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-107: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-108: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-109: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-110: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-111: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-112: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-113: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-114: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-115: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-116: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-117: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-118: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-119: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-120: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-121: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-122: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-123: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-124: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-125: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-126: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
^{MP-127: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-128: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-129: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-130: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-131: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-132: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-133: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-134: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-135: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-136: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-137: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-138: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-139: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-140: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-141: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-142: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-143: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-144: R 13: CH2O} -n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-145: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-146: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-147: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-148: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-149: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-150: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

^{MP-151: R 13, R} 14, R 15, R 16: CH 2 OH
^{MP-152: R 13, R} 14, R 15, R 16: CH2OCH 3
^{MP-153: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-154: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-155: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-156: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-157: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-158: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-159: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-160: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-161: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-162: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-163: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-164: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-165: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-166: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-167: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-168: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-169: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-170: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-171: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-172: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-173: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-174: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-175: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
MP-176: R ¹³ , R ¹⁴ , R ¹⁶ : CH _{2 On} -C ₄ H ₉ ; R ¹⁵ : CH ₂ OH
^{MP-177: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-178: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-179: R 13, R} 14: CH 2 OH; R 15: CH2O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-180: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-181: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-182: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-183: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-184: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-185: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-186: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-187: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-188: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-189: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-190: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-191: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-192: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-193: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-194: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-195: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-196: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-197: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-198: R 13: CH} 2 OCH 3; R 14: CH2OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-199: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-200: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
In the present invention, a copolymer obtained by combining two or more of the above repeating units may be used. Two or more homopolymers or copolymers may be used in combination.

  Moreover, you may use together the compound which has a 2 or more types of 1,3,5- triazine ring. Two or more kinds of discotic compounds (for example, a compound having a 1,3,5-triazine ring and a compound having a porphyrin skeleton) may be used in combination.

  These additives are preferably contained in an amount of 0.2 to 30% by mass, particularly preferably 1 to 20% by mass with respect to the cellulose ester film.

  Moreover, the triazine type compound shown by general formula (I) of Unexamined-Japanese-Patent No. 2001-235621 is also preferably used for the cellulose-ester film concerning this invention.

  The cellulose ester film according to the present invention preferably contains two or more ultraviolet absorbers.

  As the UV absorber, a polymer UV absorber can be preferably used, and in particular, a polymer type UV absorber described in JP-A-6-148430 is preferably used.

  The method for adding the UV absorber is to add the UV absorber to the dope after dissolving the UV absorber in an alcohol such as methanol, ethanol or butanol, an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane, or a mixed solvent thereof. Or you may add directly in dope composition. For an inorganic powder that does not dissolve in an organic solvent, a dissolver or a sand mill is used in the organic solvent and cellulose ester to disperse and then added to the dope.

  The amount of UV absorber used is not uniform depending on the type of UV absorber, operating conditions, etc., but when the dry film thickness of the cellulose ester film is 30 to 200 μm, it is 0.5 to 4 with respect to the cellulose ester film. 0.0 mass% is preferable, and 0.6 to 2.0 mass% is still more preferable.

<Fine particles>
The cellulose ester film according to the present invention preferably contains fine particles.

  As fine particles used in the present invention, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, and hydrated silicic acid. Mention may be made of calcium, aluminum silicate, magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.

  The average primary particle diameter of the fine particles is preferably 5 to 50 nm, and more preferably 7 to 20 nm. These are preferably contained mainly as secondary aggregates having a particle size of 0.05 to 0.3 μm. The average diameter of the fine particles is an average diameter weighted by the mass of the particles and can be measured by a light scattering method or an electron micrograph. The content of these fine particles in the cellulose ester film is preferably 0.05 to 1% by mass, particularly preferably 0.1 to 0.5% by mass. In the case of a cellulose ester film having a multilayer structure by the co-casting method, it is preferable to contain fine particles of this addition amount on the surface.

  Silicon dioxide fine particles are commercially available under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). I can do it.

  Zirconium oxide fine particles are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.

  Examples of the polymer include silicone resin, fluorine resin, 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 effect of reducing the friction coefficient while keeping the turbidity of the cellulose ester film low. In the cellulose ester film used in the present invention, the dynamic friction coefficient on the back side of the antiglare layer is preferably 1.0 or less.

<dye>
A dye may be added to the cellulose ester film used in the present invention to adjust the color. For example, a blue dye may be added to suppress the yellowness of the film. Preferred examples of the dye include anthraquinone dyes.

  The anthraquinone dye may have an arbitrary substituent at an arbitrary position from the 1st position to the 8th position of the anthraquinone. Preferred substituents include an anilino group, hydroxyl group, amino group, nitro group, or hydrogen atom. In particular, it is preferable to contain a blue dye described in JP-A-2001-154017, particularly an anthraquinone dye.

  Various additives may be batch-added to a dope that is a cellulose ester-containing solution before film formation, or an additive solution may be separately prepared and added in-line. In particular, it is preferable to add a part or all of the fine particles in-line in order to reduce the load on the filter medium.

  When the additive solution is added in-line, it is preferable to dissolve a small amount of cellulose ester in order to improve mixing with the dope. The amount of the cellulose ester is preferably 1 to 10 parts by mass, more preferably 3 to 5 parts by mass with respect to 100 parts by mass of the solvent.

  In the present invention, for example, an in-line mixer such as a static mixer (manufactured by Toray Engineering Co., Ltd.) or SWJ (Toray Static In-Pipe Mixer Hi-Mixer) is preferably used for performing in-line addition and mixing.

<Method for producing cellulose ester film>
Next, the manufacturing method of the cellulose-ester film of this invention is demonstrated.

  The cellulose ester film of the present invention is prepared by dissolving a cellulose ester and an additive in a solvent to prepare a dope, casting a dope onto an endless metal support, and casting the dope. It is carried out by a step of drying as a web, a step of peeling from a 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 process for preparing the dope will be described. The concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced, but if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy is poor. Become. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%.

  The solvent used in the dope of the present invention may be used alone or in combination of two or more. However, it is preferable from the viewpoint of production efficiency that a good solvent and a poor solvent of cellulose ester are mixed and used. The more solvent is preferable from the viewpoint of solubility of the cellulose ester. The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent. With a good solvent and a poor solvent, what dissolve | melts the cellulose ester to be used independently is defined as a good solvent, and what poorly swells or does not melt | dissolve is defined as a poor solvent. Therefore, depending on the average acetylation degree (acetyl group substitution degree) of the cellulose ester, the good solvent and the poor solvent change. For example, when acetone is used as the solvent, the cellulose ester acetate ester (acetyl group substitution degree 2.4), cellulose Acetate propionate is a good solvent, and cellulose acetate (acetyl group substitution degree 2.8) is a poor solvent.

  Although the good solvent used for this invention is not specifically limited, Organic halogen compounds, such as a methylene chloride, dioxolanes, acetone, methyl acetate, methyl acetoacetate, etc. are mentioned. Particularly preferred is methylene chloride or methyl acetate.

  Moreover, although the poor solvent used for this invention is not specifically limited, For example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone, etc. are used preferably. Moreover, it is preferable that 0.01-2 mass% of water contains in dope.

  A general method can be used as a method of dissolving the cellulose ester when preparing the dope described above. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and that the solvent does not boil under pressure, in order to prevent the generation of massive undissolved materials called gels and mamacos. Moreover, after mixing a cellulose ester with a poor solvent and making it wet or swell, the method of adding a good solvent and melt | dissolving is also used preferably.

  The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.

  The heating temperature with the addition of the solvent is preferably higher from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates. A preferable heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature.

  Alternatively, a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.

  Next, this cellulose ester solution is filtered using a suitable filter medium such as filter paper. As the filter medium, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like, but if the absolute filtration accuracy is too small, the filter medium is likely to be clogged. For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is still more preferable.

  The material of the filter medium is not particularly limited, and a normal filter medium can be used. However, a plastic filter medium such as polypropylene and Teflon (R) and a metal filter medium such as stainless steel are preferable because there is no loss of fibers. . It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose ester by filtration.

A bright spot foreign substance is when two polarizing plates are placed in a crossed Nicol state, a cellulose ester film is placed between them, light is applied from the side of one polarizing plate, and observed from the side of the other polarizing plate. It is a point (foreign matter) where light from the opposite side appears to leak, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm ² or less. More preferably, it is 100 pieces / cm < ² > or less, More preferably, it is 50 pieces / m < ² > or less, More preferably, it is 0-10 pieces / cm < ² > or less. Further, it is preferable that the number of bright spots of 0.01 mm or less is small.

  The dope can be filtered by an ordinary method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration. The increase in the difference (referred to as differential pressure) is small and preferable. A preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C.

  A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.

Here, the dope casting will be described.
The metal support in the casting (casting) step preferably has a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support. The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting step is −50 ° C. to a temperature lower than the boiling point of the solvent, and a higher temperature is preferable because the web drying rate can be increased. May deteriorate. A preferable support body temperature is 0-40 degreeC, and 5-30 degreeC is still more preferable. 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 warm air is used, wind at a temperature higher than the target temperature may be used.

  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%.

In the present invention, 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.

  Further, in the drying step of the cellulose ester film, 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, Especially preferably, it 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 order to produce the cellulose ester film for an antiglare film of the present invention, the web is stretched in the conveying direction immediately after peeling from the metal support where the residual solvent amount is large, and both ends of the web are gripped with clips or the like. It is particularly preferable to perform stretching in the width direction by a tenter method. The preferred draw ratio in both the machine direction and the transverse direction is 1.05 to 1.3 times, and more preferably 1.05 to 1.15 times. It is preferable that the area is 1.12 times to 1.44 times, and preferably 1.15 times to 1.32 times due to longitudinal and lateral stretching. This can be determined by the draw ratio in the longitudinal direction × the draw ratio in the transverse direction. If one of the draw ratios in the machine direction and the transverse direction is less than 1.05 times, the deterioration of the flatness due to ultraviolet irradiation when forming the antiglare layer is unfavorable. Moreover, even if a draw ratio exceeds 1.3 times, since planarity deteriorates and haze also increases, it is not preferable.

  In order to stretch in the longitudinal direction immediately after peeling, peeling is preferably performed at a peeling tension of 210 N / m or more, particularly preferably 220 to 300 N / m.

  The means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but it is preferably performed with hot air in terms of simplicity.

  The drying temperature in the web drying step is preferably increased stepwise from 40 to 150 ° C, more preferably from 50 to 140 ° C in order to improve dimensional stability.

  Although the film thickness of a cellulose-ester film is not specifically limited, 10-200 micrometers is used preferably. In particular, it was difficult to obtain an antiglare film excellent in flatness and hardness with a thin film of 10 to 70 μm, but according to the present invention, a thin antiglare film excellent in flatness and hardness was obtained, Moreover, since it is excellent also in productivity, it is especially preferable that the film thickness of a cellulose-ester film is 10-70 micrometers. More preferably, it is 20-60 micrometers. Most preferably, it is 35-60 micrometers.

The antiglare film of the present invention preferably has a width of 1 to 4 m.
When the width of the cellulose ester film becomes wider, the illuminance unevenness of the irradiated light at the time of UV curing cannot be ignored, not only the flatness is deteriorated, but also the unevenness of the hardness occurs, and when the antireflection layer is formed on this, the uneven reflection is generated. Become prominent. Since the anti-glare film of the present invention can provide sufficient hardness with a small amount of irradiation, even if there is unevenness of the irradiation amount in the width direction of the irradiation light, there is little unevenness of the hardness in the width direction, and anti-glare with excellent flatness Since a film is obtained, a remarkable effect is recognized with a wide cellulose ester film. In particular, those having a width of 1.4 to 4 m are preferably used, and particularly preferably 1.4 to 2 m. If it exceeds 4 m, conveyance becomes difficult.

<Physical properties>
The moisture permeability of the cellulose ester film used in the present invention, 40 ° C., or less 850g / m ² · 24h at 90% RH, preferably ^{20~800g / m 2 · 24h, 20~750g} / m 2 · 24 h is particularly preferable. The moisture permeability can be measured according to the method described in JIS Z0208.

  The breaking elongation of the cellulose ester film used in the present invention is preferably 10 to 80%, and more preferably 20 to 50%.

  The visible light transmittance of the cellulose ester film used in the present invention is preferably 90% or more, and more preferably 93% or more.

  The haze of the cellulose ester film used in the present invention is preferably less than 1%, particularly preferably 0 to 0.1%.

  The in-plane retardation value (Re) of the cellulose ester film used in the present invention is preferably 0 to 70 nm or less. More preferably, it is 0-30 nm or less, More preferably, it is 0-10 nm or less. The retardation value (Rth) in the film thickness direction is preferably 400 nm or less, preferably 10 to 200 nm, and more preferably 30 to 150 nm.

  The retardation value (Re) (Rth) can be obtained by the following equation.

Re = (nx−ny) × d
Rth = ((nx + ny) / 2−nz) × d
Here, d is the thickness (nm) of the film, the refractive index nx (also referred to as the maximum refractive index in the plane of the film, the refractive index in the slow axis direction), ny (in the direction perpendicular to the slow axis in the film plane). ) (Refractive index of the film in the thickness direction).

  The retardation values (Re) and (Rth) can be measured using an automatic birefringence meter. For example, the wavelength can be obtained at 590 nm in an environment of 23 ° C. and 55% RH using KOBRA-21ADH (Oji Scientific Instruments).

  The slow axis is preferably in the width direction ± 1 ° of the film or in the longitudinal direction ± 1 °.

[Anti-glare layer]
Next, the manufacturing method of the anti-glare layer of the anti-glare film of this invention is described.

  The antiglare layer is formed for the purpose of contributing to the film surface scattering properties due to the surface irregularity shape, internal scattering properties, and preferably hard coat properties for improving the scratch resistance of the film. Therefore, it preferably contains at least one translucent resin capable of imparting hard coat properties and at least one light diffusing particle for imparting internal scattering properties.

(Light diffusing particles)
The average particle size of the light diffusing particles needs to be 5 to 15 μm, preferably 6 to 12 μm, and more preferably 7 to 10 μm. The average particle diameter of the light diffusing particles is an average diameter weighted by the mass of the particles, and can be measured by a light scattering method or an electron micrograph. If the average particle size is less than 5 μm, the light scattering angle distribution spreads to a wide angle, which causes blurring of characters on the display, which is not preferable. On the other hand, when the thickness exceeds 15 μm, it is necessary to increase the film thickness of the antiglare layer, resulting in an increase in curling and an increase in material cost.
Specific examples of the light diffusing particles include, for example, poly ((meth) acrylate) particles, crosslinked poly ((meth) acrylate) particles, polystyrene particles, crosslinked polystyrene particles, crosslinked poly (acryl-styrene) particles, melamine resin particles, Preferred examples include resin particles such as benzoguanamine resin particles. Of these, cross-linked polystyrene particles, cross-linked poly ((meth) acrylate) particles, and cross-linked poly (acryl-styrene) particles are preferably used, and the light diffusible particles selected from these particles are used in accordance with the refractive index. By adjusting the refractive index of the light-sensitive resin, the internal haze and surface haze can be adjusted to the desired ranges, and the combination of the light-transmitting resin and the light diffusing particles, the solvent of the coating composition, the addition amount, etc. are adjusted. By doing so, the center line average roughness can be in a desired range.

Specifically, a translucent resin (having a refractive index after curing of 1.50 to 1.54) mainly composed of a tri- or higher functional (meth) acrylate monomer that is preferably used for an antiglare layer described later is used. In this case, it is preferable to combine light diffusing particles composed of a crosslinked poly (meth) acrylate polymer having an acrylic content of 20 to 100% by mass, and in particular, the light-transmitting resin and the crosslinked poly (acryl-styrene) copolymer A combination with light diffusing particles made of coalescence (refractive index: 1.48 to 1.58) is preferable.
Here, the “translucent resin having a trifunctional or higher functional (meth) acrylate monomer as a main component” means that a repeating unit composed of a trifunctional or higher functional (meth) acrylate monomer is 50 to 100 in the translucent resin. It means that it is contained by mass%. The content of the repeating unit composed of a tri- or higher functional (meth) acrylate monomer is preferably 60 to 100% by mass.

  Two or more kinds of light diffusing particles having different particle diameters may be used in combination.

The light diffusing particles are required to be contained in the formed antiglare layer in an amount of 3% by mass or more in the total solid content of the antiglare layer, and are blended so as to be contained in an amount of 3 to 30% by mass. Is preferred. More preferably, it is 4-25 mass%. More preferably, it is 5-15 mass%. If it is less than 3% by mass, the internal scattering property is insufficient, and if it exceeds 30% by mass, image blurring, surface turbidity or glare may occur.
The density of the light diffusing particles is preferably 0.8 to 3.2 g / m ² , more preferably 0.9 to 2.8 g / m ² .

The refractive indexes of the translucent resin and the light diffusing particles are preferably in the above range. The difference in refractive index between the light-transmitting resin and the light-diffusing particles (the refractive index of the light-diffusing particles−the refractive index of the light-transmitting resin) is preferably 0.008 to 0.15 as an absolute value. More preferably, it is 0.01-0.10. Particularly preferably, light diffusing particles in the range of 0.008 to 0.05 are used in an amount of 30% or more of the total light diffusing particles. By setting the range as described above, it is possible to obtain good performance such as image blur, surface turbidity, and contrast.
The refractive index of the light diffusing particles is determined by measuring the turbidity by dispersing an equal amount of the light diffusing particles in the solvent in which the refractive index is changed by changing the mixing ratio of two types of solvents having different refractive indexes. It is measured by measuring the refractive index of the solvent when the degree becomes minimum with an Abbe refractometer.
Further, the refractive index of the translucent resin can be quantitatively evaluated by directly measuring it with an Abbe refractometer or by measuring a spectral reflection spectrum or a spectral ellipsometry. When the translucent resin is curable, it indicates the refractive index after curing.

  The film thickness of the antiglare layer needs to be 8 to 40 μm, more preferably 12 to 35 μm, and particularly preferably 18 to 30 μm. If it is too thin, the hard property will be insufficient, and if it is too thick, the curling and brittleness may deteriorate and the workability may be reduced, the cost may increase, and unevenness may occur.

(Translucent resin)
The translucent 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. The binder polymer preferably has a crosslinked structure.
As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid [for example, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di ( (Meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3- Chlorohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate], ethylene oxide-modified products and caprolactone-modified products of the above esters, vinylbenzene and its derivatives [eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2- Acryloyl ethyl ester, 1,4-divinylcyclohexanone], vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination.

In order to make the binder polymer have a high refractive index, the monomer structure has a high refractive index containing at least one atom selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom. A monomer, a monomer having a fluorene skeleton in the molecule, or the like can also be selected.
Specific examples of the high refractive index monomer include (meth) acrylates having a fluorene skeleton, bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, etc. Is mentioned. Two or more of these monomers may be used in combination.

