JP2005096095A - Hard coat film and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hard coat film excellent in planarity and preventing interference irregularity caused between a hard coat layer and a base material film, and its manufacturing method. <P>SOLUTION: This hard coat film is constituted by providing the hard coat layer on at least one surface layer, which has a film thickness of 0.1-15 μm and comprises a cellulose ester with a degree of the total acyl group substitution of 2.7 or below, of a cellulose ester film having a multilayered constitution composed of at least one surface layer and a base layer composed of a plasticizer, an ultraviolet absorber and a cellulose ester with a degree of the total acyl group substitution of 2.8 or above. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a hard coat film and a method for producing the same, and more particularly to a hard coat film having excellent flatness and preventing interference unevenness generated between the hard coat layer and the base film and a method for producing the same.

  In transparent resin films used for optical applications such as a polarizing plate protective film for liquid crystal displays and a circular polarizing plate protective film used for organic EL displays, several functional thin film layers are provided to give various functions. It is painted. Examples of the functional thin film include an antistatic layer for providing an antistatic function, a hard coat layer for improving surface hardness, an undercoat layer for improving film adhesion, and an antistatic layer for preventing curling. A curl layer, an antiglare layer, an antireflection layer, or the like.

  When forming a hard-coat layer in the said transparent resin film, the hardened | cured material layer normally hardened | cured with active rays, such as an ultraviolet-ray, is applied, and an active ray is irradiated and hardened. At this time, since the refractive index of the transparent resin film and that of the hard coat layer are different, the rainbow-colored interference unevenness (interference) is caused by the interference between the light reflected on the hard coat layer surface and the light reflected on the interface between the hard coat layer and the transparent resin film. It was found that a stripe pattern was generated. In particular, when the flatness of the transparent resin film is poor, there is a problem that interference unevenness is more likely to occur. Further, when an antireflection layer is further coated on the hard coat layer, there is a problem that the quality of the reflected light becomes uneven and the quality deteriorates, and this improvement has been demanded. Furthermore, when the film on which the optical thin film is formed is stored in a rolled state under high temperature and high humidity, a phenomenon that the failure is further emphasized occurs, and the part where the color unevenness occurs is discarded, and the productivity is remarkably poor. It was a thing. In particular, a polarizing plate or an antireflection film used for the front surface of a display device has a strict requirement performance, and an optical thin film with excellent uniformity without color unevenness has been desired.

  For example, a method of scattering light reflection at the interface between the hard coat layer and the base material by making irregularities on the base material to suppress interference unevenness is disclosed (for example, see Patent Document 1). However, when the unevenness is large, the interference unevenness is reduced, but the haze increases. When the unevenness is too small, the haze is reduced, but the effect of suppressing the interference unevenness is weakened.

  Moreover, in order to reduce the refractive index difference between the base material and the hard coat layer, a method of providing an undercoat layer in which the refractive index gradually changes between the hard coat layer and the base material is disclosed (for example, However, there is a problem that interference unevenness cannot be completely eliminated if each layer is clear.

Further, the hard coat layer coating composition is coated on the base material using a solvent that swells or dissolves the base material, and the refractive index is continuously changed by eliminating the interface between the hard coat layer and the base material. Although a technique for reducing interference unevenness has been disclosed (see, for example, Patent Document 3), if a large amount of a solvent capable of swelling and dissolving the base material is used, the component constituting the base material in the hard coat layer, particularly plastic A large amount of the agent is mixed, haze increase and scratch resistance are impaired, and the flatness of the substrate is further deteriorated. Moreover, if there is little solvent which can swell and melt | dissolve a base material, the interface of a hard-coat layer and a base material will not be lost, and the effect with respect to interference nonuniformity will become inadequate. Such a phenomenon occurs even with a slight change in drying conditions after the hard coat layer is applied, and there is a problem that it is difficult to obtain an effect stably.
JP-A-8-197670 JP 2000-111706 A JP 2003-131007 A

  Accordingly, an object of the present invention is to provide a hard coat film that is excellent in flatness and prevents interference unevenness that occurs between the hard coat layer and a base film, and a method for producing the same.

The above object of the present invention is achieved by the following configurations.
(Claim 1)
At least one surface layer having a cellulose ester having a film thickness of 0.1 to 15 μm and a total acyl group substitution degree of 2.7 or less, a plasticizer, an ultraviolet absorber, and a cellulose ester having a total acyl group substitution degree of 2.8 or more A hard coat film comprising a hard coat layer on the surface layer of a cellulose ester film having a multilayer structure having a base layer having a surface.
(Claim 2)
The hard coat film according to claim 1, wherein the cellulose ester of the base layer is cellulose triacetate, and the cellulose ester of the surface layer is cellulose diacetate or cellulose acetate propionate.
(Claim 3)
The cellulose ester of the base layer is a cellulose ester having a number average molecular weight (Mn) of 80,000 to 200,000 and a weight average molecular weight (Mw) / number average molecular weight (Mn) value of 1.4 to 3.0. The hard coat film according to claim 1 or 2.
(Claim 4)
The hard coat film according to claim 1, wherein the surface layer contains fine particles.
(Claim 5)
The hard coat film according to any one of claims 1 to 4, wherein the surface layer contains a plasticizer.
(Claim 6)
6. The hard according to claim 1, wherein a plasticizer content of the surface layer adjacent to the hard coat layer is larger than an average plasticizer content of the multilayered cellulose ester film. Coat film.
(Claim 7)
The hard coat film according to claim 1, further comprising an antireflection layer on the hard coat layer.
(Claim 8)
A cellulose ester solution A for forming a base layer having a plasticizer, an ultraviolet absorber and a cellulose ester having a total acyl group substitution degree of 2.8 or more, and a surface layer having a cellulose ester having a total acyl group substitution degree of 2.7 or less. The cellulose ester solution B to be formed is formed by a co-casting method to form a cellulose ester film having a multilayer structure having at least one base layer and a surface layer having a film thickness of 0.1 to 15 μm. A method for producing a hard coat film, comprising: coating an active ray curable resin layer on the top and then irradiating with active rays to form a hard coat layer.