Polymerization of these monomers can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Therefore, the antiglare layer is composed of a monomer for forming a translucent resin such as the above-mentioned ethylenically unsaturated monomer, a photo radical initiator or a thermal radical initiator, a light diffusing particle, and an inorganic material as described later if necessary. It can be formed by preparing a coating liquid containing a filler and curing the coating liquid on a transparent support by a polymerization reaction by ionizing radiation or heat.

Photo radical (polymerization) initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfides Examples include compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples are described in the latest UV curing technology (p.159, issuer; Kazuhiro Takashiro, publisher; Technical Information Association, Inc., published in 1991), which is useful for the present invention.
Preferable examples of commercially available photocleavable photoradical (polymerization) initiators include Irgacure (651, 184, 907) manufactured by Ciba Specialty Chemicals Co., Ltd.
The photo radical (polymerization) initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer.
In addition to the photoradical (polymerization) initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p -Nitrobenzenediazonium etc. can be mentioned.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

  The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator. Of these, the use of a photoacid generator that generates cations by ultraviolet rays is preferred from the viewpoint of productivity.

Examples of photoacid generators that generate cations by ultraviolet rays include ionic curable resins such as triarylsulfonium salts and diaryliodonium salts, and nonionic curable resins such as nitrobenzyl esters of sulfonic acids. Various known photoacid generators such as curable resins described in “Electronic Materials for Imaging” (1997) edited by Electronics Materials Research Group can be used. In the present invention, when the light diffusion layer is formed as a thick film, yellow coloring may occur when a triarylsulfonium salt is used, and it is preferable to use a diaryl iodonium salt in order to suppress coloring. Regarding this, the present inventors have described in detail in Japanese Patent Application Laid-Open No. 2003-268141. As the counter ion, PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , (C ₆ F ₅ ) ₄ B ^{− and the} like are preferable. It is also a preferred embodiment to use a combination of triarylsulfonium salt and diaryliodonium salt.

Examples of the iodonium salt-type photoacid generator are described in, for example, “imaging organic material” (Bunshin Publishing Co., Ltd., Organic Electronics Materials Research Group, 1997), Japanese Patent Application Laid-Open No. 11-322900, and the like. As what is used for this invention, Preferably it is represented by the following general formula (1 ').
General formula (1 ')
(Ar ¹ ) _m −I ⁺ − (Ar ² ) _n X ⁻
Here, Ar ¹ and Ar ² each represent an aromatic hydrocarbon group or an aromatic heterocyclic group, and Ar ¹ and Ar ² may combine to form a ring. Aromatic hydrocarbon groups include phenyl, 1-naphthyl, 2-naphthyl and the like. Examples of the aromatic heterocyclic group include 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-pyrrolyl, 3-pyrrolyl, 2-thiazolyl and the like. Ar ¹ and Ar ² are preferably aromatic hydrocarbon groups, and more preferably phenyl groups. These may further have a substituent, and the substituent is not particularly limited, but those having a basicity such as an amino group are not preferable in order to neutralize the generated acid. Specific examples of the substituent include alkyl groups (methyl, ethyl, isopropyl, t-butyl, t-amyl, 2-ethylhexyl, dodecyl, etc.), cycloalkyl (cyclohexyl, cyclopentyl, etc.), aryl groups (phenyl, 2-naphthyl, etc.) ), Alkenyl group (vinyl etc.), alkoxy group (methoxy, ethoxy, isopropoxy, octyloxy, cyclohexyloxy etc.), aryloxy group (phenoxy etc.), halogen (fluorine, chlorine, bromine, iodine etc.), alkoxycarbonyl group (Ethoxycarbonyl, butoxycarbonyl, etc.), aryloxycarbonyl groups (phenoxycarbonyl, etc.), acyloxy groups (acetoxy, benzoyloxy, etc.), carbamoyl groups, acylamino groups, cyano groups, hydroxyl groups, carboxyl groups, heterocyclic groups ( - thienyl, 3-thienyl, 2-furyl, 2-pyrrolyl, oxiranyl, oxetanyl, etc.) and the like can be mentioned, which may be further substituted.

m and n each represent 1 or 2, preferably 1. When a plurality of Ar ¹ or Ar ² are present, m and n may be the same or different. X ⁻ is a counter anion of the iodonium salt and is preferably a conjugate base of a strong acid. X ⁻ includes PF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ —C ₆ H ₄ —SO ₃ ⁻ , (C ₆ F ₅ ) ₄ B ^-, Cl ^-, Br ^-, and the like, of these preferably the _{^{PF 6 -, BF 4 -,}} CF 3 SO 3 - , and particularly preferably PF ₆ ^- is.
Specific examples of the iodonium salt-type photoacid generator include the compounds (1) to (28) described in paragraphs [0078] to [0081] of JP-A No. 2003-268141. The present invention is not limited to these.

(Metal compound)
A metal compound can be used for the antiglare layer. Surprisingly, the metal compound improves the pencil hardness of the antiglare film when used with light diffusing particles having an average particle size of 5 to 15 μm. This is because the anti-glare film having a film thickness of 8 to 40 μm contains light diffusing particles having an average particle diameter of 5 to 15 μm and the effect of improving the hardness and the deformation and destruction of the translucent resin due to the inclusion of the metal compound. It is presumed to be a synergistic effect of suppressing effect. Moreover, when providing a low refractive index layer on an anti-glare layer, the interface adhesion of an anti-glare layer and a low refractive index layer is improved, and scratch resistance is improved. In particular, when the low refractive index layer contains an organosilane compound or a silane coupling agent, the effect is great. 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 antiglare layer is 0.3 to 5% by mass. When the amount is less than 0.3% by mass, the pencil hardness is not improved. When the amount exceeds 5% by mass, the light resistance tends to deteriorate.

  As the metal compound used in the present invention, a compound represented by the following general formula (1) or a chelate compound thereof can be used.

General formula (1) _An MB _xn
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 above formula (1) includes an alkoxide having two or more alkoxyl groups bonded directly 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 between the ultraviolet curable resin and the metal alkoxide, the physical properties of the coating film can be improved even by adding a small amount.

  Surprisingly, the scratch resistance of the low refractive index layer laminated on the antiglare layer containing the metal compound could be remarkably improved.

  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.

(Organosilane compound)
An organosilane compound can be used for the antiglare layer. The addition amount of the organosilane compound is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass, and still more preferably 0.05 to 10% by mass, based on the total solid content of the containing layer (addition layer). 0.1 to 5% by mass is particularly preferable.
As the organosilane compound used for the antiglare layer, the same organosilane compound as described later for the low refractive index layer can be used.

In the present invention, it is preferable to use an organosilane compound having a polymerizable group of the same type as the cured resin forming the antiglare layer, and polymerization is performed to suppress curing shrinkage and curling of the antiglare layer of the present invention formed in a thick film. The molecular weight per sex group is preferably 150 or more.

(Inorganic filler)
In the antiglare layer, the refractive index of the layer is adjusted to adjust the haze value resulting from internal scattering, and the refractive index difference from the low refractive index layer is adjusted to make the reflectance and color tone within a preferable range. Therefore, an inorganic filler may be contained in addition to the light diffusing particles. The inorganic filler is preferably made of an oxide of at least one metal selected from silicon, titanium, zirconium, aluminum, indium, zinc, tin, and antimony. Moreover, it is preferable that an average particle diameter is 0.2 micrometer or less, More preferably, it is 0.1 micrometer or less, More preferably, it is 0.06 micrometer or less. Such an inorganic filler generally has a specific gravity higher than that of an organic substance and can increase the density of the coating composition, and thus has an effect of slowing the sedimentation rate of the light diffusing particles. Such an inorganic filler does not scatter because its particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

The surface of the inorganic filler used in the antiglare layer is also preferably subjected to silane coupling treatment or titanium coupling treatment. In this case, a surface treatment agent having a functional group capable of reacting with the binder species on the filler surface is preferably used.
The amount of the inorganic filler added is preferably 10 to 90% of the total mass of the antiglare layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.

(Surfactant for antiglare layer)
In order to ensure surface uniformity such as coating unevenness, drying unevenness, point defects, etc., the antiglare layer is preferably made of either a fluorine-based surfactant or a silicone-based surfactant, or both for forming the antiglare layer. It is preferably contained in the coating composition. By increasing the surface uniformity, it becomes possible to apply at high speed, and productivity can be improved. In particular, a fluorine-based surfactant is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the antireflection film appears with a smaller addition amount.

  Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following monomer (i): Resin consisting of a corresponding repeating unit, an acrylic resin containing a repeating unit corresponding to the monomer (i) below, a methacrylic resin, or a vinyl monomer copolymerizable therewith (for example, the monomer (i) below is preferred) Are useful.

In the general formula A, R ¹¹ represents a hydrogen atom or a methyl group, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom. m represents an integer of 1 to 6, and n represents an integer of 2 to 4.

In the general formula B, R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically Specifically, it represents a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. Y is an oxygen atom, -N (H) -, and -N (CH ₃₎ - are preferred.
R ¹⁴ represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. Examples of the substituent for the alkyl group of R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a nitro group, and a cyano group. , Amino groups and the like, but not limited thereto. Examples of the linear, branched or cyclic alkyl group having 4 to 20 carbon atoms include a butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group which may be linear or branched. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., and monocyclic cycloalkyl groups such as cyclohexyl group, cycloheptyl group and bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, A polycyclic cycloalkyl group such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, or the like is preferably used.

The amount of the fluoroaliphatic group-containing monomer represented by the general formula (A) used in the fluorine-based polymer is preferably 10 mol% or more based on each monomer of the fluorine-based polymer, more preferably 15 to It is 70 mol%, More preferably, it is the range of 20-60 mol%.
Further, the amount of the monomer represented by the general formula (b) used in the fluorine-based polymer is preferably 1 mol% or more based on each monomer of the fluorine-based polymer, more preferably 5 to 70 mol%. More preferably, it is the range of 10-60 mol%.

By using a fluorine-based polymer composed of the monomer represented by the general formula (a), the surface energy of the antiglare layer is reduced due to segregation of the functional group containing F atoms on the surface of the antiglare layer, and the antiglare layer Further, when the low refractive index layer is overcoated, the antireflection performance may be deteriorated. This is presumably because minute unevenness that cannot be visually detected in the low refractive index layer deteriorates because the wettability of the curable composition used for forming the low refractive index layer deteriorates.
In order to solve such problems, by adjusting the structure and amount of the fluorine-based polymer, the surface energy of the antiglare layer preferably in ^{20mN · m -1 ~50mN · m -1} , more preferably it was found that it is effective to control the ^{30mN · m -1 ~40mN · m -1} . In order to realize the surface energy as described above, F / C, which is a ratio of a peak derived from a fluorine atom and a peak derived from a carbon atom, measured by X-ray photoelectron spectroscopy is 0.1 to 1.5. is required.

  Alternatively, by selecting a fluorine-based polymer that is extracted by the solvent that forms the upper layer when the upper layer is applied, it is not unevenly distributed on the lower layer surface (= interface), so that the adhesion between the upper layer and the lower layer is provided. The surface energy of the antiglare layer before coating the low refractive index layer can be reduced by maintaining the surface uniformity even at high speed coating and preventing the decrease in surface free energy that can provide an antireflection film with high scratch resistance. The purpose can also be achieved by controlling the range. Examples of such materials include acrylic resins, methacrylic resins, and vinyl monomers copolymerizable therewith, including repeating units corresponding to fluoroaliphatic group-containing monomers represented by the following general formula c: And the following (iv) monomers are preferred).

In the general formula C, R ²¹ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. X ² represents an oxygen atom, a sulfur atom or —N (R ²² ) —, more preferably an oxygen atom or —N (R ²² ) —, and still more preferably an oxygen atom. m is an integer from 1 to 6 (more preferably from 1 to 3, more preferably 1), and n is an integer from 1 to 18 (more preferably from 4 to 12, and even more preferably from 6 to 8). Represents. R ²² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group. X ² is preferably an oxygen atom.
In addition, two or more kinds of fluoroaliphatic group-containing monomers represented by the general formula C may be contained in the fluorine-based polymer as constituent components.

In the general formula D, R ²³ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. Y ² represents an oxygen atom, a sulfur atom or —N (R ²⁵ ) —, more preferably an oxygen atom or —N (R ²⁵ ) —, and still more preferably an oxygen atom. R ²⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group.
R ²⁴ is an optionally substituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkyl group containing a poly (alkyleneoxy) group, and an optionally substituted aromatic group. (For example, a phenyl group or a naphthyl group). A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aromatic group having 6 to 18 carbon atoms is more preferable, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is more preferable. .

The amount of the fluoroaliphatic group-containing monomer represented by the general formula C used in the fluoropolymer is preferably 10 mol% or more based on each monomer of the fluoropolymer, more preferably 50 to It is 100 mol%, More preferably, it is the range of 60-100 mol%.
Further, the amount of the monomer represented by the general formula D used in the fluoropolymer is preferably 0 mol% or more, more preferably 0 to 50 mol% based on each monomer of the fluoropolymer. More preferably, it is the range of 0-40 mol%.

The preferred weight average molecular weight of the fluoropolymer is preferably 3000 to 100,000, more preferably 5,000 to 80,000.
Furthermore, the preferable addition amount of a fluorine-type polymer is the range of 0.001-5 mass% with respect to a coating liquid, Preferably it is the range of 0.005-3 mass%, More preferably, it is 0.01-1 It is the range of mass%. If the addition amount of the fluorine-based polymer is less than 0.001% by mass, the effect is insufficient, and if it exceeds 5% by mass, the coating film may not be sufficiently dried or the performance as a coating film (for example, reflectance) , May have an adverse effect on the scratch resistance).

  Further, if the surface energy is prevented from being lowered when the low refractive index layer is overcoated on the antiglare layer, the deterioration of the antireflection performance can be prevented. For this reason, when applying an anti-glare layer, the surface tension of the coating solution is lowered by using a fluoropolymer to improve surface uniformity, maintaining high productivity by high-speed application, and after applying the anti-glare layer, corona treatment, UV treatment, By using surface treatment techniques such as heat treatment, saponification treatment, and solvent treatment, the objective can also be achieved by controlling the surface energy of the antiglare layer before application of the low refractive index layer by preventing the surface free energy from decreasing. be able to. A particularly preferable surface treatment method is corona treatment.

(Thickener)
The film of the present invention may use a thickener to adjust the viscosity of the coating solution.
The term “thickener” as used herein means that the viscosity of the liquid is increased by adding it, and is preferably 0.05 to 50 cP as the magnitude of increase in the viscosity of the coating liquid by adding it. More preferably, it is 0.10-20 cP, Most preferably, it is 0.10-10 cP.
Use of such a polymer thickener is preferable because precipitation of light diffusing particles in the coating solution can be prevented and curing shrinkage and curling at the time of curing can be suppressed at the same time.
The content of the polymer thickener is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, and 8 to 15% by mass with respect to the total solid content in the antiglare layer. It is preferable. By setting it within this range, it is possible to achieve both a thickening effect, a curing shrinkage effect, and hardness.

Examples of such thickeners include, but are not limited to:
Poly-ε-caprolactone poly-ε-caprolactone diol poly-ε-caprolactone triol polyvinyl acetate poly (ethylene adipate)
Poly (1,4-butylene adipate)
Poly (1,4-butylene glutarate)
Poly (1,4-butylene succinate)
Poly (1,4-butylene terephthalate)
polyethylene terephthalate)
Poly (2-methyl-1,3-propylene adipate)
Poly (2-methyl-1,3-propylene glutarate)
Poly (neopentyl glycol adipate)
Poly (neopentyl glycol sebacate)
Poly (1,3-propylene adipate)
Poly (1,3-propylene glutarate)
Polyvinyl butyral polyvinyl formal polyvinyl acetal polyvinyl propanal polyvinyl hexanal polyvinyl pyrrolidone polyacrylic ester polymethacrylic acid ester cellulose acetate cellulose propionate cellulose acetate butyrate

  In addition, smectite, fluorine tetrasilicon mica, bentonite, silica, montmorillonite and sodium polyacrylate described in JP-A-8-325491, ethylcellulose, polyacrylic acid, organic clay described in JP-A-10-219136, Known viscosity modifiers and thixotropic agents can be used.

(solvent)
Since the antiglare layer is often wet-coated directly on the transparent support, the solvent used in the coating composition is an important factor. The solvent should sufficiently dissolve various solutes such as the translucent resin, do not dissolve the light diffusing particles, be difficult to cause coating unevenness and drying unevenness in the coating to drying process, and not dissolve the support. It is preferable to satisfy requirements such as (necessary for preventing failure such as deterioration of flatness and whitening) and conversely swelling the support to the minimum extent (necessary for adhesion).
As the solvent, it is preferable to contain as a main solvent at least a solvent that does not swell the transparent support and does not dissolve the transparent support. As specific examples of the main solvent, when triacetyl cellulose is used for the support, various ketones (methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, etc.), various cellosolves (ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc.), In addition, various alcohols (propylene glycol, ethylene glycol, ethanol, methanol, isopropyl alcohol, 1-butanol, 2-butanol, etc.), toluene and the like are preferably used.

  In addition, the transparent support is selected from the above, by adding a small amount of a highly swellable solvent to the main solvent having a low swellability of the transparent support without deteriorating other performance and surface condition. Adhesiveness can be improved. Specifically, methyl isobutyl ketone and toluene are used as a main solvent, and methyl ethyl ketone, acetone, cyclohexanone, propylene glycol, ethylene glycol, ethanol, methanol, isopropyl alcohol, 1-butanol, 2-butanol and the like are used as a small amount of solvent. It is particularly preferable to use methyl isobutyl ketone and toluene as the main solvent and methyl ethyl ketone and cyclohexanone as the small amount of solvent. Further, for controlling the hydrophilicity of the solvent, propylene glycol, ethylene glycol, ethanol, methanol, isopropyl alcohol, 1-butanol, 2-butanol and the like can be added and used, and propylene glycol and ethylene glycol are particularly preferably used. be able to. The mixing ratio of the main solvent and the small amount of solvent is preferably 99: 1 to 50:50, more preferably 95: 5 to 60:40 in terms of mass ratio. If it exceeds 50:50, the variation in the surface quality in the drying step after coating increases, which is not preferable.

  Moreover, surface irregularities can be adjusted by adding a small amount of a solvent having a hydroxyl group to the main solvent selected from the above, which is preferable. Since the small amount of the solvent having a hydroxyl group can increase the surface unevenness by remaining until after the main solvent in the drying step of the coating composition, the vapor pressure at a certain temperature within the range of 20 to 30 ° C. Preferably it is low relative to the main solvent. For example, a preferable example is a combination of propylene glycol (vapor pressure at 20.0 ° C .: 0.08 mmHg) as a small amount solvent having a hydroxyl group with respect to methyl isobutyl ketone (vapor pressure at 21.7 ° C .: 16.5 mmHg) as the main solvent. As mentioned. The mixing ratio of the main solvent and the small amount solvent having a hydroxyl group is preferably 100: 0 to 50:50, more preferably 100: 0 to 80:20 in terms of mass ratio. If it exceeds 50:50, the stability of the coating solution and the variation in surface quality in the drying step after coating increase, which is not preferable. In particular, in order to suppress surface scattering due to surface irregularities as in the present invention, it is more preferably 100: 0 to 97: 3.