  According to the present invention, it is possible to provide a hard coat film excellent in flatness and preventing interference unevenness generated between the hard coat layer and the base film and a method for producing the same.

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

  In the present invention, at least one surface layer having a cellulose ester having a film thickness of 0.1 to 15 μm and a total acyl group substitution degree of 2.7 or less, a plasticizer, an ultraviolet absorber, and a total acyl group substitution degree of 2.8. A hard coat layer is provided on the surface layer of the cellulose ester film having a multilayer structure including the base layer having the above cellulose ester.

  As a result of earnestly examining the above-mentioned problems, the present inventor has laminated a layer having cellulose esters having different degrees of total acyl group substitution into a cellulose ester film having a multi-layer structure. The interference unevenness generated between the layers can be prevented, and further, by forming a cellulose ester film having a multilayer structure by a co-casting method, it is excellent in flatness, and the interference unevenness is further improved. As soon as it has been found that a coated film can be obtained, the present invention has been achieved.

  Hereinafter, the present invention will be described in detail.

[Base layer]
First, the base layer having the cellulose ester according to the present invention will be described. The cellulose ester, plasticizer, and fine particles used for the surface layer have the same characteristics as those used for the base layer.

  The cellulose ester used in the base layer of 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, etc., JP-A-10-45804, Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in U.S. Pat. No. 8,231,761, U.S. Pat. No. 2,319,052 can be used. Alternatively, an ester of an aromatic carboxylic acid and cellulose and cellulose acylate described in JP-A Nos. 2002-179701, 2002-265639, and 2002-265638 are also preferably used. Among the above description, the lower fatty acid ester of cellulose particularly preferably used is cellulose triacetate for the base layer and cellulose diacetate or cellulose acetate propionate for the surface layer described later. These cellulose esters should be used in combination. You can also.

  The cellulose ester used for the base layer is a cellulose ester having a total acyl group substitution degree of 2.8 or more. As the cellulose ester used for the surface layer described later, those having a total acyl group substitution degree of 2.7 or less are used. Except for this point, those having the same characteristics as the cellulose ester used in the base layer are used. The cellulose ester used in the base layer may be a cellulose ester having a total acyl group substitution degree of 2.8 or more and a cellulose ester having a total acyl group substitution degree of 2.7 or less. The total acyl group substitution degree of 2.8 should just be 2.8 or more.

  The cellulose ester used other than cellulose triacetate has an acyl group having 2 to 4 carbon atoms as a substituent, and when the substitution degree of the acetyl group is X and the substitution degree of the propionyl group is Y, the following formula (a ) And (b) at the same time.

Formula (a) 2.8 ≦ X + Y ≦ 3.0
Formula (b) 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 can be used. 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.

  The molecular weight of the cellulose ester used in the base layer according to the present invention is preferably 80,000 to 200,000 in terms of number average molecular weight (Mn). 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 preferably has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio, Mw / Mn of 1.4 to 3.0, more preferably 1.7 to 3.0. The range is 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 weight 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 3 products manufactured by Showa Denko KK)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000-500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.

  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 acetylcellulose, 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, the degree of decomposition can be defined by the commonly used weight average molecular weight (Mw) / number average molecular weight (Mn). That is, in the process of acetylation of cellulose triacetate, the weight average molecular weight (Mw) is used as one index of the reaction degree for allowing the acetylation reaction to be carried out for a sufficient time for acetylation without being excessively decomposed. ) / Number average molecular weight (Mn).

  An example of a method for producing a cellulose ester is shown below: 100 parts by mass of a flocculent linter as a cellulose raw material was crushed, 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 the method 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. It easily forms a coordination compound, that is, a complex with a ligand, and forms scum (insoluble starch, turbidity) derived from many insoluble calcium.

  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, particularly preferably in the range of 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).

  The base layer of the present invention contains a plasticizer and an ultraviolet absorber in addition to the cellulose ester.

  Examples of the plasticizer include triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, trinaphthyl phosphate, trixyl phosphate, tris ortho-biphenyl phosphate, 1 Phosphate ester plasticizers such as 1,4-phenylene-tetraphenyl phosphate, phthalates such as diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dicyclohexyl terephthalate, dimethyl cyclohexyl phthalate Acid ester plasticizers, triacetin, tributyrin, butylphthalate Butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, etc. glycolic acid ester based plasticizers. Among them, a phthalate ester or glycolate ester plasticizer is preferable because it hardly causes hydrolysis of cellulose ester, and the optical film of the present invention preferably contains two or more plasticizers. One type is preferably a polyhydric alcohol ester plasticizer. Other plasticizers are not particularly limited. Preferably, a polyhydric alcohol ester, a phthalic acid ester, a citric acid ester, a fatty acid ester, a glycolate plasticizer or the like of a different type from the polyhydric alcohol ester plasticizer is used.

  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 (1).

General formula (1)
R _1- (OH) _n
Here, R ₁ is an n-valent organic group, n is a positive integer of 2 or more, and the OH group is an alcoholic 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.

  In the present invention, the monocarboxylic acid used in the polyhydric alcohol ester is not particularly limited, and known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid and the like 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 larger molecular weight is preferable because it is less likely to volatilize, and a smaller one is preferable 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 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 mass ratio between the polyhydric alcohol ester plasticizer and 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.

  The cellulose ester film according to the present invention preferably contains an ultraviolet absorber from the viewpoint of preventing deterioration when placed outdoors as an image display device. As the ultraviolet absorber, those having excellent absorption ability of ultraviolet rays having a wavelength of 370 nm or less and little absorption of visible light having a wavelength of 400 nm or more can be preferably used. For example, the transmittance at 380 nm is preferably less than 20%, more preferably less than 10%, and particularly preferably less than 5%.

  Examples of ultraviolet absorbers include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like in the present invention. It is not limited to.

  Although the specific example of an ultraviolet absorber 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 (Straight and side chain dodecyl) -4-methylphenol (TINUVIN171: Ciba Specialty Chemicals)
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 Specialty Chemicals)
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)
In the optical film of the present invention, a benzotriazole-based UV absorber or a benzophenone-based UV absorber that is highly transparent as an UV absorber and excellent in the effect of preventing the deterioration of a polarizing plate and liquid crystal can be preferably used. A benzotriazole-based ultraviolet absorber with less unnecessary coloring is particularly preferred. Further, it is preferable that the ultraviolet absorber does not bleed out or volatilize in the film forming process.

  In addition, a discotic compound described later is also preferably used as the ultraviolet absorber.

  The ultraviolet absorber is preferably added in an amount of 0.1% by mass to 10% by mass, and particularly preferably 0.5% by mass to 5% by mass.

  The cellulose ester film according to the present invention preferably contains the following discotic compound as another additive for improving haze and planarity.

  As the discotic compound preferably used in the present invention, a triazine compound is preferable. In particular, a compound having a 1,3,5-triazine ring can be preferably used as the discotic compound.

  Among them, the compound having a 1,3,5-triazine ring is preferably a compound represented by the following general formula (2).

In the general formula (2), 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 (2) is particularly preferably a melamine compound.

In the melamine compound, in the general formula (2), 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.

  In addition, several R shown below represents 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-butoxyphenyl (35) p-biphenylyl (36) 4-phenylthiophenyl (37) 4-chlorophenyl (38) 4-benzoylphenyl (39) 4-acetoxyphenyl (40) 4-benzoyloxyphenyl ( 41) 4-phenoxycarbonylphenyl (42) 4-methoxyphenyl (43) 4-anilinophenyl (44) 4-isobutyrylaminophenyl (45) 4-phenoxycarbonylaminophenyl (46) 4- (3-ethyl (Ureido) 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 -Diphenylphenyl (54) 3,4-diphenylthiophenyl (55) 3,4-dichlorophenyl (56) 3,4-dibenzoylphenyl (57) 3,4-diacetoxyphenyl (58) 3,4-dibenzoyl Oxyphenyl (59) 3,4-diphenoxycarbonylphenyl (60) 3,4-dimethoxyphenyl (61) 3,4-dianilinophenyl (62) 3,4-dimethylphenyl (63) 3,4-diphenoxy Phenyl (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-tribenzoylphenyl (72) 3,4,5-triacetoxyphenyl (73) 3,4,5-tribenzoyloxyphenyl (74) 3,4,5-triphenoxycarbonylphenyl (75) 3,4,5-trimethoxyphenyl (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-phenoxycarbonylphenyl (108) 4-methoxyphenyl (109) 4-anilinophenyl (110) 4-isobutyrylaminophenyl (111) 4-phenoxycarbonylaminophenyl (112) 4- (3-ethyl (Ureido) 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 (136) 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 (241) 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-I Butyrylaminophenyl (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-ethoxycarbonyl Phenyl (270) 2-Butoxyphenyl (271) 2-Methylphenyl (272) 2-Chlorophenyl (273) 2-Phenylthiophenyl (274) 2-Benzoylphenyl (275) 2-Acetoxyphenyl (276) 2-Benzoyloxy Phenyl (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-dibenzoyl Enyl (294) 3,4-diacetoxyphenyl (295) 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-diethoxycarbonylphenyl (304) 3,5-didodecyloxyphenyl (305) 3,5-dimethylphenyl (306) 3,5-dichlorophenyl (307) 3,5-dibenzoyl Phenyl (308) 3,5-diacetoxyphenyl (309) 3,5-dimethoxyphenyl (3 0) 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-di Dodecyloxyphenyl (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-diisobutyrylaminopheny (326) 2,4-diphenoxyphenyl (327) 2,4-dihydroxyphenyl (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-dihydroxyphenyl (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-diisobutyrylaminophenyl (354) 2,6-diphenoxyphenyl (355) 2,6-dihydroxyphenyl (356) 3,4,5-tributylphenyl (357) 3,4,5-tri (2-methoxy-2-ethoxy) Til) phenyl (358) 3,4,5-triphenylphenyl (359) 3,4,5-triethoxycarbonylphenyl (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-triisobutyrylaminophenyl (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-triethoxycarbonylphenyl (374) 2,4,6-tridodecyloxyphenyl (375) 2,4,6-trimethyl Phenyl (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-triisobutyrylaminophenyl (382) 2,4,6-triphenoxyphenyl (383) 2,4,6- Trihydroxyphenyl (384) Pentafluorophenyl (385) Pentachlorophenyl (386) Pentamethoxyphenyl (38 ) 6-N-methylsulfamoyl-8-methoxy-2-naphthyl (388) 5-N-methylsulfamoyl-2-naphthyl (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 -Naphtyl (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-naphthyl (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 (3) 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 (2).