Next, the low refractive index layer will be described below.
[Low refractive index layer]
The refractive index of the low refractive index layer in the antireflection film of the present invention is preferably 1.30 to 1.55, and preferably 1.30 to 1.45. When the refractive index is less than 1.30, the antireflection performance is improved, but the mechanical strength of the film is lowered, and when it exceeds 1.55, the antireflection performance is remarkably deteriorated.
Further, the low refractive index layer preferably satisfies the following formula (I) from the viewpoint of reducing the reflectance.
Formula (I)
(Mλ / 4) × 0.7 <n1 × d1 <(mλ / 4) × 1.3
In the formula, m is a positive odd number, n1 is the refractive index of the low refractive index layer, and d1 is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 500 to 550 nm.
In addition, satisfy | filling said numerical formula (I) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (I) exists in the said wavelength range.

[Low refractive index layer mainly composed of organosilane, hydrolyzate and / or condensation reaction product of organosilane]
The low refractive index layer is a cured film formed by applying, drying, and curing a curable composition containing, for example, organosilane, a hydrolyzate of the organosilane and / or a condensation reaction product as a main component. Here, “a curable composition mainly composed of an organosilane, a hydrolyzate of the organosilane and / or a condensation reaction product” means that the hydrosilane of the organosilane and the organosilane when the low refractive index layer is formed. This means that the decomposition product and / or condensation reaction product is contained in such an amount that it can function as a binder, and preferred ranges of organosilane, hydrolyzate of the organosilane and / or condensation reaction product are as described below. It is.
The low refractive index layer preferably contains inorganic fine particles in addition to the hydrolyzate and / or condensation reaction product of organosilane. The material for forming the low refractive index layer is described below.

(Organosilane compound for low refractive index layer)
The organosilane compound used in the present invention will be described in detail. This compound can be used as a binder for the low refractive index layer as it is or as a hydrolyzate or condensate. The general formula is shown below.
General _{^{formula: (R 10) m -Si (}} X) 4-m
In the above general formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, t-butyl, sec-butyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.

X represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group (an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group and an ethoxy group), a halogen atom (for example, Cl, Br, I, etc.), and R ^2. COO groups (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples include CH ₃ COO groups and C ₂ H ₅ COO groups), preferably alkoxy groups, particularly preferably. Is a methoxy group or an ethoxy group.
m represents an integer of 0 to 3. When R ¹⁰ or X there are a plurality, a plurality of R ¹⁰ or X groups may be different, even the same, respectively. m is preferably 0, 1 or 2.

The substituent contained in R ¹⁰ is not particularly limited, but is a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl group, ethyl group, i -Propyl group, propyl group, t-butyl group etc.), aryl group (phenyl group, naphthyl group etc.), aromatic heterocyclic group (furyl group, pyrazolyl group, pyridyl group etc.), alkoxy group (methoxy group, ethoxy group) , I-propoxy group, hexyloxy group, etc.), aryloxy group (phenoxy group, etc.), alkylthio group (methylthio group, ethylthio group, etc.), arylthio group (phenylthio group, etc.), alkenyl group (vinyl group, 1-propenyl group) Etc.), acyloxy groups (acetoxy group, acryloyloxy group, methacryloyloxy group, etc.), alkoxycarbonyl groups (me Toxylcarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-methyl-N-octylcarbamoyl group) Etc.), acylamino groups (acetylamino group, benzoylamino group, acrylamino group, methacrylamino group, etc.) and the like, and these substituents may be further substituted. In the present specification, even if a hydrogen atom is replaced by a single atom, it is treated as a substituent for convenience.
When there are a plurality of R ¹⁰ , at least one is preferably a substituted alkyl group or a substituted aryl group. Among these, the substituted alkyl group or substituted aryl group preferably further has a vinyl polymerizable group.

  Preferred compounds in the present invention are tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltri Methoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltri Methoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethyl Xysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Trialkoxysilanes such as glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane; dimethyl Examples thereof include dialkoxysilanes such as dimethoxysilane and dimethyldiethoxysilane. Among these, tetramethoxysilane, tetraethoxysilane, and γ-acryloxypropyltrimethoxysilane are preferable from the viewpoints of dispersion stability of the inorganic particles in the cured composition and scratch resistance.

  In the present invention, the organosilane compound can be used in the coating composition after hydrolysis or partial condensation thereof. It is preferable that at least one of hydrolysis and condensation reaction of organosilane is performed in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium. From the viewpoint of production stability and storage stability of the inorganic oxide fine particle liquid, an acid catalyst is used in the present invention. At least one of (inorganic acids, organic acids) and a metal chelate compound is used. Among inorganic acids, hydrochloric acid, sulfuric acid, nitric acid, and organic acids preferably have an acid dissociation constant (pKa value (25 ° C.)) of 4.5 or less in water. Among organic acids, methanesulfonic acid, oxalic acid, phthalic acid, and malonic acid are preferable, and oxalic acid is particularly preferable.

In the present invention, the metal chelate compound used for the formation of the hydrolyzate of organosilane and the condensation reaction is represented by the general formula R ³ OH (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms). alcohol of the general formula R ⁴ COCH ₂ COR ⁵ (wherein, the R ⁴ is an alkyl group having 1 to 10 carbon atoms, R ⁵ represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms having 1 to 10 carbon atoms. And at least one metal chelate compound having a metal selected from Zr, Ti and Al as a central metal.

  The metal chelate compound can be suitably used without particular limitation as long as it has a metal selected from Zr, Ti or Al as a central metal. Within this category, two or more metal chelate compounds may be used in combination. Specific examples of the metal chelate compound used in the present invention include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n Zirconium chelate compounds such as propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium , Titanium chelate compounds such as diisopropoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum Diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (Ethyl acetoacetate) Aluminum chelate compounds such as aluminum can be mentioned.

  Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

  The hydrolysis and condensation reaction of the organosilane can be performed without a solvent or in a solvent. By this reaction, the curable composition of the present invention can be produced. When a solvent is used, the concentration of the hydrolyzate of organosilane and its partial condensate can be appropriately determined. As the solvent, an organic solvent is preferably used in order to uniformly mix the components. For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are preferable. The solvent preferably dissolves the organosilane and the catalyst. In addition, it is preferable in the process that an organic solvent is used as a coating solution or a part of the coating solution, and those that do not impair the solubility or dispersibility when mixed with other materials such as a fluorine-containing polymer are preferable.

  Among these, examples of the alcohols include monohydric alcohols and dihydric alcohols. Among these, monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

  Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate. These organic solvents can be used alone or in combination of two or more. The concentration of the solid content relative to the solvent in the reaction is not particularly limited, but is usually in the range of 1% by mass to 90% by mass, and preferably in the range of 20% by mass to 70% by mass.

  In the hydrolysis and condensation reaction, usually 0.3 to 2 mol, preferably 0.5 to 1 mol of water is added to 1 mol of the hydrolyzable group of the organosilane, and in the presence or absence of the solvent. Under stirring and in the presence of an acid catalyst at 25-100 ° C. When the hydrolyzable group is an alkoxy group and the acid catalyst is an organic acid, since the carboxyl group or sulfo group of the organic acid supplies protons, the amount of water added can be reduced, such as the alkoxy group of organosilane. The amount of water added to 1 mol of the hydrolyzable group is 0 to 2 mol, preferably 0 to 1.5 mol, more preferably 0 to 1 mol, and particularly preferably 0 to 0.5 mol. When alcohol is used as the solvent, it is also preferred that substantially no water is added.

  The amount of the acid catalyst used is 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based on the hydrolyzable group when the acid catalyst is an inorganic acid, and the acid catalyst is an organic acid. However, when water is added, the optimal amount of use is 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based on the hydrolyzable group. When substantially no water is added, it is 1 to 500 mol%, preferably 10 to 200 mol%, more preferably 20 to 200 mol%, still more preferably 50 to 50 mol% with respect to the hydrolyzable group. 150 mol%, particularly preferably 50 to 120 mol%. The reaction is carried out by stirring at 25 to 100 ° C., but is preferably controlled by the reactivity of organosilane.

The organosilane hydrolyzate and condensation reaction product used in the present invention may have a chain or a three-dimensional network structure. Moreover, as for the mass average molecular weight of these compounds, it is preferable that the mass average molecular weight in conversion of ethylene glycol is 300-10000. When the mass average molecular weight is in the above range, the coating and storage stability of the curable composition are good, and the scratch resistance of the cured film can be sufficiently secured, which is preferable. The mass average molecular weight in terms of ethylene glycol is more preferably 300 to 9000, and particularly preferably 300 to 8000.
The mass average molecular weight is a molecular weight expressed in terms of ethylene glycol by DMF and differential refractometer detection using a GPC analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation). It is.

(Fluorine-containing organosilane compound for low refractive index layer)
The organosilane compound for the low refractive index layer may contain no fluorine, or may be a mixture of a non-fluorinated organosilane compound and a fluorine-containing organosilane compound. By using a fluorine-containing organosilane compound, the refractive index of the low refractive index layer can be lowered, and antifouling properties can be imparted to the surface of the antireflection film. Hereinafter, the fluorine-containing organosilane compound will be described in detail. Although there is no restriction | limiting in a fluorine-containing organosilane compound, The compound represented by the general formula [1]-[4] shown below is preferable. This will be sequentially described below.

Formula _{[1] (Rf-L 1} ) n -Si (R 11) 4-n
In the above formula, Rf represents a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated aromatic group having 6 to 14 carbon atoms. Rf may be further substituted with another substituent. Rf is preferably a linear, branched or cyclic fluoroalkyl group having 3 to 10 carbon atoms, and more preferably a linear fluoroalkyl group having 4 to 8 carbon atoms. L ₁ represents a divalent linking group having 10 or less carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms. The alkylene group is a linear or branched, substituted or unsubstituted alkylene group that may have a linking group (for example, ether, ester, amide) inside. The alkylene group may have a substituent, and preferable substituents in that case include a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group. R ¹¹ represents an alkyl group, a hydroxyl group or a hydrolyzable group, preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom. When there are a plurality of Rf, L ₁ and R ^11, each may be the same or different. n represents an integer of 1 to 3.

Among the fluorine-containing silane compounds represented by the general formula [1], a fluorine-containing silane compound represented by the following general formula [2] is preferable.
Formula _{[2] C n F 2n +} 1 - (CH 2) m -Si (R) 3
In the above formula, n represents an integer of 10 or more, and m represents an integer of 1 to 5. R represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom. n is preferably 4 to 10, m is preferably 1 to 3, and R is preferably a methoxy group, an ethoxy group, or a chlorine atom.

  Specific examples of the fluorine-containing silane coupling agent represented by the general formula [1] or [2] are shown below, but are not limited thereto.

_{C 3 F 7 CH 2 CH 2} Si (OC 2 H 5) 3 A-41
_{C 8 F 17 CH 2 CH 2} Si (CH 3) (OCH 3) 2 A-42
_{C 10 F 21 CH 2 CH 2} Si (OCH 3) 3 A-43
_{C 10 F 21 CH 2 CH 2} Si (OC 2 H 5) 3 A-44
_{C 12 F 24 CH 2 CH 2} Si (OCH 3) 3 A-45
C ₁₄ F ₂₉ CH ₂ CH ₂ Si (OCH ₃ ) ₃ A-46

  Among these specific examples, (A-1), (A-3), (A-43), (A-45), and (A-46) are preferable, and (A-43) is particularly preferable. These compounds can be synthesized, for example, by the method described in JP-A-11-189599.

In addition, in the present invention, a fluorine-containing silane compound containing a perfluoropolyether group is preferred from the viewpoint of improving surface lubricity in addition to antifouling properties. The compounds having preferred structures will be described below in order.
General formula [3]

Wherein R _f is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is an iodine atom or a hydrogen atom, Y is a hydrogen atom or a lower alkyl group, Z is a fluorine atom or a trifluoromethyl group , R ¹ is a hydrolyzable group, R ² is hydrogen or an inert monovalent organic group, a, b, c, d are integers of 0 to 200, e is 0 or 1, and m and n are 0 to 0. (The integer of 2 and p represent the integer of 1-10.)
R _f in the general formula [3] is usually a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, preferably a CF ₃ group, a C ₂ F ₅ group, or a C ₃ F ₇ group. is there. Examples of the lower alkyl group for Y usually include those having 1 to 5 carbon atoms. Examples of the hydrolyzable group of R ¹ include halogen atoms such as chlorine atom, bromine atom and iodine atom, R ³ O group, R ³ COO group, (R ⁴ ) ₂ C═C (R ³ ) CO group, ( R ³ ) ₂ C═NO group, R ⁵ C═NO group, (R ⁴ ) ₂ N group, and R ³ CONR ⁴ group are preferred. (Wherein R ³ is usually an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as an alkyl group or an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, and R ⁴ is a hydrogen atom or an alkyl group. A lower aliphatic hydrocarbon group having 1 to 5 carbon atoms such as a group, and R ⁵ is a divalent aliphatic hydrocarbon group usually having 3 to 6 carbon atoms such as an alkylidene group.) More preferably, chlorine An atom, a CH ₃ O group, and a C ₂ H ₅ O group. R ² is a hydrogen atom or an inert monovalent organic group, and is preferably a monovalent hydrocarbon group usually having 1 to 4 carbon atoms such as an alkyl group. a, b, c and d are integers of 0 to 200, preferably 1 to 50. m and n are integers of 0 to 2, preferably 0. p is an integer of 1 or 2 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5. The number average molecular weight is preferably 5 × 10 ² to 1 × 10 ^5, more preferably 1 × 10 ³ to 1 × 10 ⁴ .

Further, as a preferable structure of the fluorine-containing silane compound represented by the general formula [3], R _f is C ₃ F ₇ group, a is an integer of 1 to 50, b, c and d Is a compound in which e is 1, z is a fluorine atom, and n is 0, that is, a compound represented by the following general formula [4].
General formula [4]

(In the formula, Y, m, R ¹ and p represent the same meaning as described above, and q represents an integer of 1 to 50.)

  These fluorine-containing silane compounds can be obtained by treating a commercially available perfluoropolyether with silane. For example, as disclosed in JP-A-1-294709.

A compound having a perfluoropolyether group represented by the following general formula is also preferable because of its excellent antifouling property.
General formula [5]
_{Rf5 [- (L 5) n} -X-R 51 -Si (OR 52) 3] m
(Wherein the perfluoropolyether group RF5, the R ₅₁ is an alkylene group, a R ₅₂ represents an alkyl group, L ₅ is a -CO-, X is _{-O -, - NR 53 -,} - S-, _{-SO 2 -, - SO 2 NR} 53 -, - a group selected from NR ₅₃ CO-, n is 0 or 1, m is .R ₅₃ representing 2 following the natural numbers respectively a hydrogen atom or having 3 or less carbon Represents an alkyl group.)
Of the perfluoropolyether groups Rf5 in the general formula [5], examples of the monovalent group include the following general formulas [51], [52], and [53], but are limited to these structural formulas. It will never be done. Moreover, a bivalent thing may be sufficient. In this case, an alkoxysilane compound is bonded to both ends of the Rf5 group. The molecular weight of the perfluoropolyether group is not particularly limited, but from the viewpoint of stability and ease of handling, a number average molecular weight of 500 to 10,000, more preferably 500 to 2,000 is used. .
Formula [51] F (CF ₂ CF ₂ CF ₂ O) _j −
[52] CF ₃ (OCF (CF ₃ ) CF ₂ ) _m (OCF ₂ ) _l −
Formula [53] F (CF (CF ₃ ) CF ₂ O) _k −
Here, j, k, l and m in the above general formula [51], [52] or [53] represent a natural number of 1 or more.
Specific examples of preferred compounds are described in, for example, JP-A-10-148701.

Moreover, the compound of the following general formula is mentioned as an organosilazane compound with high reactivity in the case of hardening.
General formula [6]
_{[C n F 2n + 1 C} m H 2m Si (CH 3) 2] 2 -NH
In the formula, n is an integer of 4 or more, and m is 2 or 3. Examples of such a disilazane compound include the following.
[C ₄ F ₉ C ₂ H ₄ (CH ₃ ) ₂ Si] ₂ NH
[C ₄ F ₉ C ₃ H ₆ (CH ₃ ) ₂ Si] ₂ NH
[C ₈ F ₁₇ C ₂ H ₄ (CH ₃ ) ₂ Si] ₂ NH
[C ₈ F ₁₇ C ₃ H ₆ (CH ₃ ) ₂ Si] ₂ NH
[C ₈ F ₁₇ C ₃ H ₆ (CH ₃ ) (C ₂ H ₅ ) Si] ₂ NH
[C ₁₀ F ₂₁ C ₃ H ₆ (CH ₃ ) ₂ Si] ₂ NH
These compounds are used alone or in combination. These are disclosed in JP-A-10-26703.

  In the present invention, as the fluorine compound to be used, the alkoxysilane compound having a perfluoropolyether group represented by the above general formulas [3] to [5] is more resistant to abrasion than a compound having a simple perfluoroalkyl group. From the viewpoint of properties and water repellency. The reason for this is not necessarily clear, but it is conceivable that there is a considerable interaction between fluorine compound groups, or that the interaction between the alkoxysilane compound group, which is a polar group, and the underlying layer changes.

  Further, it is preferable to use the compounds described in JP 2000-191977 A, JP 2000-204319 A, JP 2000-328001 A, etc. as the high-molecular fluorine-containing silane compound since there are few coating failures.

It is preferable that the fluorine-containing silane compound is partially condensed with a non-fluorine-containing organosilane compound in advance for excellent stability of the coated surface. In addition, it is particularly preferable from the viewpoint of antifouling durability to use an organosilane compound represented by the following general formula [7] in the fluorine-containing organosilane compound-containing layer.
General formula [7]
R ₇₁ -Si (OR ₇₂ ) ₃
(In the formula, R ₇₁ represents a long-chain hydrocarbon group having 10 or more carbon atoms, R ₇₂ represents an alkyl group. The long-chain hydrocarbon group R ₇₁ preferably has 10 or more carbon atoms. The chain may be branched or branched, and may contain an unsaturated bond, a cyclic structure such as an aromatic ring, etc. However, a straight chain having 12 to 20 carbon atoms is preferably selected. By such molecular design, the alkoxysilano group portion of the general formula (7) can interact with SiO ₂ and the like of the antireflection layer, and the hydrophobicity of the long-chain hydrocarbon group R ₇₁ portion is increased. When these are used in combination with an alkoxysilane compound having a perfluoropolyether group represented by the general formulas [3] to [5], these effects are synergized, Solvent resistance, water repellency, abrasion resistance Sex is greatly improved.