  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-C4H9; 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: 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-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; R 16: 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: CH 2 OCH 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, R14} : 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: CH 2 O-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: 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-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.

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

  The cellulose ester film according to the present invention preferably contains fine particles. In particular, it is preferable to contain in the surface layer mentioned later.

  As fine particles used in the present invention, as examples of inorganic compounds, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, Mention may be made of 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 size 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 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, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above 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 antireflection layer is preferably 1.0 or less.

<dye>
A dye can also be added to the cellulose ester film used in the present invention for color adjustment. 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 order to perform in-line addition and mixing in the present invention, for example, an in-line mixer such as a static mixer (manufactured by Toray Engineering) or SWJ (Toray static type in-tube mixer Hi-Mixer) is preferably used.

<Organic solvent>
An organic solvent that dissolves cellulose ester and is useful for forming a cellulose ester solution or dope can be methylene chloride (methylene chloride), a chlorinated organic solvent, and is suitable for dissolving cellulose ester, particularly cellulose triacetate. Examples of non-chlorine organic solvents include methyl acetate, ethyl acetate, amyl acetate, methyl acetoacetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2- Trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2- Examples include propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, and the like. When these organic solvents are used for cellulose triacetate, a dissolution method at room temperature can be used, but an insoluble material can be obtained by using a dissolution method such as a high-temperature dissolution method, a cooling dissolution method, or a high-pressure dissolution method. Can be reduced, which is preferable. Although methylene chloride can be used for cellulose esters other than cellulose triacetate, methyl acetate, ethyl acetate, and acetone can be preferably used without using methylene chloride. Particularly preferred is methyl acetate. In the present invention, an organic solvent having good solubility with respect to the cellulose ester is referred to as a good solvent, and has a main effect on dissolution, and an organic solvent used in a large amount among them is a main (organic) solvent or a main ( Organic) solvent.

  The dope according to the present invention preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms in addition to the organic solvent. These are used as a gelling solvent that casts the dope on a metal support and then the solvent begins to evaporate and the ratio of alcohol increases and the web gels, making the web strong and easy to peel off from the metal support. When these ratios are small, there is also a role of promoting dissolution of the cellulose ester of the non-chlorine organic solvent. Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Of these, ethanol is preferred because it has excellent dope stability, has a relatively low boiling point, good drying properties, and no toxicity. These organic solvents are called poor solvents because they are not soluble in cellulose esters by themselves. Moreover, you may contain 0.01-2 mass% water in dope.

[Surface]
Next, the surface layer having the cellulose ester according to the present invention will be described.

  The cellulose ester film according to the present invention has a film thickness of 0.1 to 15 μm and a cellulose acylate film having a multilayer structure in which at least one surface layer having a cellulose ester having a total acyl group substitution degree of 2.7 or less is provided on the base layer. It is a feature.

  The inventor of the present invention discloses the organic solvent used in the hard coat layer coated on the surface layer by using a cellulose ester having a total acyl group substitution degree of 2.7 or less. Even without having such a special organic solvent, it has been found that the interface between the surface layer and the hard coat layer is eliminated, and the unevenness of interference can be prevented by continuously changing the refractive index. It is up to you.

  In this invention, the total acyl group substitution degree of the cellulose ester used for a surface layer is 2.7 or less, Preferably it is the range of 1.9-2.7. As the cellulose ester having a total acyl group substitution degree in this range, those similar to the cellulose ester used in the base layer are used, and cellulose diacetate or cellulose acetate propionate is preferable. The total acyl group substitution degree can be adjusted by adjusting the esterification conditions (temperature, time, stirring) and hydrolysis conditions of the cellulose ester as described above.

  The layer configuration may be two or more, and a plurality of layers may be included in the surface layer or the base layer. Preferably, three layers are preferred, two surface layers and one base layer, and three layers are preferred because a sufficient effect can be obtained to produce an excellent hard coat film of the present invention.

  The film thickness per surface layer is in the range of 0.1 to 15 μm, and in order to obtain the effects of the present invention, it is preferably in the range of 0.5 to 15 μm, and more preferably in the range of 1 to 10 μm. It is especially preferable that it is 5-10 micrometers. When the surface layer is a plurality of layers, the thicknesses of the layers may be the same or different.

  The surface layer preferably contains the aforementioned fine particles. Among them, 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.

  The surface layer according to the present invention preferably contains a plasticizer. As the plasticizer, a plasticizer used for the base layer can be used. The plasticizer content is preferably greater than the average plasticizer content in the cellulose ester film having a multilayer structure.

  Further, the surface layer may contain additives such as the ultraviolet absorber, dye, and organic solvent.