  When the fluorine-containing silane compound is used for the antifouling layer, the ratio of the fluorine-free organosilane to 100 parts by mass of the fluorine-containing organosilane compound is preferably 1 part by mass or more and 150 parts by mass or less, more preferably 1 part by mass or more. 50 parts by mass. By setting it within this range, antifouling properties and scratch resistance are excellent.

(Inorganic fine particles for low refractive index layer)
The amount of the inorganic fine particles is preferably ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance may be deteriorated. It is preferable to be inside.
Since the inorganic fine particles are contained in the low refractive index layer, a low refractive index is desirable. Examples thereof include fine particles of magnesium fluoride and silica. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.
The average particle size of the inorganic fine particles is preferably 30% or more and 100% or less, more preferably 35% or more and 80% or less, and still more preferably 40% or more and 60% or less of the thickness of the low refractive index layer. That is, when the thickness of the low refractive index layer is 100 nm, the particle size of the silica fine particles is preferably 30 nm to 100 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
If the particle size of the inorganic fine particles is too small, the effect of improving the scratch resistance is reduced. Therefore, it is preferable to be within the above range. The inorganic fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.
Here, the average particle diameter of the inorganic fine particles can be measured by a Coulter counter.

In order to further reduce the increase in the refractive index of the low refractive index layer, the inorganic fine particles preferably have a hollow structure, and the refractive index of the inorganic fine particles is 1.17 to 1.40, more preferably 1. It is 17-1.35, More preferably, it is 1.17-1.30. Here, the refractive index represents the refractive index of the entire particle, and does not represent the refractive index of only the inorganic material of the outer shell in the case of inorganic fine particles having a hollow structure. At this time, when the radius of the void in the particle is a and the radius of the particle outer shell is b, the porosity x represented by the following formula (II) is preferably 10 to 60%, more preferably 20 to 60. %, Most preferably 30-60%.
(Formula II)
^{x = (4πa 3/3)} / (4πb 3/3) × 100

If the refractive index of the hollow inorganic fine particles is made lower and the porosity is increased, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. From the viewpoint of scratch resistance, the refractive index is 1 Particles with a low refractive index of less than .17 do not hold.
The refractive index of the inorganic fine particles can be measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

Further, at least one kind of inorganic fine particles (hereinafter referred to as “small-size inorganic fine particles”) having an average particle size of less than 25% of the thickness of the low refractive index layer is referred to as “inorganic fine particles (hereinafter referred to as“ small size inorganic fine particles ”). It may be used in combination with “large-size inorganic fine particles”.
Since the small-sized inorganic fine particles can exist in the gaps between the large-sized inorganic fine particles, they can contribute as a retaining agent for the large-sized inorganic fine particles.
When the low refractive index layer is 100 nm, the average particle size of the small-sized inorganic fine particles is preferably 1 nm to 20 nm, more preferably 5 nm to 15 nm, and particularly preferably 10 nm to 15 nm. Use of such inorganic fine particles is preferable in terms of raw material costs and a retaining agent effect.

Inorganic fine particles are treated with physical surface treatment such as plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to improve the affinity and binding properties with the binder component. Chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. Of these, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
The coupling agent is used as a surface treatment agent for the inorganic fine particles of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution. It is preferable to make it contain.
The inorganic fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

[Low refractive index layer mainly composed of fluoropolymer]
The low refractive index layer is a cured film formed, for example, by applying, drying and curing a curable composition containing a fluorine-containing polymer as a main component. Here, “a curable composition containing a fluorine-containing polymer as a main component” means that the fluorine-containing polymer is contained in an amount capable of functioning as a binder polymer when a low refractive index layer is formed. And the preferable range of content of a fluoropolymer is as below-mentioned.
In addition to the fluorine-containing polymer, the low refractive index layer preferably contains at least one of inorganic fine particles and an organosilane compound. The material for forming the low refractive index layer is described below.

(Fluoropolymer for low refractive index layer)
The fluorine-containing polymer has a coefficient of dynamic friction of 0.03 to 0.20, a contact angle with water of 90 to 120 °, and a sliding angle of pure water of 70 ° or less when formed into a cured coating, and heat or ionizing radiation. The polymer that is crosslinked by the above is preferable in terms of productivity improvement in the case of coating and curing the roll film while transporting the web.
Further, when the antireflection film is mounted on the image display device, the lower the peel strength from the commercially available adhesive tape, the easier it is to peel off after sticking a sticker or memo. More preferred is 100 gf or less. Further, the higher the surface hardness measured with a microhardness meter, the harder it is to scratch. Therefore, the surface hardness is preferably 0.3 GPa or more, and more preferably 0.5 GPa or more.

  The fluorine-containing polymer used for the low refractive index layer is preferably a fluorine-containing polymer containing a fluorine atom in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. Examples of such a fluorine-containing polymer include hydrolysates and dehydration condensates of perfluoroalkyl group-containing silane compounds [for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane]. And a fluorine-containing copolymer having a fluorine-containing monomer unit and a cross-linking reactive unit as constituent units. In the case of a fluorinated copolymer, the main chain preferably consists of only carbon atoms. That is, it is preferable that the main chain skeleton does not have an oxygen atom or a nitrogen atom.

  Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3- Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, etc. However, perfluoroolefins are preferable, and hexafluoropropylene is particularly preferable from the viewpoint of refractive index, solubility, transparency, availability, and the like.

  Examples of the crosslinking reactive unit include a structural unit obtained by polymerization of a monomer having a self-crosslinking functional group in the molecule such as glycidyl (meth) acrylate and glycidyl vinyl ether; carboxyl group, hydroxy group, amino group, sulfo group A structural unit obtained by polymerization of a monomer having, for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc. And a structural unit in which a crosslinkable reactive group such as a (meth) acryloyl group is introduced by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride to act on a hydroxy group).

  In addition to the fluorine-containing monomer unit and the cross-linking reactive unit, from the viewpoint of solubility in a solvent, film transparency, and the like, a monomer not containing a fluorine atom is appropriately copolymerized to introduce another polymerization unit. You can also There are no particular limitations on the monomer units that can be used in combination, such as olefins [ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.], acrylic esters [methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2 -Ethylhexyl], methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl) Vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.], vinyl esters [vinyl acetate, vinyl propionate, vinyl cinnamate, etc.], acrylamides [N-tertbutylacrylamide, N-silane] B hexyl acrylamide], methacrylamides, and acrylonitrile derivatives.

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the fluoropolymer.

Particularly useful fluorine-containing polymers are random copolymers of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing crosslinking reaction alone (radical reactive group such as (meth) acryloyl group, ring-opening polymerizable group such as epoxy group and oxetanyl group).
These cross-linking reactive group-containing polymer units preferably occupy 5 to 70 mol%, particularly preferably 30 to 60 mol% of the total polymer units of the polymer.

  A preferred form of the fluorine-containing polymer for the low refractive index layer is a copolymer represented by the general formula 1.

In General Formula 1, L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, It may have a branched structure, may have a ring structure, or may have a heteroatom selected from O, N and S.
Preferred examples include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O — **, * — (CH ₂ ). _{6 -O - **, * - (} CH 2) 2 -O- (CH 2) 2 -O - **, * -CONH- (CH 2) 3 -O - **, * -CH 2 CH (OH ) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (* represents a linking site on the polymer main chain side, and ** represents a linking on the (meth) acryloyl group side) Represents a part). m represents 0 or 1;

  In general formula 1, X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In the general formula 1, A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dust / antifouling properties, etc., can be selected as appropriate, depending on the purpose, depending on the single or multiple vinyl monomers It may be configured.

  Preferred examples include methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, vinyl ethers such as allyl vinyl ether, vinyl acetate, vinyl propionate, butyric acid. (Meth) such as vinyl esters such as vinyl, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane Acrylates, styrene, styrene derivatives such as p-hydroxymethylstyrene, crotonic acid, maleic acid, itaconic acid Can be mentioned unsaturated carboxylic acids and derivatives thereof, more preferably ether derivatives, vinyl ester derivatives, particularly preferably a vinyl ether derivative.

x, y, and z represent mol% of each constituent component, and 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65 are preferable, and 35 ≦ x ≦ 55, and 30 ≦ y ≦ 65 are more preferable. 60, 0 ≦ z ≦ 20, particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10. However, x + y + z = 100.
A particularly preferred form of the copolymer used in the present invention is General Formula 2.

In general formula 2, X represents the same meaning as in general formula 1, and the preferred range is also the same.
n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.
B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example of A in the said General formula 1 is applicable.
x, y, z1 and z2 each represent mol% of each repeating unit, and x and y preferably satisfy 30 ≦ x ≦ 60 and 5 ≦ y ≦ 70, respectively, more preferably 35 ≦ x ≦ 55. 30 ≦ y ≦ 60, particularly preferably 40 ≦ x ≦ 55 and 40 ≦ y ≦ 55. z1 and z2 preferably satisfy 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65, more preferably 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10, and 0 ≦ z1 ≦ 10, 0 It is particularly preferable that ≦ z2 ≦ 5. However, x + y + z1 + z2 = 100.

For the copolymer represented by the general formula 1 or 2, for example, a (meth) acryloyl group is introduced into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component by any one of the methods described above. Can be synthesized. As the reprecipitation solvent used at this time, isopropanol, hexane, methanol and the like are preferable.
Preferable specific examples of the copolymer represented by the general formula 1 or 2 include those described in paragraphs [0035] to [0047] of JP-A-2004-45462. It can be synthesized by the method.

(Inorganic fine particles for low refractive index layer)
As the inorganic fine particles for the low refractive index layer “mainly containing a fluorine-containing polymer”, the above-mentioned “organosilane, a hydrolyzate of the organosilane and / or a condensation reaction product” are used for the low refractive index layer. The same inorganic fine particles can be preferably used.

(Organosilane compound for low refractive index layer and its derivatives)
The curable composition contains at least one selected from the group consisting of an organosilane compound, a hydrolyzate of the organosilane, and a partial condensate of the hydrolyzate of the organosilane. In particular, it is preferable in terms of achieving both the antireflection ability and the scratch resistance.
Hereinafter, a reaction solution containing a hydrolyzate of organosilane or a partial condensate thereof is also referred to as a “sol component”.
This organosilane compound, or its sol component, functions as a binder for the low refractive index layer by applying the curable composition and then condensing in a drying and heating step to form a cured product. Moreover, when it has the said fluoropolymer, the binder which has a three-dimensional structure is formed by irradiation of actinic light.

The organosilane compound is preferably represented by the following general formula [A].
Formula [A]
(R ¹⁰ ) _m -Si (X) _4-m
In the general formula [A], R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
X represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I or the like). ), And R ² COO (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably An alkoxy group, particularly preferably a methoxy group or an ethoxy group.
m represents an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

When R ¹⁰ or X there are a plurality, a plurality of R ¹⁰ or X groups may be different, even the same, respectively.
The substituent contained in R ¹⁰ is not particularly limited, but a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy (phenoxy etc.) ), Alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxy) Carbonyl, etc.), aryloxy Carbonyl groups (such as phenoxycarbonyl), carbamoyl groups (such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl), acylamino groups (acetylamino, benzoylamino, acrylicamino, methacrylamino) Etc.), and these substituents may be further substituted.

When there are a plurality of R ^{10 s} , at least one is preferably a substituted alkyl group or a substituted aryl group.
Among the organosilane compounds represented by the general formula [A], an organosilane compound having a vinyl polymerizable substituent represented by the following general formula [B] is preferable.

In the general formula [B], R ¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom and a chlorine atom are preferred, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom and a chlorine atom are more preferred, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, * -COO-** is more preferable, and * -COO-** is particularly preferable. * Represents a position bonded to ═C (R ¹ ) —, and ** represents a position bonded to L.

  L represents a divalent linking chain. Specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group having a linking group (for example, ether, ester, amide, etc.) inside, and a linking group inside. A substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an alkylene group having a linking group therein is preferred, an unsubstituted alkylene group, an unsubstituted arylene group Further, an alkylene group having an ether or ester linking group inside is more preferable, an unsubstituted alkylene group, and an alkylene group having an ether or ester linking group inside is particularly preferable. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

n represents 0 or 1. n is preferably 0. When there are a plurality of Xs, the plurality of Xs may be the same or different.
R ¹⁰ has the same meaning as in formula [A], preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
X has the same meaning as in the general formula [A], preferably a halogen atom, a hydroxyl group or an unsubstituted alkoxy group, more preferably a chlorine atom, a hydroxyl group or an unsubstituted alkoxy group having 1 to 6 carbon atoms, a hydroxyl group or a carbon number of 1 -3 alkoxy groups are more preferred, and methoxy groups are particularly preferred.

  Two or more compounds of the general formula [A] and general formula [B] may be used in combination. Although the specific example of a compound represented by general formula [A] and general formula [B] is shown, it is not limited to the following.

  Of these, (M-1), (M-2), and (M-5) are particularly preferable.

  When used as a sol component, the hydrolyzate of the organosilane compound or the partial condensate of the hydrolyzate is generally produced by treating the organosilane compound in the presence of a catalyst. . Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples thereof include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; metal chelate compounds having a metal such as Zr, Ti or Al as a central metal. In the present invention, it is preferable to use a metal chelate compound, an acid catalyst of inorganic acids and organic acids. Inorganic acids are preferably hydrochloric acid and sulfuric acid, and organic acids are preferably those having an acid dissociation constant (pKa value (25 ° C.)) of 4.5 or less in water, and further, acid dissociation constants in hydrochloric acid, sulfuric acid and water. Is preferably an organic acid having an acid dissociation constant of 2.5 or less in hydrochloric acid, sulfuric acid or water, more preferably an organic acid having an acid dissociation constant of 2.5 or less in water. Specifically, methanesulfonic acid, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

As the metal chelate compound, (wherein, R ³ represents an alkyl group having 1 to 10 carbon atoms) Formula R ³ OH alcohol and R ⁴ COCH ₂ COR ⁵ (formula represented by, R ⁴ is the number of carbon atoms 1 to 10 alkyl groups, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or a compound represented by an alkoxy group having 1 to 10 carbon atoms), and is selected from Zr, Ti, and Al. Any metal having a central metal as the metal can be used without any particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has the general formula Zr (OR ³ ) _p1 (R ⁴ COCHCOR ⁵ ) _p2 , Ti (OR ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 , and Al (OR ³ ) _r1 (R ⁴ Those selected from the group of compounds represented by COCHCOR ⁵ ) _r2 are preferred, and serve to promote the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.
R ³ and R ⁴ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ⁵ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be p1 + p2 = 4, q1 + q2 = 4, and r1 + r2 = 3, respectively.

Specific examples of these metal chelate compounds include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.
Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

  Moreover, it is preferable that a β-diketone compound and / or a β-ketoester compound is further added to the composition for a low refractive index layer. This will be further described below.

The β-diketone compound and / or β-ketoester compound is preferably a β-diketone compound and / or β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ^5, which is a composition for a low refractive index layer. It acts as a stability improver. Here, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. That is, by coordinating to the metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the condensation reaction of the hydrolyzate of organosilane compound or its partial condensate by these metal chelate compounds is promoted. It is thought that the action which suppresses the effect | action to make and the effect | action which improves the storage stability of the obtained composition is made | formed. R ⁴ and R ⁵ constituting the β- diketone compound and / or β- ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and / or β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-sec-butyl, acetoacetic acid-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane -Dione, 5-methyl-hexane-dione and the like can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and / or β-ketoester compounds may be used alone or in combination of two or more. In the present invention, the β-diketone compound and / or β-ketoester compound is preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. If it is less than 2 mol, the storage stability of the resulting composition may be inferior, which is not preferable.

The compounding amount of the organosilane compound is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and most preferably 1 to 10% by mass based on the total solid content of the low refractive index layer.
The organosilane compound may be added directly to the curable composition (coating liquid for internal scattering layer, low refractive index layer, etc.), but the organosilane compound is treated in the presence of a catalyst in advance. It is preferable to prepare a hydrolyzate of the compound or a partial condensate thereof, and adjust the curable composition using the obtained reaction solution (sol solution). In the present invention, first, the hydrolysis of the organosilane compound is performed. Or a composition containing a partial condensate thereof and a metal chelate compound, and a liquid obtained by adding a β-diketone compound and / or a β-ketoester compound to at least one layer of an internal scattering layer or a low refractive index layer It is preferable to coat the coating liquid so that it is contained.

  5-100 mass% is preferable, the usage-amount of the sol component of the organosilane with respect to a fluorine-containing polymer in a low refractive index layer has more preferable 5-40 mass%, 8-35 mass% is still more preferable, 10-30 mass % Is particularly preferred. If the amount used is small, it is difficult to obtain the effect of the present invention, and if the amount used is too large, the refractive index increases or the shape / surface shape of the film deteriorates.

(Sol-gel material)
Various sol-gel materials can also be used as the material for the low refractive index layer. As such a sol-gel material, metal alcoholates (alcohols such as silane, titanium, aluminum, and zirconium), organoalkoxy metal compounds, and hydrolysates thereof can be used. In particular, alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, it is also preferable to use (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.). In particular, the use of a fluorine-containing silane compound is preferable in terms of lowering the refractive index of the layer and imparting water and oil repellency.

(Other substances contained in the composition for the low refractive index layer)
In addition to the aforementioned fluorine-containing polymer, inorganic fine particles, and organosilane compound, various additives, radical polymerization initiators, and cationic polymerization initiators can be added to the low refractive index layer composition as necessary. . At this time, the concentration of solids such as additives is appropriately selected according to the use, but is generally about 0.01 to 60% by mass, preferably 0.5 to 50% by mass, particularly preferably. It is about 1% to 20% by mass.

  Curing agents such as polyfunctional (meth) acrylate compounds, polyfunctional epoxy compounds, polyisocyanate compounds, aminoplasts, polybasic acids or anhydrides thereof from the viewpoint of interfacial adhesion with the lower layer directly in contact with the low refractive index layer Can also be added in small amounts. When adding these, it is preferable to set it as the range of 30 mass% or less with respect to the total solid of a low-refractive-index layer film, It is more preferable to set it as the range of 20 mass% or less, The range of 10 mass% or less It is particularly preferable that

  In addition, for the purpose of imparting properties such as antifouling properties, water resistance, chemical resistance, and slipping properties, a known silicone compound or fluorine compound antifouling agent, slipping agent, and the like may be appropriately added. When these additives are added, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass.

  Preferable examples of the silicone compound include those having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. It is done. Although there is no restriction | limiting in particular in molecular weight, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000. Although there is no restriction | limiting in particular in silicone atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.8 mass%, and 30.0-37.0. Most preferably, it is mass%. Examples of preferred silicone compounds are X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-170DX, X-22-176D, X, manufactured by Shin-Etsu Chemical Co., Ltd. -22-1821 (named above), manufactured by Chisso Corporation, FM-0725, FM-7725, FM-4421, FM-5521, FM6621, FM-1121, Gelest DMS-U22, RMS-033, RMS- 083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, FMS123, FMS131, FMS141, FMS221 (named above) but not limited thereto.

As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF _{2) 8} CF _3, even _{-CH 2 CH 2 (CF 2)} 4 H , etc.), a branched structure (e.g. _{-CH (CF 3) 2, -CH} 2 CF (CF 3) 2, -CH (CH ₃ ) CF ₂ CF ₃ , —CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.), and alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl groups) , A perfluorocyclopentyl group or an alkyl group substituted with these, and may have an ether bond (for example, —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ C). _{4 F 8 H, -CH 2 CH} 2 OCH 2 CH 2 C 8 F 17, -CH 2 CH 2 OCF 2 CF 2 O F ₂ CF ₂ H, etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.

  It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the low refractive index layer film. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferred fluorine-based compounds include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink Co., Ltd., Megafac F-171. , F-172, F-179A, defender MCF-300 (trade name), etc., but are not limited thereto.

  For the purpose of imparting properties such as dust resistance and antistatic properties, a known cationic surfactant or a dustproof agent such as a polyoxyalkylene compound, an antistatic agent, or the like can be appropriately added. These dustproofing agent and antistatic agent may contain the structural unit as a part of the function in the above-mentioned silicone compound or fluorine compound. When these are added as additives, it is preferably added in the range of 0.01 to 20% by mass, more preferably in the range of 0.05 to 10% by mass of the total solid content of the low n layer. Particularly preferably 0.1 to 5% by mass. Examples of preferred compounds include, but are not limited to, Dainippon Ink Co., Ltd., Megafac F-150 (trade name), Toray Dow Corning Co., Ltd., SH-3748 (trade name), and the like. Do not mean.

  In addition, an inorganic filler other than the above-described inorganic fine particles can be added to the composition for a low refractive index layer in an addition amount within a range that does not impair the desired effect of the present invention. As the inorganic filler, those described above can be used.

(Solvent for low refractive index layer)
As a solvent used in the coating composition for forming the low refractive index layer, it is possible to dissolve or disperse each component, to easily form a uniform surface in the coating process and the drying process, and to ensure liquid storage stability. Various solvents selected from the viewpoint of having an appropriate saturated vapor pressure can be used. From the viewpoint of the drying load, it is preferable that a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature as a main component and a small amount of a solvent having a boiling point of 100 ° C. or higher for adjusting the drying speed.

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

  Examples of the solvent having a boiling point of 100 ° C or higher include, for example, octane (125.7 ° C), toluene (110.6 ° C), xylene (138 ° C), tetrachloroethylene (121.2 ° C), chlorobenzene (131.7 ° C), Dioxane (101.3 ° C.), dibutyl ether (142.4 ° C.), isobutyl acetate (118 ° C.), cyclohexanone (155.7 ° C.), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C.), Examples thereof include 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

[Transparent conductive layer]
The antireflection film of the present invention is preferably provided with a transparent conductive layer for the purpose of antistatic from the viewpoint of preventing static electricity on the film surface. The transparent conductive layer is effective when there is a demand for lowering the surface resistance value from the display side or when dust on the surface or the like becomes a problem. As a method of forming the transparent conductive layer, for example, a method of applying a conductive coating liquid containing conductive particles and a reactive curable resin, or a metal or metal oxide that forms a transparent film is deposited or sputtered. And a known method such as a method of forming a conductive thin film. In the case of coating, the method is not particularly limited, and an optimum method is selected from known methods such as roll coating, gravure coating, bar coating, extrusion coating, etc., depending on the characteristics of the coating liquid and the coating amount. You can do it.
The transparent conductive layer can be formed on the transparent support or the internal scattering layer directly or via a primer layer that strengthens adhesion with them.

  The thickness of the transparent conductive layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and further preferably from 0.05 to 5 μm. When used in a layer close to the outermost layer, sufficient antistatic properties can be obtained even if the film is thin. The surface resistance of the transparent conductive layer is preferably 105 to 1012 Ω / sq, more preferably 105 to 109 Ω / sq, and most preferably 105 to 108 Ω / sq. The surface resistance of the transparent conductive layer can be measured by a four probe method.

It is preferable that the transparent conductive layer is substantially transparent. Specifically, the haze of the transparent conductive layer is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and most preferably 1% or less. preferable. The transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more.
The transparent conductive layer preferably has excellent strength, and the specific antistatic layer has a pencil hardness of 1 kg (as defined in JIS-K-5400), preferably H or higher. More preferably, it is more preferably 3H or more, and most preferably 4H or more.

(Electrically conductive particles)
The average particle diameter of the primary particles of the conductive particles used for the transparent conductive layer is preferably 1 to 150 nm, more preferably 5 to 100 nm, and most preferably 5 to 70 nm. The average particle diameter of the conductive particles in the formed transparent conductive layer is 1 to 200 nm, preferably 5 to 150 nm, more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the conductive particles is an average diameter weighted by the mass of the particles, and can be measured by a light scattering method or an electron micrograph.
The specific surface area of the energizing particles is preferably 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

The conductive particles are preferably inorganic fine particles made of a metal oxide or nitride. Examples of metal oxides or nitrides include tin oxide, indium oxide, zinc oxide and titanium nitride. Tin oxide and indium oxide are particularly preferred.
The conductive particles are mainly composed of oxides or nitrides of these metals, and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and a halogen atom are mentioned. In order to increase the conductivity of tin oxide and indium oxide, it is preferable to add Sb, P, B, Nb, In, V and a halogen atom. Particularly preferred are tin oxide containing Sb (ATO) and indium oxide containing Sn (ITO). The ratio of Sb in ATO is preferably 3 to 20% by mass. The ratio of Sn in ITO is preferably 5 to 20% by mass.

The conductive particles may be surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina and silica. Silica treatment is particularly preferred. Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. Two or more kinds of surface treatments may be performed in combination.
The shape of the conductive particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape.

The ratio of the conductive inorganic fine particles in the transparent conductive layer is preferably 20 to 90% by mass, preferably 25 to 85% by mass, and more preferably 30 to 80% by mass.
Two or more kinds of conductive particles may be used in combination in the transparent conductive layer.

  The conductive particles can be used in the transparent conductive layer in a dispersion state. As the dispersion medium for the conductive particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Examples of dispersion media include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (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 Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1 Methoxy-2-propanol). Among these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable. The conductive particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (for example, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill, and a sand grinder mill and a high-speed impeller mill are particularly preferable. 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.

(Binder for transparent conductive layer)
The transparent conductive layer can use a crosslinked polymer as a binder. The crosslinked polymer preferably has an anionic group. The polymer having a crosslinked anionic group has a structure in which the main chain of the polymer having an anionic group is crosslinked. The anionic group has a function of maintaining the dispersed state of the conductive particles. The crosslinked structure has a function of reinforcing the transparent conductive layer by imparting a film-forming ability to the polymer.

  Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.

The polyolefin main chain is composed of a saturated hydrocarbon. The polyolefin main chain is obtained, for example, by an addition polymerization reaction of an unsaturated polymerizable group.
The polyether main chain has repeating units bonded by an ether bond (—O—). The polyether main chain is obtained, for example, by a ring-opening polymerization reaction of an epoxy group.
In the polyurea main chain, repeating units are bonded by a urea bond (—NH—CO—NH—). The polyurea main chain is obtained, for example, by a condensation polymerization reaction between an isocyanate group and an amino group. The polyurethane main chain has repeating units bonded by urethane bonds (—NH—CO—O—).
The polyurethane main chain is obtained, for example, by a polycondensation reaction between an isocyanate group and a hydroxyl group (including an N-methylol group).

The polyester main chain has repeating units bonded by an ester bond (—CO—O—). The polyester main chain is obtained, for example, by a polycondensation reaction between a carboxyl group (including an acid halide group) and a hydroxyl group (including an N-methylol group).
In the polyamine main chain, repeating units are bonded by an imino bond (—NH—). The polyamine main chain is obtained, for example, by a ring-opening polymerization reaction of an ethyleneimine group.
The polyamide main chain has repeating units bonded by an amide bond (—NH—CO—). The polyamide main chain is obtained, for example, by a reaction between an isocyanate group and a carboxyl group (including an acid halide group).
The melamine resin main chain is obtained, for example, by a polycondensation reaction between a triazine group (eg, melamine) and an aldehyde (eg, formaldehyde). In the melamine resin, the main chain itself has a crosslinked structure.

The anionic group is bonded directly to the main chain of the polymer or bonded to the main chain via a linking group. The anionic group is preferably bonded to the main chain as a side chain via a linking group.
Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono), and a sulfonic acid group and a phosphoric acid group are preferable.
The anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated.
The linking group that binds the anionic group and the polymer main chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof.

  The crosslinked structure chemically bonds (preferably covalently bonds) two or more main chains. The cross-linked structure is preferably covalently bonded to three or more main chains. The cross-linked structure is preferably composed of a divalent or higher valent group selected from —CO—, —O—, —S—, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and combinations thereof.

  The crosslinked polymer having an anionic group is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. The proportion of the repeating unit having an anionic group in the copolymer is preferably 2 to 96% by mass, more preferably 4 to 94% by mass, and most preferably 6 to 92% by mass. The repeating unit may have two or more anionic groups. The proportion of the repeating unit having a crosslinked structure in the copolymer is preferably 4 to 98% by mass, more preferably 6 to 96% by mass, and most preferably 8 to 94% by mass.

The repeating unit of the polymer having a crosslinked anionic group may have both an anionic group and a crosslinked structure. Further, other repeating units (repeating units having neither an anionic group nor a crosslinked structure) may be contained.
Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or quaternary ammonium group has a function of maintaining the dispersed state of the inorganic fine particles, like the anionic group. In addition, even if the amino group, the quaternary ammonium group and the benzene ring are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure, the same effect can be obtained.

In a repeating unit having an amino group or a quaternary ammonium group, the amino group or quaternary ammonium group is directly bonded to the main chain of the polymer or bonded to the main chain through a linking group. The amino group or quaternary ammonium group is preferably bonded to the main chain as a side chain via a linking group.
The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, Is more preferably an alkyl group of 1 to 6.

  The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer main chain is a divalent group selected from -CO-, -NH-, -O-, an alkylene group, an arylene group, and combinations thereof. Preferably there is. When the crosslinked polymer having an anionic group contains a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, and 0.08 to 30% by mass. % Is more preferable, and 0.1 to 28% by mass is most preferable.

  For example, the following reactive organosilicon compound described in JP-A-2003-39586 can be used in combination with the binder. The reactive organosilicon compound is used in the range of 10 to 100% by mass with respect to the total of the ionizing radiation curable resin and the reactive organosilicon compound. In particular, when the ionizing radiation curable organosilicon compound (3) below is used, it is possible to form a conductive layer using only this as a resin component.

(1) Silicon alkoxide is a compound represented by R _m Si (OR ′) _n , wherein R and R ′ represent an alkyl group having 1 to 10 carbon atoms, and m and n are integers such that m + n = 4, respectively. It is. For example, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrapentaethoxysilane, Tetrapenta-iso-propoxysilane, tetrapenta-n-proxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Methyl tributoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, dimethyl ethoxy silane, dimethyl methoxy silane, dimethyl propoxy silane, dimethyl butyl Kishishiran, methyldimethoxysilane, methyldiethoxysilane, hexyl trimethoxysilane.

(2) Silane coupling agent For example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxy Silane, aminosilane, methyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3 (Trimethoxysilyl) propyl] ammonium chloride, methyl trichlorosilane, dimethyl dichlorosilane, and the like.

(3) Ionizing radiation curable silicon compound A plurality of groups that undergo reactive crosslinking by ionizing radiation, for example, organosilicon compounds having a molecular weight of 5,000 or less having a polymerizable double bond group. Such reactive organosilicon compounds may be one end vinyl functional polysilane, both end vinyl functional polysilane, one end vinyl functional polysiloxane, both end vinyl functional polysiloxane, or a vinyl functionality obtained by reacting these compounds. Examples include polysilane, vinyl functional polysiloxane, and the like.

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

  In order to further develop the antistatic function, as disclosed in Japanese Patent Application Laid-Open No. 2003-39586, the conductive particles are dispersed in the internal scattering layer of the present invention to have a function as an anisotropic conductive film. It is also preferable.

[About other layers]
[Other layers]
Examples of other layers that may be provided between the transparent support and the antiglare layer of the present invention include a moisture proof layer, an adhesion improving layer, and a rainbow unevenness (interference unevenness) preventing layer. These layers can be formed by a known method.

[Production Method of Antiglare Film and Antireflection Film]
The antireflection film of the present invention can be formed by the following method, but is not limited to this method. The formation of the antiglare film is the same as the method for producing the antireflection film.
(Preparation of coating solution)
First, a coating solution containing components for forming each layer is prepared. In that case, the raise of the moisture content in a coating liquid can be suppressed by suppressing the volatilization amount of a solvent to the minimum. The moisture content in the coating solution is preferably 5% or less, more preferably 2% or less. The suppression of the volatilization amount of the solvent is achieved by improving the hermeticity at the time of stirring after putting each material into the tank, minimizing the air contact area of the coating liquid during the transfer operation, and the like. Moreover, you may provide the means to reduce the moisture content in a coating liquid during application | coating or before and after that.

  In the coating solution for forming the antiglare layer, almost all foreign matters having a size corresponding to the dry film thickness (about 50 nm to 120 nm) of the low refractive index layer directly formed thereon (pointing to 90% or more) It is preferable to perform filtration that can be removed. Since the light diffusing particles for imparting the amount are equal to or greater than the film thickness of the low refractive index layer, the filtration is preferably performed on the intermediate liquid to which all materials other than the light diffusing particles are added. In addition, when a filter capable of removing foreign substances having a small particle size as described above is not available, almost all foreign substances corresponding to the wet film thickness (about 8 to 40 μm) of the layer directly formed thereon are removed. It is preferable to perform filtration. By such means, the point defects of the layer formed directly thereon can be reduced.

(Application)
Next, a coating solution for forming an antiglare layer and, if necessary, a low refractive index layer is applied onto the cellulose ester film by an application method such as an extrusion method (die coating method) or a micro gravure method, Heat and dry. Thereafter, the monomer and curable resin for forming the antiglare layer or the low refractive index layer are cured by light irradiation and / or heating. Thereby, an anti-glare layer and a low refractive index layer are formed.

(Dry)
The antiglare layer and the low refractive index layer are coated on the cellulose ester film directly or via another layer, and then conveyed by a web to a heated zone to dry the solvent. In this case, the temperature of the drying zone is preferably 25 ° C. to 140 ° C., the first half of the drying zone is relatively low temperature, and the second half is preferably relatively high temperature. However, it is preferably below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize. For example, some of the commercially available photo radical generators used in combination with ultraviolet curable resins volatilize around several tens of percent within a few minutes in warm air at 120 ° C. Some acrylate monomers and the like undergo volatilization in warm air at 100 ° C. In such a case, it is preferable that it is below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize as described above.

Moreover, the dry wind after apply | coating the coating composition of each layer on this cellulose-ester film has a wind speed of the coating-film surface of 0.1-2 m / w while the solid content concentration of the said coating composition is 1-50%. It is preferable to be in the second range in order to prevent drying unevenness.
Moreover, after apply | coating the coating composition of each layer on this cellulose-ester film, the temperature difference of the conveyance roll and base material film which contact the surface opposite to the application surface of a base film in a drying zone is 0 degreeC- When the temperature is within the range of 20 ° C., drying unevenness due to heat transfer unevenness on the transport roll can be prevented, which is preferable.

  It is also possible to control the surface irregularities to some extent by the drying conditions. In this invention, it discovered that the formation of surface unevenness | corrugation can be suppressed by applying a dry wind early after application | coating, and made it possible to control to a preferable surface unevenness | corrugation range.

(Curing)
After the solvent drying zone, the coating is cured by passing through a zone where the coating is cured by ionizing radiation and / or heat on the web. When the coating film is ionizing radiation curable, the light source for forming the cured coating layer can be used without limitation as long as it is a light source that generates ionizing radiation. 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. The irradiation conditions vary depending on individual lamps, the dose of ionizing radiation, preferably ^{5mJ / cm 2 ~100mJ / cm 2} , more preferably from ^{20mJ / cm 2 ~80mJ / cm 2} . At that time, the irradiation distribution in the width direction of the web is preferably 50 to 100%, more preferably 80 to 100%, including both ends with respect to the central maximum irradiation. Further, when it is necessary to purge nitrogen gas or the like to lower the oxygen concentration in order to promote surface hardening, the oxygen concentration is preferably 0.01% to 5%, and the distribution in the width direction is 2% or less in terms of oxygen concentration Is preferred.

  Conventional antiglare films have not been able to obtain an antiglare film having a pencil hardness of 4H or more and excellent flatness at such a low irradiation dose. In the case of an anti-glare film that does not require much hardness, the amount of irradiation can be further reduced, so that an anti-glare film can be produced at a speed much higher than the coating speed limited by the ability of the ultraviolet irradiation section, and the productivity Is significantly improved.

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

  Further, when the curing rate (100-residual functional group content) of the antiglare layer becomes a certain value less than 100%, a low refractive index layer is provided on the low refractive index layer by ionizing radiation and / or heat. If the curing rate of the lower antiglare layer is higher than that before providing the low refractive index layer when the is cured, the adhesion between the antiglare layer and the low refractive index layer is improved, which is preferable.

The antireflection film produced as described above can be used for a liquid crystal display device by forming a polarizing plate using the antireflection film. In this case, it arrange | positions on the outermost surface of a display by providing an adhesive layer on one side. The antireflection film of the present invention is preferably used for at least one of the two protective films sandwiching the polarizing film in the polarizing plate from both sides.
Since the antireflection film of the present invention also serves as a protective film, the production cost of the polarizing plate can be reduced. Further, by using the antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance, antifouling property and the like can be obtained.

  When producing a polarizing plate using an antireflection film as one of the surface protective films of two polarizing films, the antireflection film is used as a transparent support on the side opposite to the side having the antireflection structure. It is preferable to improve the adhesion on the adhesive surface by hydrophilizing the surface of the film, that is, the surface to be bonded to the polarizing film. The hydrophilized surface is effective for improving the adhesiveness with the adhesive layer mainly composed of polyvinyl alcohol. As the hydrophilic treatment of the antireflection film, the following saponification treatment is preferably performed.

(Saponification treatment)
(1) Method of immersing in alkaline solution This is a method in which an antireflection film is immersed in an alkaline solution under appropriate conditions, and all surfaces having reactivity with alkali on the entire surface of the film are saponified, and special equipment Is preferable from the viewpoint of cost. The alkaline liquid is preferably a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 mol / L, particularly preferably 1 to 2 mol / L. The liquid temperature of a preferable alkali liquid is 30-75 degreeC, Most preferably, it is 40-60 degreeC.
The combination of the saponification conditions is preferably a combination of relatively mild conditions, but can be set according to the material and configuration of the antiglare antireflection film and the target contact angle.
After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by immersing in a dilute acid so that the alkaline component does not remain in the film.