[Multilayer cellulose ester film]
The cellulose ester film having a multilayer structure according to the present invention is obtained by forming the surface layer dope and the base layer dope with different compositions by a co-casting method or a sequential casting method. The co-casting method has excellent quality uniformity, and the sequential casting has a high film forming speed and excellent productivity. In the present invention, it is preferable that the substrate film is formed by a co-casting method because the flatness of the substrate film is particularly required for interference unevenness.

  In the present invention, the total film thickness of the cellulose ester film is not particularly limited and is 10 to 500 μm, preferably 10 to 80 μm, the surface layer is thinner than the base layer, and the surface layer thickness is usually as described above. 0.1 to 15 μm, and it is desirable that the entire film thickness, the surface layer and the base layer should be constant, within ± 10% of the average film thickness in both the width and the longitudinal direction of the film, preferably It is desirable that the variation be within ± 5%, more preferably within ± 1%.

  The cellulose ester film having a multilayer structure according to the present invention preferably has a light transmittance (of visible light) of 90% or more, more preferably 92% or more, and further preferably 94% or more. % Is preferable, more preferably less than 0.5%, still more preferably less than 0.1%. In particular, 0% is most preferable.

[Manufacture of cellulose ester film of multilayer structure]
The layer structure of the cellulose ester film having a multilayer structure useful for the hard coat film of the present invention is a multilayer film having a base layer and at least one surface layer as described above, and the multilayer structure may be three or more layers. However, a three-layer structure having one surface layer on each side of the base layer is more preferable.

  Hereinafter, the manufacturing method of the cellulose-ester film of a multilayer structure is demonstrated.

  FIG. 1 schematically shows a cross section of a film having a three-layer structure, in which 1 and 3 are surface layers, and 2 is a base layer.

[Co-casting and sequential casting]
The cellulose ester film having a multilayer structure in the present invention is obtained by laminating a dope in multiple layers by co-casting or sequential casting in a solution casting film forming process.

  FIG. 2 is a diagram showing a co-casting die and cast to form a multi-layered web (the web may also be referred to as a dope film immediately after casting). As shown in FIG. 2, the co-casting has a plurality of slits (three in FIG. 2, surface slits 13 and 15, and base layer slit 14) in the die portion 11 of the co-casting die 10. A web 20 having a multilayer structure of surface layer 21 / base layer 22 / surface layer 23 is formed on the metal support 16 by casting the surface layer dope 17, the base layer dope 18, and the surface layer dope 19 simultaneously from the respective slits. To do.

  FIG. 3 is a view showing a sequential casting die and a web having a multilayer structure. As shown in FIG. 3, the sequential casting is performed by placing a plurality of (three in FIG. 3) surface layer casting dies 30, base layer dies 31, and surface layer casting dies 32 above the metal support 16. First, a surface layer dope 33 which is one surface layer is cast from the surface layer die 30 to form a surface layer dope film 36 on the metal support 16, and then a base layer dope 34 is formed on the base layer die. A base layer dope film 37 is formed on the surface layer dope film 36 from the surface layer 31, and a surface layer dope 35 is cast from the next surface layer die 32 to form a surface layer dope film 38, whereby the surface layer / base layer / surface layer A multilayer construction web 39 is formed.

  FIG. 4 is a view showing a cross section of another type of co-casting die. In the co-casting die 50 in which three layers are joined in the main body, the base layer dope 56 and the surface layer dopes 55 and 57 are introduced into the base layer slit 52 and the surface layer slits 51 and 53, respectively. Are merged at the merging slit 58, pass through the slit 54 in a laminar flow, and are cast in three layers on the metal support 16.

  It is preferred to cast the multi-layer web as shown in FIGS. 2, 3 and 4 so that the surface layer is wider than the base layer and the base web is wrapped by the surface web.

[Solution casting film forming method]
The cellulose ester film of the present invention is formed by a solution casting film forming method. Here, the solution casting film forming method according to the present invention will be described with reference to FIG.

  FIG. 5 is a view schematically showing a dope preparation process of the solution casting film forming apparatus according to the present invention.

  FIG. 6 is a diagram schematically showing from the casting process to the drying process of the solution casting film forming apparatus according to the present invention.

  The following processes will be described with reference to the three-layer co-casting as an example.

(1) Cellulose ester solution preparation process:
The dope preparation step on the upper side of the paper in FIG. 5 is for the base layer, and the dope preparation step on the lower side of the paper is for the surface layer.

  Cellulose ester is dissolved in an organic solvent mainly composed of a good solvent for cellulose ester while stirring the cellulose ester and additives such as a crushed piece of a film to be reused as part of the raw material and a plasticizer in stirring vessel 101. In this step, the solution 100 is formed. For dissolution, a method performed at normal pressure, a method performed below the boiling point of the main solvent, a high-temperature dissolution method performed by pressurization above the boiling point of the main solvent, a cooling dissolution method performed by cooling and a high-pressure dissolution method performed at a considerably high pressure However, in the present invention, the high temperature dissolution method is preferably used. After dissolution, the cellulose ester solution 100 is filtered by a liquid feed pump 102 through a filter 103 (filter press type), left stationary in a stock tank 104 and defoamed, and a liquid feed pump 105 (pressure type metering gear pump) for casting. Etc. are often used), and are transferred by a conduit 108 for mixing in a confluence tube 120 that joins an in-line additive solution 110 containing an ultraviolet absorber via a filter 106. When the dope used for the base layer is a cellulose ester solution 100 containing a plasticizer and an ultraviolet absorber, the dope may be sent directly to the casting die after passing through the filter 106.

  When using the in-line additive liquid 110 containing additives (other than a matting agent) such as an ultraviolet absorber, the liquid is prepared and fed through lines indicated by 111 to 117. The in-line additive solution obtained by dissolving the additive and cellulose ester in the organic solvent in the dissolution vessel 111 may be sent by the pump 112, filtered by the filter 113, and returned to the dissolution vessel 111 through the switching valve 119 and circulated as necessary. Alternatively, it may be stored in the stock tank 114 as it is. The liquid is fed through the conduit 117 via the pump 115 and the filter 116.

  Here, filtration will be described. The cellulose ester solution is filtered using an appropriate filter medium such as filter paper for filter press. As the filtering material in the present invention, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters, etc., but if the absolute filtering accuracy is too small, there is a problem that the filtering material is likely to be clogged. Filter media with an accuracy of 8 μm or less are preferred, filter media in the range of 1-8 μm are more preferred, and filter media in the range of 3-6 μm are even more preferred. Examples of filter paper include No. of Azumi Filter Paper Co., Ltd., a commercially available product. 244 and 277 can be mentioned and are preferably used. Further, the material of the filter medium for filtration is not particularly limited, and a normal filter medium can be used. However, a plastic filter medium such as polypropylene or Teflon (R) or a metal filter medium such as stainless steel may cause the fibers to fall off. Less preferred. Filtration can be performed by a normal method, but the method of filtering while heating or keeping the temperature at a temperature in a range not lower than the boiling point of the organic solvent used under normal pressure and in a range where the organic solvent does not boil is a filter medium. The increase in differential pressure before and after (hereinafter sometimes referred to as filtration pressure) is small and preferable. The preferred temperature range depends on the organic solvent used, but is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C. The filtration pressure is preferably as small as possible, preferably 0.3 to 1.6 MPa, more preferably 0.3 to 1.2 MPa, and still more preferably 0.3 to 1.0 MPa. In addition, you may add an ultraviolet absorber to a cellulose-ester solution in the dissolution pot 101 previously.

(2) Preparation Step of Inline Additive Solution Containing Fine Particles Here, the inline additive solution containing the fine particle dispersion used for the surface layer dope will be described. The preparation method of the fine particle dispersion containing the organic solvent such as lower alcohol used for the cellulose ester solution, the resin described later and the matting agent fine particle described later is particularly suitable if it can be sufficiently uniformly dispersed in the liquid. Although there is no limitation, the following method is preferable.

  In FIG. 5 (bottom of the paper surface of FIG. 5), the in-line additive liquid 110A containing fine particles is a cellulose ester solution obtained by stirring and dissolving a cellulose ester in an organic solvent in a dissolution / dispersion vessel 111A. Separately, a fine particle dispersion dispersed with a disperser (not shown) such as Menton Goleen or Sand Mill is added. Here, the in-line additive solution 110A containing fine particles is obtained by sufficiently stirring and stabilizing the dispersion. This in-line additive solution 110A is passed through a filter 113A by a liquid feed pump 112A and, if necessary, through a switching valve 119A and sent to a dissolution / dispersion vessel 110A to repeatedly circulate the same operation several times to remove aggregates. You may let them. Thereafter, the switching valve 119A is switched, the in-line additive liquid 110A is temporarily transferred to the stock tank 114A, and after stationary deaeration, transferred by a liquid feed pump 115A (for example, a pressurized metering gear pump), filtered by a filter 116A, and a conduit. Transfer via 117A. Further, the liquid may be fed through the liquid feed pump 115A, the filter 116A, and the conduit 117A without being left in the stock tank 114A. When the surface layer has different compositions on the front side and the back side, a liquid preparation step similar to that shown for 150A can be provided separately.

  In addition, the process of preparing the cellulose ester solution 100A for surface layer of FIG. 5 is the same as the 101-108 line of the above-mentioned cellulose ester solution 100 in the 101A-108A line. 101A to 108A correspond to 101 to 108. The cellulose ester solution 100A and the fine particle in-line additive solution 110A are merged at the merge point 120A.

  Note that the cellulose ester 100 can be used for the base layer and the surface layer by using the 101-108 line and the 101A-108A line in common.

  Examples of the method for preparing the fine particle dispersion according to the present invention include the following three types.

(Preparation method A)
After stirring and mixing the organic solvent and the fine particles, dispersion is performed with a disperser. This is a fine particle dispersion.

(Preparation method B)
After stirring and mixing the organic solvent and the fine particles, dispersion is performed with a disperser to obtain a fine particle dispersion. Separately, add a small amount of resin (resin with good dispersibility to fine particles and moderate viscosity to the liquid, and compatible with cellulose ester or cellulose ester) to an organic solvent, and stir and dissolve the resin solution. prepare. The fine particle dispersion is added to this, stirred and sufficiently dispersed to obtain a fine particle dispersion.

(Preparation method C)
A small amount of resin (a resin having good dispersibility with respect to fine particles and compatible with cellulose ester or cellulose ester) is added to an organic solvent, and dissolved by stirring. Fine particles are added to this and sufficiently dispersed with a disperser to obtain a fine particle dispersion.