  In the saponification treatment, the lower the contact angle with water on the surface of the transparent support opposite to the side having the internal scattering layer or the low refractive index layer, the better from the viewpoint of adhesiveness to the polarizing film. In such a dipping method, alkali damage is caused from the surface having the internal scattering layer and the low refractive index layer to the inside at the same time, so that it is important to set the necessary minimum reaction conditions. When the contact angle to water of the transparent support on the opposite surface is used as an index of damage to each layer due to alkali, particularly when the transparent support is triacetylcellulose, preferably 10 to 50 degrees, more preferably Is 30 to 50 degrees, more preferably 40 to 50 degrees. If it is 50 degrees or more, there is a problem in the adhesion to the polarizing film, which is not preferable. On the other hand, if it is less than 10 degrees, the damage received by the antireflection film is too large, and the physical strength is impaired, which is not preferable.

(2) Method of applying alkaline solution As a means for avoiding damage to each film in the above-mentioned immersion method, the alkaline solution is applied only to the surface opposite to the surface having the internal scattering layer or antireflection film under appropriate conditions. An alkaline solution coating method of heating, washing with water and drying is preferably used. The application in this case means that an alkaline solution or the like is brought into contact only with the surface to be saponified, and in addition to the application, it may be carried out by spraying or contacting a belt containing the solution. Including. By adopting these methods, a separate facility and process for applying an alkaline solution are required, which is inferior to the immersion method (1) from the viewpoint of cost. On the other hand, since the alkali solution contacts only the surface to be saponified, the opposite surface can have a layer using a material that is weak against the alkali solution. For example, vapor deposition films and sol-gel films have various effects such as corrosion, dissolution, and peeling due to alkali solution, so it is not desirable to use the immersion method. Is possible.

  In any of the saponification methods (1) and (2), since each layer can be formed by unwinding from a roll-shaped support, a series of operations can be performed in addition to the above-described antireflection film manufacturing process. You can go. Furthermore, the polarizing plate can be produced more efficiently than the same operation with a single wafer by continuously performing the pasting step with the polarizing plate made of the unwound support.

(3) Method of protecting and saponifying an antiglare layer and an antireflection layer with a laminate film When the antiglare layer and / or the low refractive index layer is insufficient in resistance to an alkaline solution as in the above (2) After the final layer is formed, the laminate film is bonded to the surface on which the final layer is formed and then immersed in an alkaline solution to hydrophilize only the side of the triacetyl cellulose opposite to the surface on which the final layer is formed. The laminate film can be peeled off. Even in this method, only the surface opposite to the surface on which the final layer of the triacetyl cellulose film is formed is subjected to the hydrophilization treatment necessary for the polarizing plate protective film without damage to the antiglare layer and the low refractive index layer. Can do. Compared with the method (2), the laminate film is generated as waste, but there is an advantage that a device for applying a special alkaline solution is unnecessary.

(4) Method of immersing in alkaline solution after forming up to antiglare layer Up to antiglare layer is resistant to alkaline solution, but when low refractive index layer is insufficiently resistant to alkaline solution, after forming up to antiglare layer It is also possible to soak both surfaces in an alkali solution to hydrophilize both surfaces, and then form a low refractive index layer on the antiglare layer. Although the manufacturing process becomes complicated, there is an advantage that the interlayer adhesion between the antiglare layer and the low refractive index layer is improved particularly when the low refractive index layer has a hydrophilic group such as a fluorine-containing sol-gel film.

(5) Method of forming an antiglare layer or an antireflection layer on a previously saponified triacetyl cellulose film Saponified by, for example, pre-immersing the triacetyl cellulose film in an alkali solution, either directly or on the other side An internal scattering layer and a low refractive index layer may be formed through the layers. In the case of saponification by dipping in an alkaline solution, interlayer adhesion between the antiglare layer or other layers and the triacetyl cellulose surface hydrophilized by saponification may deteriorate. In such a case, after the saponification, only the surface on which the antiglare layer or other layer is formed is treated with corona discharge, glow discharge or the like to remove the hydrophilic surface, and then the internal scattering layer or other layer. Can be dealt with by forming Further, when the antiglare layer or other layer has a hydrophilic group, the interlayer adhesion may be good.

  Below, the polarizing plate using the antireflection film of this invention and the liquid crystal display device using this polarizing plate are demonstrated.

[Polarizer]
A preferred polarizing plate of the present invention has the antireflection film of the present invention as at least one of a polarizing film protective film (polarizing plate protective film). As described above, the polarizing plate protective film has a water contact angle of 10 on the surface of the transparent support opposite to the side having the internal scattering layer and the low refractive index layer, that is, the surface to be bonded to the polarizing film. It is preferable to be in the range of degrees to 50 degrees.
By using the antireflection film of the present invention as a protective film for a polarizing plate, it is possible to produce a polarizing plate having a light scattering function or an antireflection function excellent in physical strength and light resistance. Can be realized.
Further, by preparing a polarizing plate using the antireflection film of the present invention as one of the protective films for polarizing plates and an optical compensation film having optical anisotropy described later as the other protective film of the polarizing film, In addition, it is possible to improve the visibility and contrast in a bright room of a liquid crystal display device and to produce a polarizing plate that can greatly widen the vertical and horizontal viewing angles.

(Optical compensation film)
By using the optical compensation film for the polarizing plate, the viewing angle characteristics of the liquid crystal display screen can be improved, and the optical compensation film can be preferably used on the opposite side of the antireflection film of the present invention across the polarizer. The compensation form may be affixed on the protective film on one side of the polarizing plate with an adhesive, or may be used as a protective film on one side. From the viewpoint of the thickness of the polarizing plate, it is particularly desirable to use the antireflection film of the present invention as the protective film on one side and the optical compensation film as the protective film on the opposite side across the polarizer. The optical compensation film may contain a material having optical anisotropy in the film itself, stretch the film, or both, so that the film itself has a specific optical anisotropy. Alternatively, an optically anisotropic layer (retardation layer) may be provided on the film.
As the optical compensation film, a known film can be used, but in terms of widening the viewing angle, a film having a layer having optical anisotropy made of a compound having a discotic structural unit is desirable. There are wide view films (WV-A, WV-SA) manufactured by Fuji Photo Film, but not limited thereto.
Further, in order to improve the contrast and color of the liquid crystal display, the optical anisotropy (Re, Rth) is small and substantially optically isotropic, and further the optical anisotropy (Re , Rth) having a small wavelength dispersion is preferably used, and in the case of a reflective display, it is also preferable to use a film having a function of a λ / 4 plate composed of one or a plurality of films.
When the optical compensation film is used as a protective film for the polarizing film, the surface on the side to be bonded to the polarizing film is preferably saponified, and is preferably performed according to the saponifying process.

(Polarizing film)
As the polarizing film, a known polarizing film or a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.
That is, at the time of stretching by applying tension while holding both ends of a continuously supplied polymer film by a holding means, the film is stretched at least 1.1 to 20.0 times in the film width direction, and the film is held at both ends. The direction of travel of the film is such that the angle between the direction of travel of the film at the exit of the step of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. The film can be manufactured by a stretching method in which both ends of the film are bent. In particular, a film whose absorption axis is inclined by 45 ° with respect to the longitudinal direction is preferably used from the viewpoint of productivity of the polarizing plate.
The method for stretching the polymer film is described in detail in paragraphs [0020] to [0030] of JP-A-2002-86554.

[Image display device]
The antireflection film of the present invention includes a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode tube display (CRT), a field emission display (FED), and a surface electric field display (SED). The present invention can be applied to such an image display device. Since the antireflection film of the present invention has a transparent support, the transparent support side is adhered to the image display surface of the image display device.

  It is particularly preferable to prepare a polarizing plate using the antireflection film of the present invention as one side of the surface protective film of the polarizing film and use it on the surface of the liquid crystal display device. In this case, transmissive and reflective types of modes such as twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell (OCB), etc. Alternatively, it can be preferably used for a transflective liquid crystal display device. In particular, it can be preferably used for VA, IPS, OCB, etc. as a use for large liquid crystal televisions, etc., and it can also be preferably used for TN, STN, etc. if it is used for small and medium display devices. For applications such as liquid crystal televisions, the diagonal of the display screen is 13 inches or more, particularly preferably 20 inches or more. Since the antireflection film of the present invention has a surface haze value, roughness and the like in a preferable range, there is substantially no problem of glare and it can be used without limitation with regard to definition, but it is XGA or less (aspect ratio) In a display device of 3: 4, it can be particularly preferably used for 1024 × 768 or less).

  The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625) (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Proceed) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for widening the viewing angle. ), (3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).

  The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between the upper part and the lower part of the liquid crystal cell. It is disclosed in the specifications of Japanese Patent Nos. 45882525 and 5410422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. For this reason, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

  In an ECB mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and is most frequently used as a color TFT liquid crystal display device, and is described in many documents. For example, it is described in “EL, PDP, LCD display” published by Toray Research Center (2001).

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass.
In addition, hereinafter, the antiglare layer coating liquids D and E using titanium alkoxide in the coating liquid for the antiglare layer in [Example B], and the antiglare film using the coating liquids D and E for the antiglare layer ( Example B1-2, B1-3), antireflection film using the antiglare film (Example B2-2, B2-3), polarizing plate using the antiglare film or antireflection film (Example B201) -2, B201-3 to Examples B202-2, B202-3), liquid crystal display devices using the polarizing plates (Examples B301-2, B301-3 to Examples B302-2, B302-3), etc. , A description of direct examples of the invention (see also Tables 6-10, etc.).
On the other hand, no metal compound such as titanium alkoxide is used in the coating solution for the antiglare layer. Examples described in [Example A] (see also Tables 1 to 5) and other examples described in [Example B] Examples (Example B1-1, Example B2-1, Example B201-1, Example B202-1, Example B301-1, Example B302-1) are not examples of the present invention. It is a description as a reference example for understanding the invention.

[Example A]
[Preparation of antiglare film]

(Adjustment of cellulose ester solution)
─────────────────────────────────────
Composition of cellulose ester solution A ------------------------------
Cellulose ester (acetyl group substitution degree 2.9, Mn = 16000,
Mw / Mn = 1.7) 100.0 parts trimethylolpropane tribenzoate (polyhydric alcohol ester, plasticizer)
5.0 parts ethylphthalyl ethyl glycolate (plasticizer) 5.0 parts 2-hydroxy-4-benzyloxybenzophenone (ultraviolet absorber) 1.0 part Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd., fine particles) 0. 15 parts methylene chloride 440.0 parts ethanol 35.0 parts ─────────────────────────────────────

─────────────────────────────────────
Composition of cellulose ester solution B ─────────────────────────────────────
Cellulose ester (acetyl group substitution degree 2.9, Mn = 16000,
Mw / Mn = 1.7) 100.0 parts triphenyl phosphate (plasticizer) 12.0 parts 2-hydroxy-4-benzyloxybenzophenone (ultraviolet absorber) 1.0 part Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd.) 0.15 parts Methylene chloride 440.0 parts Ethanol 35.0 parts ──────────────────────────────── ─────

(Production of cellulose ester film)
Cellulose ester solutions A and B were prepared using the described cellulose ester, plasticizer, ultraviolet absorber, fine particles, and solvent. That is, the solvent was put into an airtight container, the remaining materials were put in order while stirring, and completely dissolved and mixed while heating and stirring. The fine particles were added dispersed in a part of the solvent. After the temperature was lowered to the temperature at which the solution was cast and allowed to stand overnight, a defoaming operation was performed. Filtration using 244 gave cellulose ester solutions A and B.

  Next, the cellulose ester solution whose temperature was adjusted to 33 ° C. was fed to a die and uniformly cast from a die slit onto a stainless steel belt. The cast part of the stainless steel belt was heated from the back with hot water of 37 ° C. After casting, the dope film on the metal support (referred to as web after casting on the stainless steel belt) is dried by applying hot air of 44 ° C., and the residual solvent amount at the time of peeling is peeled off at 120% by mass, Tension is applied at the time of peeling so that the longitudinal draw ratio is 1.1 times, and then the web end is gripped by a tenter so that the draw ratio is 1.1 times in the width direction at 130 ° C. Stretched. After stretching, hold for several seconds while maintaining its width, release the width holding after relaxing the tension in the width direction, and further carry it for 20 minutes in the third drying zone set at 125 ° C. to perform drying, Cellulose ester films A and B with a film thickness of 50 μm having a width of 1.5 m, a width of 1.5 cm at the end, and a height of 8 μm were prepared.

(Adjustment of antiglare layer coating solution)
─────────────────────────────────────
Composition of coating solution A for anti-glare layer ──────────────────────────────────────
PETA 540.0 parts polymethyl methacrylate solution (20%) 300.0 parts Irgacure 184 20.0 parts 8 μm crosslinked polystyrene particle toluene dispersion (30%) 17.0 parts 8 μm crosslinked acrylic-styrene particle toluene dispersion (30 %) 133.0 parts Toluene 47.0 parts Cyclohexanone 98.0 parts Silicone oil “X-22-164C” 0.1 part ───────────────────── ────────────────

─────────────────────────────────────
Composition of coating solution B for antiglare layer ──────────────────────────────────────
PETA 540.0 parts polymethyl methacrylate solution (20%) 300.0 parts Irgacure 184 20.0 parts 6 μm crosslinked polystyrene particle toluene dispersion (30%) 17.0 parts 6 μm crosslinked acrylic-styrene particle toluene dispersion (30 %) 133.0 parts Toluene 47.0 parts Cyclohexanone 98.0 parts Silicone oil “X-22-164C” 0.1 part ───────────────────── ────────────────

─────────────────────────────────────
Composition of Coating Solution C for Antiglare Layer ─────────────────────────────────────
PETA 540.0 parts polymethyl methacrylate solution (20%) 300.0 parts Irgacure 184 20.0 parts 3.5 μm crosslinked polystyrene particle toluene dispersion (30%) 17.0 parts 3.5 μm crosslinked acrylic-styrene particle toluene Dispersion (30%) 133.0 parts Toluene 47.0 parts Cyclohexanone 98.0 parts Silicone oil “X-22-164C” 0.1 part ───────────────── ────────────────────

The compounds used are shown below.
PETA: mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate [KAYARAD PET-30: manufactured by Nippon Kayaku Co., Ltd.] Polymethyl methacrylate solution (20%): polymethyl methacrylate having a molecular weight of 120,000 (Aldrich) 30% toluene solution Irgacure 184: Polymerization initiator [Ciba Specialty Chemicals Co., Ltd.]

3.5 μm crosslinked polystyrene particle toluene dispersion (30%): 30 wt% toluene dispersion of SX-350H [average particle size 3.5 μm crosslinked polystyrene particles, refractive index 1.60, manufactured by Soken Chemical Co., Ltd.], Polytron Use after dispersion at 10,000 rpm for 20 minutes with a disperser. 6 μm crosslinked polystyrene particle toluene dispersion (30%): [Crosslinked with the same composition as SX-350H, average particle size 6.0 μm, refractive index 1.60. Polystyrene particles] 30% toluene dispersion, Polytron disperser used after dispersion for 20 minutes at 10,000 rpm. 8 μm cross-linked polystyrene particle toluene dispersion (30%): [Same composition as SX-350H, average particle size 8.0 μm, cross-linked polystyrene particles having a refractive index of 1.60] in a 30% toluene dispersion, 20% at 10,000 rpm in a polytron disperser. Use after dispersion: 3.5 μm crosslinked acrylic-styrene particle toluene dispersion (30%): 30% toluene dispersion of SX-350HL [average particle size 3.5 μm, refractive index 1.55, manufactured by Soken Chemical Co., Ltd.] , Used after dispersion for 20 minutes at 10,000 rpm with a Polytron disperser. 6 μm crosslinked acrylic-styrene particle toluene dispersion (30%): [same composition as SX-350HL, average particle size 6.0 μm, refractive index 1 .55 cross-linked acrylic-styrene particles] 30% toluene dispersion, polytron disperser used after dispersion for 20 minutes at 10,000 rpm. 8 μm cross-linked acrylic-styrene particles toluene dispersion (30%): [same as SX-350HL 30% toluene dispersion of a cross-linked acrylic-styrene particle having a composition, an average particle size of 8.0 μm, and a refractive index of 1.55] 20 minutes after use distributed 10000rpm

X22-164C: methacryl-modified polydimethylsiloxane at both ends (Shin-Etsu Chemical Co., Ltd.)

(Coating of antiglare layer)
Prepare coating solutions A, B, and C for an antiglare layer, apply them on the surfaces of cellulose ester films A and B using a micro gravure coater, dry at 90 ° C, and then use an ultraviolet lamp. The illuminance of the irradiated part is 100 mW / cm ² , the irradiation amount is 80 mJ / cm ² , the coating layer is cured to form an antiglare layer with a thickness of 25 μm, and an antiglare film (Examples A1-1, 2 and Comparative Examples) A1-1 to 4) were prepared. Further, an antiglare layer was formed in the same manner except that the thickness of the antiglare layer was 7.5 μm, and antiglare films (Comparative Examples A1-5 to 10) were produced. Further, an antiglare layer was formed in the same manner except that the coating layer was cured by setting the irradiation amount of the irradiation part of the ultraviolet lamp to 150 mJ / cm ² , and an antiglare film (Examples A1-3, 4, Comparative Example A1). -11 to 20) were produced. Further, an antiglare layer was formed in the same manner as in Example A1-1 except that the illuminance of the ultraviolet lamp was changed to ²⁰ , 50, 150, 200 mW / cm ^2, and an antiglare film (Examples A1-5 to 8) ) Was produced. The obtained antiglare film is shown in Table 1.

(Saponification treatment of antiglare film)
The anti-glare films (Examples A1-1 to A1-8, Comparative Examples A1-1 to A1-20) obtained as described above were subjected to the following saponification treatment.
A 1.5 mol / L aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.005 mol / L dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C.
The produced antiglare film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Next, after immersing in the dilute sulfuric acid aqueous solution for 1 minute, the dilute sulfuric acid aqueous solution was sufficiently washed away by immersing in water. Finally, the sample was thoroughly dried at 120 ° C. In this way, saponified antiglare films (Examples A101-1 to 8 and Comparative Examples A101-1 to 20) were produced.

[Evaluation]
The obtained saponification-treated antiglare film was evaluated as follows.

<< Flatness index; Evaluation of minute irregularities >>
Laser displacement meter: Keyence Co., Ltd., Model: LT-8100, Resolution: 0.2 μm, Scan with a laser displacement meter in the width direction to measure fine undulations on the surface, flatness of anti-glare film Evaluated.