  Preparation method A is excellent in dispersibility of silicon dioxide fine particles, and preparation method C is excellent in that the silicon dioxide fine particles are difficult to reaggregate. The preparation method B is a preferable preparation method that is excellent in both dispersibility of the silicon dioxide fine particles and difficulty in reaggregation of the silicon dioxide fine particles.

  The in-line additive solution containing the fine particle dispersion prepared by the preparation methods A to C is added to the cellulose ester solution and stirred to form a dope, but the in-line additive solution 110A and the cellulose ester solution 100A are joined by the in-line mixer 121A. It is preferable to mix well to obtain a dope containing fine particles. The dope containing the fine particles may contain an ultraviolet absorber, and in this case, it is preferably added to the cellulose ester solution.

  In the above preparation method, the concentration of silicon dioxide when the silicon dioxide fine particles are mixed with an organic solvent and dispersed is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and still more preferably 15 to 20% by mass. The higher the dispersion concentration, the lower the liquid turbidity with respect to the amount added, and the lower the haze of the film obtained, and there is no aggregate, which is preferable.

  The organic solvent used is preferably the organic solvent used for the dope, but is not particularly limited. Examples of lower alcohols used for the dope include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like, and ethanol is particularly preferable.

  As a resin that helps dispersibility of fine particles, improves dispersibility, and is compatible with cellulose ester, cellulose ester used for dope may be used. At this time, it can be preferably used because it is not easily clogged. For example, Actflow series resins commercially available from Soken Chemical Co., Ltd. can be preferably used.

(Distributor)
As the disperser for dispersing the fine particles, a normal disperser can be used. Dispersers can be broadly divided into media dispersers and medialess dispersers. For dispersion of silicon dioxide fine particles, a medialess disperser is preferred because of low haze. Examples of the media disperser include a ball mill, a sand mill, and a dyno mill. Examples of the medialess disperser include an ultrasonic type, a centrifugal type, and a high pressure type. In the present invention, a high pressure disperser is preferable. A high-pressure dispersion device is a device that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and a solvent are mixed at high speed through a narrow tube.

  When processing with a high-pressure dispersion apparatus, for example, the maximum pressure condition inside the apparatus is preferably 10 MPa or more in a thin tube having a tube diameter of 1 to 2000 μm. More preferably, it is 20 MPa or more. Further, at that time, those having a maximum reaching speed of 100 m / second or more and those having a heat transfer speed of 420 kJ / hour or more are preferable. The high-pressure dispersing apparatus as described above includes an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, and other manton gorin type high-pressure dispersing apparatuses such as a homogenizer manufactured by Izumi Food Machinery Co., Ltd. Examples include UHN-01 manufactured by Wakki Co., Ltd.

  The in-line additive liquid 110A eliminates the stagnation in the stock tank 114A, and if possible, does not use the liquid feed pump 115A, and is transferred by the pipe 117A immediately after filtration by the final filter 116A. This is desirable because generation of new aggregates can be suppressed.

  The filter for the in-line additive liquid containing fine particles is preferably placed immediately before the in-line mixer.For example, large aggregates generated from the path due to filter medium exchange or the like can be filtered once from the fine particle dispersion in the liquid feed. It is preferable to use a metal filter having an organic solvent resistance that can be used for a long period of time and has the absolute filtration accuracy as a filter medium for reliably removing relatively large foreign substances. The filter medium is preferably a metal, particularly stainless steel, from the viewpoint of durability. From the viewpoint of clogging, it is preferable to have a porosity of 60 to 80%. Therefore, it is most preferable to filter with a metal filter medium having an absolute filtration accuracy of 30 to 60 μm and a porosity of 60 to 80%, thereby reliably removing coarse foreign substances over a long period of time. Is preferable. Examples of metal filter media having an absolute filtration accuracy of 30 to 60 μm and a porosity of 60 to 80% include NF-10, NF-12, and NF-13 of Fine pore NF series manufactured by Nippon Seisen Co., Ltd. Any of these is preferably used.

(3) Dope preparation process:
The dope preparation steps 150 and 150A referred to here are steps in which the cellulose ester solution and the in-line additive solution are sufficiently mixed with mixers 121 and 121A such as an in-line mixer to form a dope.

  150 is a step for preparing a base layer and 150A is a dope for a surface layer containing fine particles.

  The cellulose ester solution 100 or 100A and the in-line additive solution 110 or 110A are combined with each other by a merging tube 120 or 120A, and sufficiently mixed by a mixer 121 or 121A such as an in-line mixer to be used for a base layer or a surface layer. Dope. Also. As an in-line mixer that can be preferably used in the present invention, for example, a static mixer SWJ (Toray static type in-pipe mixer Hi-Mixer, manufactured by Toray Engineering) can be exemplified and preferably used.

  In the later-described co-casting die, the dope prepared by changing the components according to the respective purposes is supplied to each slit. The viscosity of the dope used for the base layer is preferably 50 to 10,000 Pa · s (at 35 ° C.), particularly preferably 50 to 1,000 Pa · s. The viscosity of the dope used for the surface layer is preferably 0.1 to 5,000 Pa · s, more preferably 5 to 1,000 Pa · s, still more preferably 10 to 500 Pa · s, and particularly preferably 10 ~ 50 Pa · s. In the present invention, the viscosity of the surface layer dope is preferably lower than that of the base layer.

  Hereinafter, an example of production of the cellulose ester film according to the present invention will be described with reference to FIG.