  The measuring method is to place the film on a flat and horizontal table, fix both ends of the width to the table with tape, and set the measuring camera parallel to the table. It set so that the space | interval of a sample film might be set to 25 mm, and scanned and measured with the moving speed of 5 cm / min. The measurement was performed from the back side provided with an antiglare layer in order to observe deformation such as undulation of the film itself. The value obtained by the measurement is the state and size of minute irregularities on the film.

A: Unevenness due to film deformation is less than 0.5 μm ○: Unevenness due to film deformation is less than 0.5 to 1.0 μm Δ: Unevenness due to film deformation is less than 1.0 to 3.0 μm ×: Due to film deformation Unevenness is more than 3.0μm

<<Flatness; Visual evaluation >>
Each sample was cut into a size of 90 cm in width and 100 cm in length, and a height of 1.5 m so that five 40 W fluorescent lamps (FLR40S-EX-D / M manufactured by Matsushita Electric) were arranged and the sample stage could be illuminated from an angle of 45 °. The film samples were placed on the sample stage, and the unevenness that was reflected on the back side of the film was visually observed and judged as follows. By this method, it is possible to determine “tsun” and “wrinkle”.

◎: All five fluorescent lights look straight ○: Some fluorescent lights appear to be bent slightly △: Fluorescent lights appear to be slightly bent overall ×: Fluorescent lights appear to swell greatly

《Pencil hardness evaluation》
As an index of scratch resistance, pencil hardness evaluation described in JIS K5400 was performed. After conditioning the light diffusion film at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, using a 2H-5H test pencil specified in JIS S6006, with a load of 4.9 N, the following determination was made. The highest hardness that was evaluated as OK was taken as the evaluation value.
In evaluation of n = 5, there is no scratch to one scratch: OK
In evaluation of n = 5, 3 or more scratches: NG

《Scratch resistance》
The steel wool # 0000, the surface of the antiglare layer by reciprocating 10 times while applying a load of 1000 g, back to is adhered black tape was visually observed occurrence of scratches in the green lamp, per area 1 cm ² The number of wounds was determined.

《Adhesion》
On the surface of each sample that has an antiglare layer, cut in 11 vertical and 11 horizontal cuts with a cutter knife in a grid pattern, and carve a total of 100 square squares. After a 340-hour weather resistance test according to a carbon arc lamp manufactured by Co., Ltd., a black panel temperature of 83 ° C. and a rainy condition, evaluation was performed according to the following criteria.
The antireflection film sample was conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%. On the surface of each sample that has an antiglare layer, 11 vertical and 11 horizontal cuts are made in a grid pattern with a cutter knife, and a total of 100 square squares are carved, and Nitto Denko Corporation ) Made of polyester adhesive tape (No. 31B). After 30 minutes, the tape was quickly peeled off in the vertical direction, and the number of squares peeled off was counted and evaluated according to the following four criteria. The same adhesion evaluation was performed 3 times and the average was taken.
A: No peeling was observed at 100 mm.
○: peeling of 1 to 2 mm was observed at 100 mm.
Δ: Peeling of 3 to 10 mm was observed at 100 mm (within tolerance).
X: Peeling of 11 mm or more was observed at 100 mm.

(Summary)
From the results shown in Table 2, the following is clear.
What used the cellulose-ester film B containing the phosphate ester type plasticizer (Comparative Example A101-2-4,8-10,12-14,18-20) was inferior in planarity and adhesiveness. Met.
Moreover, what formed the thin (7.5 micrometer) anti-glare layer (Comparative Example A101-5-10, 15-20) was inferior in pencil hardness and scratch resistance. And when the film thickness of an anti-glare layer is thin, those using light diffusing particles (8 μm) having a large average particle diameter (Comparative Examples A101-5, 8, 15, 18) have too high surface haze ( 25%), and the scratch resistance was slightly inferior.
On the other hand, even when the film thickness of the antiglare layer is appropriate (25 μm), the antiglare layer coating liquid C containing light diffusing particles having a small average particle diameter (3.5 μm) is used (Comparative Example A101). -1,4,11,14) was slightly inferior in scratch resistance.
On the other hand, the anti-glare film of the present invention (Examples A101-1 to 8) is suitable on the surface of the cellulose ester film A containing two kinds of plasticizers other than the phosphate ester and the ultraviolet absorber. The antiglare layer coating liquids A and B containing light diffusing particles within the average particle size range (8 μm to 6 μm) are cured after application to form an antiglare layer within an appropriate thickness range (25 μm). It was within an appropriate surface haze range (1%), and was excellent in all of adhesion, pencil hardness, scratch resistance, and flatness. In particular, even when the amount of ionizing radiation was 100 mJ / cm ² or less (Examples A101-1, 2), all were excellent. This excellent performance was not changed when the irradiation light amount of ionizing radiation was fixed at 80 mJ / cm ² and the illuminance of ionizing radiation was changed to 20, 50, 100, 150 mJ (Examples A101-5 to 8). ).

[Preparation of antireflection film]
(Preparation of sol solution a)
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. Thereafter, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of coating solution for low refractive index layer)
────────────────────────────────────────
Composition of coating liquid A for low refractive index layer ─────────────────────────────────────────
-Thermally crosslinkable fluorine-containing polymer containing polysiloxane and hydroxyl group (JTA113, solid content concentration 6%, refractive index: 1.44, manufactured by JSR Corporation) 13 parts by mass-Colloidal silica dispersion MEK-ST-L
(Trade name, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 1.3 parts by mass, the sol solution a 0.6 parts by mass, methyl ethyl ketone 5 parts by mass, cyclohexanone 0.6 parts by mass, Leveling agent Calculated to be 0.3% by mass of the total coating liquid amount ─────────────────────────────── ──────────

  After stirring the mixed solution, it was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution A for a low refractive index layer. The refractive index of the layer formed with this coating solution was 1.45.

(Coating of low refractive index layer)
On the antiglare film (Examples A1-1 to 8, Comparative Examples A1-1 to A-20), the coating solution A for the low refractive index layer is used, and the thickness of the low refractive index layer is adjusted to 95 nm. And the low-refractive-index layer was formed with the micro gravure coating system, and the anti-reflective film sample (Example A2-1 to 8, Comparative Example A2-1 to 20) was produced.

The curing conditions are shown below.
(1) Drying: 80 ° C. for 120 seconds (2) Pre-irradiation heat treatment: 95 ° C. for 5 minutes (3) UV curing: 90 ° C. for 1 minute, nitrogen so that the atmosphere has an oxygen concentration of 0.01% by volume or less. While purging, a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used to obtain an irradiance of 120 mW / cm ² and an irradiation amount of 240 mJ / cm ² .
(4) Post-irradiation heat treatment: 30 ° C. for 5 minutes

(Saponification treatment of antireflection film)
The antireflection film sample obtained as described above was subjected to the following saponification treatment.
A 1.5 mol / L aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.005 mol / L dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C.
The prepared antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Next, after immersing in the dilute sulfuric acid aqueous solution for 1 minute, the dilute sulfuric acid aqueous solution was sufficiently washed away by immersing in water. Finally, the sample was thoroughly dried at 120 ° C. In this way, saponified antireflection films (Examples A102-1 to 8 and Comparative Examples A102-1 to 20) were produced.

[Evaluation]
The obtained saponified antireflection film was evaluated in the same manner as the saponified antiglare film.

(Summary)
The evaluation of the antireflection film shown in Table 3 is inferior in flatness and adhesiveness using the cellulose ester film B containing a phosphate ester type plasticizer as in the antiglare film shown in Table 2. Those having a thin (7.5 μm) antiglare layer are inferior in pencil hardness and scratch resistance, and have a large average particle diameter when the antiglare layer is thin (8 μm) In the case of using, the surface haze becomes too large and the scratch resistance is slightly inferior. In addition, even when the film thickness of the antiglare layer is appropriate (25 μm), an antiglare layer coating solution C containing light diffusing particles having a small average particle diameter (3.5 μm) is scratch resistant. A little inferior in sex.
Further, a protective film containing light diffusing particles within an appropriate average particle diameter range (8 μm to 6 μm) on the surface of the cellulose ester film A containing two kinds of plasticizers other than phosphate ester and an ultraviolet absorber. After applying the coating liquid A or B for the glare layer, the coating is cured to form an antiglare layer within an appropriate thickness range (25 μm), and further, the coating liquid A for the low refractive index layer is coated thereon and cured. The antireflective film of the present invention having a low refractive index layer has a surface haze within an appropriate range (1%), and is excellent in all of adhesion, pencil hardness, scratch resistance, and flatness. It was. In particular, even when the amount of ionizing radiation applied was 100 mJ / cm ² or less (Examples A102-1, 2), all were excellent. This excellent performance was not changed even when the irradiation light amount of ionizing radiation was fixed at 80 mJ / cm ² and the illuminance of ionizing radiation was changed to 20, 50, 100, 150 mJ (Examples A102-5 to 8). ).

[Production of polarizing plate with antiglare film]
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. A saponified antiglare film (Examples A101-1 to 8 and Comparative Examples A101-1 to 20) is coated with a polyvinyl alcohol adhesive, and the support side (triacetylcellulose) of the antiglare film is on the polarizing film side. It stuck on the one side of the polarizing film so that it might become. Further, the disc surface of the discotic structural unit is inclined with respect to the support surface, and the angle formed by the disc surface of the discotic structural unit and the support surface changes in the depth direction of the optically anisotropic layer. Wide-view film SA with an optically anisotropic layer “Side-view film SA” {Fuji Photo Film Co., Ltd.} is saponified and attached to the other side of the polarizing film using a polyvinyl alcohol adhesive I attached. Thus, polarizing plates with antiglare films (Examples A201-1 to 8 and Comparative Examples A201-1 to 20) were produced. These polarizing plates with an antiglare film (Examples A201-1 to 8 and Comparative Examples A201-1 to 20) were evaluated for pencil hardness, scratch resistance, and adhesion. As a result, a saponified antiglare film (Examples) was obtained. A101-1 to 8 and Comparative Example A101-1 to 20) were obtained.

[Production of polarizing plate with antireflection film]
Similar to the production of a polarizing plate with an antiglare film, except that a saponified antireflection film (Example A 102-1 to 8, Comparative Example A 102-1 to 20) is used in place of the saponified antiglare film. Thus, polarizing plates with antireflection films (Examples A202-1 to 8, Comparative Examples A202-1 to 20) were produced. These polarizing plates with antireflection films (Examples A202-1 to 8 and Comparative Examples A202-1 to 20-20) were evaluated for pencil hardness, scratch resistance, and adhesion. As a result, a saponified antireflection film (Examples) was obtained. A performance similar to that of A102-1 to 8 and Comparative Example A102-1 to 20) was obtained.

[Production of liquid crystal display device]
A liquid crystal panel for viewing angle measurement was produced as follows, and the characteristics as a liquid crystal display device were evaluated.

  The polarizing plates on both sides of the 15-inch display VL-150SD manufactured by Fujitsu were previously peeled off, and the polarizing plates with antiglare films prepared above (Examples A201-1 to 8 and Comparative Examples A201-1 to 20) were used. Each was bonded to the glass surface of the liquid crystal cell.

  At that time, the direction of bonding of the polarizing plate is such that the surface of the optical compensation film (retardation film) is on the liquid crystal cell side, and the absorption axis is in the same direction as the polarizing plate previously bonded. The liquid crystal display devices (Examples A301-1 to 8 and Comparative Examples A301-1 to A20-1) were respectively produced.

  The polarizing plates on both sides of the 15-inch display VL-150SD manufactured by Fujitsu were previously peeled off, and the polarizing plates with antireflection films prepared above (Examples A202-1 to 8, Comparative Examples A202-1 to 20) were used. Each was bonded to the glass surface of the liquid crystal cell.

  At that time, the direction of bonding of the polarizing plate is such that the surface of the optical compensation film (retardation film) is on the liquid crystal cell side, and the absorption axis is in the same direction as the polarizing plate previously bonded. The liquid crystal display devices (Examples A302-1 to A302-1, Comparative Example A302-1 to 20) were manufactured.

[Evaluation]
<Evaluation of visibility>
Each liquid crystal display device thus obtained was allowed to stand for 100 hours at 60 ° C. and 90% RH, and then returned to 23 ° C. and 55% RH. As a result, when the surface of the display device was observed, the one using the antiglare antireflection film of the present invention was excellent in flatness, whereas the comparative polarizing plate had fine wavy unevenness and eyes. It was easy to get tired.

A: No wavy unevenness is observed on the surface. O: A slight wavy unevenness is observed on the surface. Δ: A slight wavy unevenness is slightly observed on the surface. X: A fine wavy unevenness is observed on the surface.

<Evaluation of coating unevenness>
The coating unevenness was observed visually and evaluated with the following evaluation scale.

◎: Application unevenness is not recognized. ○: Slight unevenness is observed at the end. △: White and weak application spots are observed. ×: Application spots that appear white in the width direction are observed.

<Evaluation of uneven reflection color>
About each liquid crystal display device, the screen was set as black display, and the reflection unevenness of the surface was evaluated visually.

◎: Color unevenness of reflected light is not known and black appears to be dark ○: Color unevenness of reflected light is slightly recognized Δ: Color unevenness of reflected light is recognized, but there is no practical problem ×: Reflected light I'm worried about uneven color

  Separately, the viewing angle was measured in each liquid crystal display device by EZ-contrast manufactured by ELDIM. The viewing angle was expressed in the range of the tilt angle from the normal direction with respect to the panel surface where the contrast ratio at the time of white display and black display of the liquid crystal cell is 10 or more. As a result, in the liquid crystal display devices of the present invention using the polarizing plate of the present invention (Examples A301-1 to 8 and Examples A302-1 to 8), a field of view of 160 ° or more when measured from an oblique 45 ° direction. It was confirmed to be a horn. Moreover, even if there was a reflection of a fluorescent lamp from an oblique direction, it looked black, the color of reflected light was not uneven, and the eyes did not get tired. On the other hand, in the comparative liquid crystal display devices (Comparative Examples A301-1 to 20 and Comparative Example A302-1 to 20), black from an oblique direction does not appear due to fine wavy unevenness, and the visibility is inferior. Visibility improvement effect by corner enlargement had declined.

(Summary)
From the results shown in Tables 4 and 5, the following is clear.
What used the cellulose-ester film B containing the phosphate ester type plasticizer was inferior in visibility, coating unevenness, and reflection color unevenness.

(result)
The antiglare film of the present invention has excellent adhesion and flatness as well as hardness and scratch resistance, and can be cured with a low irradiation light quantity, so that it is excellent in productivity, particularly a thin film or wide cellulose ester film substrate. Even if it was the anti-glare film manufactured using this, not only was it excellent in hardness and scratch resistance, but also an anti-glare film excellent in adhesion and flatness was obtained. In addition, by providing an antireflection layer on the antiglare film, there is no uneven color of reflected light, and the effect of widening the viewing angle is obtained by using it for a polarizing plate. was gotten.

[Example B]
[Preparation of antiglare film]

(Adjustment of cellulose ester solution and production of cellulose ester film)
Cellulose ester solutions A and B were prepared in the same manner as in Example A, and cellulose ester films A and B were prepared in the same manner as in Example A.

(Adjustment of antiglare layer coating solution)
─────────────────────────────────────
Composition of coating solution D for anti-glare layer ─────────────────────────────────────
PETA 540.0 parts polymethyl methacrylate solution (20%) 300.0 parts Irgacure 184 20.0 parts Ti (OBu) ₄ 20.0 parts 8 μm crosslinked polystyrene particle toluene dispersion (30%) 17.0 parts 8 μm crosslinked Acrylic-styrene particle toluene dispersion (30%) 133.0 parts Toluene 47.0 parts Cyclohexanone 98.0 parts Silicone oil “X-22-164C” 0.1 part ──────────── ─────────────────────────

─────────────────────────────────────
Composition of coating solution E for antiglare layer ──────────────────────────────────────
PETA 540.0 parts polymethyl methacrylate solution (20%) 300.0 parts Irgacure 184 20.0 parts Ti (OBu) ₄ 20.0 parts 5 μm crosslinked polystyrene particle toluene dispersion (30%) 17.0 parts 5 μm crosslinked Acrylic-styrene particle toluene dispersion (30%) 133.0 parts Toluene 47.0 parts Cyclohexanone 98.0 parts Silicone oil “X-22-164C” 0.1 part ──────────── ─────────────────────────

The compounds used are shown below.
PETA: a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate [KAYARAD PET-30: manufactured by Nippon Kayaku Co., Ltd.]
Polymethyl methacrylate solution (20%): 30% toluene solution of polymethyl methacrylate having a molecular weight of 120,000 (manufactured by Aldrich) Irgacure 184: polymerization initiator [manufactured by Ciba Specialty Chemicals Co., Ltd.]

Ti (OBu) ₄ : Tetra-n-butoxy titanium [manufactured by Nippon Soda Co., Ltd.]
3.5 μm crosslinked polystyrene particle toluene dispersion (30%): 30 wt% toluene dispersion of SX-350H [average particle size 3.5 μm crosslinked polystyrene particles, refractive index 1.60, manufactured by Soken Chemical Co., Ltd.], Polytron Use after dispersion at 10,000 rpm for 20 minutes in a disperser. 5 μm crosslinked polystyrene particle toluene dispersion (30%): [Cross-linked with the same composition as SX-350H, average particle size 5.0 μm, refractive index 1.60. Polystyrene particles] 30% toluene dispersion, Polytron disperser used after dispersion for 20 minutes at 10,000 rpm. 8 μm cross-linked polystyrene particle toluene dispersion (30%): [Same composition as SX-350H, average particle size 8.0 μm, cross-linked polystyrene particles having a refractive index of 1.60] in a 30% toluene dispersion, 20% at 10,000 rpm in a polytron disperser. Use after dispersion: 3.5 μm crosslinked acrylic-styrene particle toluene dispersion (30%): 30% toluene dispersion of SX-350HL [average particle size 3.5 μm, refractive index 1.55, manufactured by Soken Chemical Co., Ltd.] , Used after dispersion for 20 minutes at 10,000 rpm with a Polytron disperser. 5 μm crosslinked acrylic-styrene particle toluene dispersion (30%): [Same composition as SX-350HL, average particle size 5.0 μm, refractive index 1 .55 cross-linked acrylic-styrene particles] 30% toluene dispersion, polytron disperser used after dispersion for 20 minutes at 10,000 rpm. 8 μm cross-linked acrylic-styrene particles toluene dispersion (30%): [same as SX-350HL 30% toluene dispersion of a cross-linked acrylic-styrene particle having an average particle size of 8.0 μm and a refractive index of 1.55] in a polytron disperser 20 minutes after use distributed 10000rpm

X22-164C: methacryl-modified polydimethylsiloxane at both ends (Shin-Etsu Chemical Co., Ltd.)

(Coating of antiglare layer)
Prepare coating solutions A, D, and E for the antiglare layer, apply them on the surfaces of cellulose ester films A and B using a micro gravure coater, dry at 90 ° C, and then use an ultraviolet lamp. The illuminance of the irradiated part is 100 mW / cm ² , the irradiation amount is 80 mJ / cm ² , the coating layer is cured, and an antiglare layer with a thickness of 25 μm is formed. B1-1 to 3) were produced. Table 6 shows the obtained antiglare film.

[Evaluation]
The following evaluation was performed about the obtained anti-glare film.

<< Flatness index; Evaluation of minute irregularities >>
Laser displacement meter: Keyence Co., Ltd., Model: LT-8100, Resolution: 0.2 μm, Scan with a laser displacement meter in the width direction to measure fine undulations on the surface, flatness of anti-glare film Evaluated.

  The measuring method is to place the film on a flat and horizontal table, fix both ends of the width to the table with tape, and set the measuring camera parallel to the table. It set so that the space | interval of a sample film might be set to 25 mm, and scanned and measured with the moving speed of 5 cm / min. The measurement was performed from the back side provided with an antiglare layer in order to observe deformation such as undulation of the film itself. The value obtained by the measurement is the state and size of minute irregularities on the film.

A: Unevenness due to film deformation is less than 0.5 μm ○: Unevenness due to film deformation is less than 0.5 to 1.0 μm Δ: Unevenness due to film deformation is less than 1.0 to 3.0 μm ×: Due to film deformation Unevenness is more than 3.0μm

<<Flatness; Visual evaluation >>
Each sample was cut into a size of 90 cm in width and 100 cm in length, and a height of 1.5 m so that five 40 W fluorescent lamps (FLR40S-EX-D / M manufactured by Matsushita Electric) were arranged and the sample stage could be illuminated from an angle of 45 °. The film samples were placed on the sample stage, and the unevenness that was reflected on the back side of the film was visually observed and judged as follows. By this method, it is possible to determine “tsun” and “wrinkle”.

◎: All five fluorescent lights look straight ○: Some fluorescent lights appear to be bent slightly △: Fluorescent lights appear to be slightly bent overall ×: Fluorescent lights appear to swell greatly

《Pencil hardness evaluation》
As an index of scratch resistance, pencil hardness evaluation described in JIS K5400 was performed. After conditioning the light diffusion film at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, using a 2H-5H test pencil specified in JIS S6006, with a load of 4.9 N, the following determination was made. The highest hardness that was evaluated as OK was taken as the evaluation value.
In evaluation of n = 5, there is no scratch to one scratch: OK
In evaluation of n = 5, 3 or more scratches: NG

《Scratch resistance》
The steel wool # 0000, the surface of the antiglare layer by reciprocating 10 times while applying a load of 1000 g, back to is adhered black tape was visually observed occurrence of scratches in the green lamp, per area 1 cm ² The number of wounds was determined.

《Adhesion》
On the surface of each sample that has an antiglare layer, cut in 11 vertical and 11 horizontal cuts with a cutter knife in a grid pattern, and carve a total of 100 square squares. After a 340-hour weather resistance test according to a carbon arc lamp manufactured by Co., Ltd., a black panel temperature of 83 ° C. and a rainy condition, evaluation was performed according to the following criteria.
The antireflection film sample was conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%. On the surface of each sample that has an antiglare layer, 11 vertical and 11 horizontal cuts are made in a grid pattern with a cutter knife, and a total of 100 square squares are carved, and Nitto Denko Corporation ) Made of polyester adhesive tape (No. 31B). After 30 minutes, the tape was quickly peeled off in the vertical direction, and the number of squares peeled off was counted and evaluated according to the following four criteria. The same adhesion evaluation was performed 3 times and the average was taken.
A: No peeling was observed at 100 mm.
○: peeling of 1 to 2 mm was observed at 100 mm.
Δ: Peeling of 3 to 10 mm was observed at 100 mm (within tolerance).
X: Peeling of 11 mm or more was observed at 100 mm.

(Summary)
From the results shown in Table 7, the following is clear.
What used the cellulose-ester film B containing the phosphate ester type plasticizer (Comparative Example B1-1-3) was inferior in planarity and adhesiveness.
On the other hand, the antiglare film of the present invention (Examples B1-1 to B3) is appropriate on the surface of the cellulose ester film A containing two kinds of plasticizers other than the phosphate ester and the ultraviolet absorber. Applicable anti-glare layer coating liquids A, D and E containing a metal compound (tetra-n-butoxytitanium) together with light diffusing particles within an average particle diameter range (8 μm to 5 μm) are cured to an appropriate thickness. An antiglare layer having a thickness in the range (25 μm) was formed to have an appropriate surface haze range (1%), and was excellent in adhesion, pencil hardness, scratch resistance, and flatness.

[Preparation of antireflection film]
(Preparation of coating solution for low refractive index layer)
A coating solution B for a low refractive index layer was prepared as follows.
A mixture of 32.1 g of normal ethyl silicate (SiO ₂ concentration 28 wt%) and 1.22 g of nonadecafluorododecyltrimethoxysilane in 55.0 g of isopropyl alcohol, 10 g of pure water and 1.69 g of nitric acid with a concentration of 61 wt%. The mixture was mixed and stirred at 50 ° C. for 1 hour to prepare a matrix-forming component liquid (M-1) having a solid concentration of 10% by weight.

  Subsequently, 6.7 g of the matrix-forming component liquid (M-1) was added to a hollow silica fine particle sol (isopropyl alcohol silica sol, average particle diameter 40 nm, shell thickness 6 nm, silica concentration 20 mass%, silica particle refractive index 1.30, Prepared in accordance with Preparation Example 4 of Kai 2002-79616) and mixed with 0.63 g and diluted with isopropyl alcohol to obtain a coating solution B for a low refractive index layer having a solid content concentration of 1.0% by weight. Prepared.

(Coating of low refractive index layer)
On the antiglare film (Examples B1-1 to 3 and Comparative Examples B1-1 to 3), the low refractive index layer coating liquid B is applied by a microgravure method, and the low refractive index after curing. Antireflection film samples (Examples B2-1 to B3 and Comparative Examples B2-1 to B3) were prepared by adjusting the layer thickness to 95 nm. Immediately before the application of the low refractive index layer, 1.5% by weight of 3-isocyanatopropyltriethoxysilane based on the total solid content was added to the coating solution for the low refractive index layer.

The curing conditions are shown below.
(1) Drying: 90 ° C. for 150 seconds (2) Pre-irradiation heat treatment: 120 ° C. for 10 minutes (3) UV curing: 90 ° C. for 1 minute, nitrogen so that the oxygen concentration is 0.01 vol% or less. While purging, a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used to obtain an irradiance of 120 mW / cm ² and an irradiation amount of 240 mJ / cm ² .
(4) Post-irradiation heat treatment: 30 ° C. for 5 minutes

[Evaluation]
About the obtained anti-reflective film, evaluation similar to the said anti-glare film was performed.

(Summary)
The evaluation of the antireflection film shown in Table 8 is inferior in flatness and adhesion, as in the antiglare film shown in Table 7, using the cellulose ester film B containing a phosphate ester plasticizer. (Comparative Example B2-1 to 3).
Further, on the surface of the cellulose ester film A containing two kinds of plasticizers other than phosphate ester and an ultraviolet absorber, a metal compound (with a light diffusing particle within an appropriate average particle diameter range (8 μm to 5 μm)) ( Anti-glare layer coating solutions A, D and E containing (tetra-n-butoxytitanium) are cured after coating to form an anti-glare layer within an appropriate thickness range (25 μm), and a low refractive index layer The antireflective film of the present invention in which the coating liquid B was applied and then cured to form a low refractive index layer has a surface haze within an appropriate range (1%), adhesion, pencil hardness, It was excellent in scratching and flatness. (Example B2-1 to 3).

[Production of polarizing plate with antiglare film]

(Back surface saponification treatment of anti-glare film)
The following saponification treatment was performed on the antiglare film samples (Examples B1-1 to B3 and Comparative Examples B1-1 to B3).
A 1.5 mol / L aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.005 mol / L dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C.
A laminate was affixed to the antiglare layer side of the produced antiglare film, immersed in the above sodium hydroxide aqueous solution for 2 minutes, and then immersed in water to sufficiently wash away the sodium hydroxide aqueous solution. Next, after immersing in the dilute sulfuric acid aqueous solution for 1 minute, the dilute sulfuric acid aqueous solution was sufficiently washed away by immersing in water. Finally, the sample was sufficiently dried at 120 ° C., and the adhered laminate was peeled off. Thus, the back surface saponification-treated anti-glare films (Example B101-1 to Comparative Example B101-1 to B101-3) were produced.

  A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. A polyvinyl alcohol adhesive is used for the antiglare film (Examples B101-1 to B3, Comparative Example B101-1 to B101-3) so that the support side (triacetyl cellulose) of the antiglare film is the polarizing film side. Affixed to one side of the polarizing film. Further, the disc surface of the discotic structural unit is inclined with respect to the support surface, and the angle formed by the disc surface of the discotic structural unit and the support surface changes in the depth direction of the optically anisotropic layer. Wide-view film SA with an optically anisotropic layer “Side-view film SA” {Fuji Photo Film Co., Ltd.} is saponified and attached to the other side of the polarizing film using a polyvinyl alcohol adhesive I attached. In this way, polarizing plates with an antiglare film (Example B201-1 to Example B201-1 to Comparative Example B201-1 to 3) were produced. When evaluation of pencil hardness, scratch resistance, and adhesion was performed on these polarizing plates with an antiglare film (Example B201-1 to Comparative Example B201-1 to Comparative Example B201-1 to 3), an antiglare film (Example B1-1) was used. -3, the same performance as Comparative Examples B1-1 to 3) was obtained.

[Production of polarizing plate with antireflection film]
Polarized light with antireflection film in the same manner as the production of polarizing plate with antiglare film, except that an antireflection film (Examples B2-1 to B3, Comparative Example B2-1 to B2-1) is used instead of the antiglare film. Plates (Example B202-1 to Example B202-1 to Comparative Example B202-1 to Example B202-1) were produced. When these pencils with antireflection film (Example B202-1 to Comparative Example B202-1 to Comparative Example B202-1 to 3) were evaluated for pencil hardness, scratch resistance, and adhesion, an antireflection film (Example B2-1) was obtained. -3 and Comparative Examples B2-1 to 3) were obtained.

[Production of liquid crystal display device]
A liquid crystal panel for viewing angle measurement was produced as follows, and the characteristics as a liquid crystal display device were evaluated.

  The polarizing plates on both sides of the 15-inch display VL-150SD manufactured by Fujitsu were peeled off in advance, and the polarizing plates with antiglare films (Example B201-1 and Comparative Example B201-1) prepared above were respectively used for liquid crystal cells. Bonded to the glass surface.

  At that time, the direction of bonding of the polarizing plate is such that the surface of the optical compensation film (retardation film) is on the liquid crystal cell side, and the absorption axis is in the same direction as the polarizing plate previously bonded. The liquid crystal display devices (Example B301-1 and Comparative Example B301-1) were respectively produced.

  The polarizing plates on both sides of the 15-inch display VL-150SD manufactured by Fujitsu were previously peeled off, and the above-prepared polarizing plates with antireflection films (Example B202-1 and Comparative Example B202-1) were respectively used in the liquid crystal cell. Bonded to the glass surface.

  At that time, the direction of bonding of the polarizing plate is such that the surface of the optical compensation film (retardation film) is on the liquid crystal cell side, and the absorption axis is in the same direction as the polarizing plate previously bonded. The liquid crystal display devices (Example B302-1, Comparative Example B302-1) were produced.

[Evaluation]
<Evaluation of visibility>
Each liquid crystal display device thus obtained was allowed to stand for 100 hours at 60 ° C. and 90% RH, and then returned to 23 ° C. and 55% RH. As a result, when the surface of the display device was observed, the one using the antiglare antireflection film of the present invention was excellent in flatness, whereas the comparative polarizing plate had fine wavy unevenness and eyes. It was easy to get tired.

A: No wavy unevenness is observed on the surface. O: A slight wavy unevenness is observed on the surface. Δ: A slight wavy unevenness is slightly observed on the surface. X: A fine wavy unevenness is observed on the surface.

<Evaluation of coating unevenness>
The coating unevenness was observed visually and evaluated with the following evaluation scale.

◎: Application unevenness is not recognized. ○: Slight unevenness is observed at the end. △: White and weak application spots are observed. ×: Application spots that appear white in the width direction are observed.

<Evaluation of uneven reflection color>
About each liquid crystal display device, the screen was set as black display, and the reflection unevenness of the surface was evaluated visually.

◎: Color unevenness of reflected light is not known and black appears to be dark ○: Color unevenness of reflected light is slightly recognized Δ: Color unevenness of reflected light is recognized, but there is no practical problem ×: Reflected light I'm worried about uneven color

  Separately, the viewing angle was measured in each liquid crystal display device by EZ-contrast manufactured by ELDIM. The viewing angle was expressed in the range of the tilt angle from the normal direction with respect to the panel surface where the contrast ratio at the time of white display and black display of the liquid crystal cell is 10 or more. As a result, in the liquid crystal display devices of the present invention using the polarizing plate of the present invention (Example B301-1 to Example B303-1 to Example B302-1 to 3), a field of view of 160 ° or more when measured from an oblique 45 ° direction. It was confirmed to be a horn. Moreover, even if there was a reflection of a fluorescent lamp from an oblique direction, it looked black, the color of reflected light was not uneven, and the eyes did not get tired. On the other hand, in the comparative liquid crystal display devices (Comparative Examples B301-1 to B303-1 and Comparative Example B302-1 to 3), black from an oblique direction does not appear due to fine wavy unevenness, and the visibility is inferior. Visibility improvement effect by corner enlargement had declined.

(Summary)
From the results shown in Tables 9 and 10, the following is clear.
What used the cellulose-ester film B containing the phosphate ester type plasticizer was inferior in visibility, coating unevenness, and reflection color unevenness.

(result)
The antiglare film of the present invention has excellent adhesion and flatness as well as hardness and scratch resistance, and can be cured with a low irradiation light quantity, so that it is excellent in productivity, particularly a thin film or wide cellulose ester film substrate. Even if it was the anti-glare film manufactured using this, not only was it excellent in hardness and scratch resistance, but also an anti-glare film excellent in adhesion and flatness was obtained. In addition, by providing an antireflection layer on the antiglare film, there is no uneven color of reflected light, and the effect of widening the viewing angle is obtained by using it for a polarizing plate. was gotten.

Claims (16)

On a cellulose ester film containing at least two kinds of plasticizers selected from ultraviolet absorbers and plasticizers other than phosphoric ester plasticizers, at least one kind of translucent resin and at least one kind of light diffusibility An anti-glare film having an anti-glare layer formed by coating particles and a curable resin composition (A) containing at least one metal compound selected from the group consisting of titanium alkoxides, zirconium alkoxides and their chelate compounds The content of the phosphate ester plasticizer in the cellulose ester film is less than 1% by mass, and the average particle size of the light diffusing particles in the antiglare layer is 5 to 15 μm, An anti-glare film, wherein the film thickness of the anti-glare layer is 8 to 40 μm, and the surface haze on the anti-glare layer coating side is 15% or less. 2. The antiglare film according to claim 1, wherein the surface haze is 10% or less and the internal haze is 10 to 90%. The antiglare film according to claim 1 or 2 , wherein a pencil hardness with a load of 4.9N is 4H or more. The cellulose ester film has a total acyl group substitution degree of 2.6 to 2.9, a number average molecular weight (Mn) of 80000 to 200000, and a mass average molecular weight (Mw) / number average molecular weight (Mn) of 1.4 to 3 0.0, the cellulose ester solution is cast and then biaxially stretched, and the translucent resin in the antiglare layer contains an ionizing radiation curable compound, and the antiglare layer is The curable resin composition (A) is coated on the cellulose ester film and then irradiated with ionizing radiation to cure the curable resin composition (A). The anti-glare film according to claim 3 . -Proof translucent resin glare layer is at least a compound containing two or more ethylenically unsaturated groups characterized by containing any one of claims 1 to 4 in one molecule The anti-glare film as described in 2. The antiglare film according to any one of claims 1 to 5 , wherein at least one plasticizer contained in the cellulose ester film is a polyhydric alcohol ester plasticizer. At least one plasticizer contained in the cellulose ester film is selected from citrate ester plasticizers, glycolate plasticizers, phthalate ester plasticizers, and fatty acid ester plasticizers. The antiglare film according to any one of claims 1 to 6 . At least one UV absorber which the cellulose ester film contains is proof according to any one of claims 1 to 7, characterized in that the benzophenone ultraviolet absorber or triazine-based UV absorber Dazzle film. An antireflection film comprising a low refractive index layer having a refractive index lower than that of the antiglare layer on the antiglare film according to any one of claims 1 to 8 . A polarizing plate comprising the antiglare film according to any one of claims 1 to 8 or the antireflection film according to claim 9 on at least one side. At least one of the antiglare film according to any one of claims 1 to 8, the antireflection film according to claim 9 , and the polarizing plate according to claim 10 is disposed. An image display device. On a cellulose ester film containing at least two kinds of plasticizers selected from ultraviolet absorbers and plasticizers other than phosphoric ester plasticizers, at least one kind of translucent resin and at least one kind of light diffusibility An anti-glare film having an anti-glare layer formed by coating particles and a curable resin composition (A) containing at least one metal compound selected from the group consisting of titanium alkoxides, zirconium alkoxides and their chelate compounds A manufacturing method of
Contains an ultraviolet absorber and at least two plasticizers, has a total acyl group substitution degree of 2.6 to 2.9, a number average molecular weight (Mn) of 80,000 to 200,000, and a weight average molecular weight (Mw). / A cellulose ester solution containing a cellulose ester having a number average molecular weight (Mn) value of 1.4 to 3.0 is cast on a support and dried until it can be peeled off. On a cellulose ester film having a phosphate ester plasticizer content of less than 1% by mass obtained by biaxial stretching and drying.
At least one kind of metal selected from the group consisting of at least one kind of translucent resin, at least one kind of light diffusing particles having an average particle diameter of 5 to 15 μm , titanium alkoxide, zirconium alkoxide and their chelate compounds. A curable resin composition (A) containing a compound is coated, irradiated with ionizing radiation, and the resin composition (A) is cured with an amount of ionizing radiation of 5 to 100 mJ / cm ^2. A method for producing an antiglare film. The method for producing an antiglare film according to claim 12 , wherein the thickness of the layer obtained by curing the resin composition (A) is 8 to 40 µm. Illuminance of the ionizing radiation irradiation section for curing the curable wood composition (A) The production method of the antiglare film according to claim 12 or claim 13 characterized in that it is a 50~150mW / cm ^2. The cellulose ester film is stretched in the longitudinal direction (conveying direction) in a state containing a solvent after peeling from the support, and then stretched in the transverse direction by a tenter. method for producing an antiglare film according to any one of 12 to claim 14. The method for producing an antiglare film according to any one of claims 12 to 15 , wherein the curable resin composition (A) is cured while applying a tension.