(4) Co-casting process:
The base layer dope is introduced into the dope supply port 202 of the co-casting die 200, and the surface layer dope containing fine particles is introduced into the surface layer supply port 201 and / or 203 and co-cast.

  FIG. 6 shows, for example, three layers of dope from a co-casting die 200 at a casting position on an endless metal support 204 that moves indefinitely, such as a stainless steel belt or a rotating metal drum 204. It is a process of co-casting. The surface of the metal support 204 is preferably a mirror surface. A co-casting die 200 (for example, a pressure-type co-casting die) is preferable because it can prepare three slit shapes in the die portion and easily make the film thickness uniform. As the co-casting die, those shown in FIG. 2 or FIG. 4 are preferably used, but are not limited thereto. The co-casting die 200 includes a coat hanger die and a T die, and any of them is preferably used.

  In the case of sequential casting, two or more single-layer dies are shifted on the metal support 204 and two or more types of dope amounts are supplied to form a multilayer doped film.

(5) Solvent evaporation step:
For example, a web 206 having a three-layer structure (referred to as a dope film after casting a dope on a metal support) is heated or cooled on the metal support 204 so that the web 206 is transferred from the metal support 204 to the web 206. This is a step of evaporating the solvent until it can be peeled off. In order to evaporate the solvent, there are a method of applying air to the web 206 and / or a method of transferring heat from the back surface of the metal support 204 by liquid or gas, a method of transferring heat from the front and back by radiant heat, and the like. This method is preferable because of good drying efficiency. A method of combining them is also preferable. In the case of backside liquid heat transfer, it is preferable to heat the web temperature on the metal support below the boiling point of the main solvent of the organic solvent used in the dope or the organic solvent having the lowest boiling point. The surface temperature of the metal support for casting is 10 to 55 ° C., the temperature of the solution is 25 to 60 ° C., and the temperature of the solution is preferably equal to or higher than the temperature of the support. More preferably, the temperature is set to a temperature of The higher the solution temperature and the support temperature, the faster the solvent can be dried. However, if the temperature is too high, foaming or flatness may be deteriorated. Although the more preferable range of the temperature of a support body is dependent on the organic solvent to be used, it is 20-55 degreeC, and the more preferable range of solution temperature is 35-45 degreeC.

(7) Peeling process:
In this step, the web 206 having the solvent evaporated on the metal support 204 is peeled off at the peeling position 205. The peeled web 206 is sent to the next (7) drying step (described later). If the amount of residual solvent (explained later) of the web 206 at the time of peeling is too large, it will be difficult to peel off, or conversely if it is dried too much on the metal support 204, it will be difficult to peel off, Part of 206 is peeled off. In the present invention, when the thin web is peeled from the metal support, it is preferably peeled with a force within 300 N / m from the lowest tension that can be peeled off, and more preferably within 200 N / m.

  There is a gel casting method (gel casting) as a method for increasing the film-forming speed (the film-forming speed can be increased because peeling occurs while the amount of residual solvent is as large as possible). For example, a poor solvent for the cellulose ester is added to the dope, and the dope is cast and then gelled, and the temperature of the metal support is lowered to gel. By gelling on the metal support 204 and increasing the strength of the film at the time of peeling, peeling can be accelerated and the film forming speed can be increased. It is preferable to peel in the range of 5 to 150% by mass depending on the setting of the drying conditions of the web 206 on the metal support 204, the length of the metal support 204, etc. If the web 206 is too soft, the flatness at the time of peeling is impaired, or slippage or vertical streaks due to peeling tension are likely to occur, and the amount of residual solvent to be peeled can be determined based on the balance between economic speed and quality. Accordingly, in the present invention, the temperature at the peeling position on the metal support 204 is preferably 0 to 40 ° C, more preferably 10 to 30 ° C.

  In order to maintain good flatness of the cellulose ester film during production, the amount of residual solvent when peeling from the metal support is preferably 10 to 150% by mass, more preferably 80 to 150% by mass. More preferably, it is 100-130 mass%. The ratio of the good solvent contained in the residual organic solvent of the web at the time of peeling is preferably 30 to 90%, more preferably 50 to 85%, and particularly preferably 60 to 80%.

  In the present invention, the residual solvent amount can be expressed by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
Here, M is the mass of the web at any point in time, and the ratio of the components volatilized by this drying can be determined by gas chromatography. N is the mass when the M is dried at 110 ° C. for 3 hours. The measurement is performed by gas chromatography connected to a headspace sampler. In the present invention, gas chromatography 5890 type SERISII manufactured by Hewlett-Packard Company and headspace sampler HP7694 type were used, and the measurement was performed under the following measurement conditions.

Headspace sampler heating conditions: 120 ° C, 20 minutes GC introduction temperature: 150 ° C
Temperature rise: 40 ° C, hold for 5 minutes → 100 ° C (8 ° C / min)
Column: J-W DB-WAX (inner diameter 0.32 mm, length 30 m).

  In the present invention, the drying time on the metal support of the web from dope casting to peeling is preferably a peelable time and within 120 seconds, more preferably 30 to 120 seconds, and further 30 -90 seconds are preferred. The surface property of the web peeled in this range is good. When the metal compound thin film described below is applied to the cellulose ester film after drying, it has excellent flatness and no cracks when repeatedly exposed to high temperature and high humidity conditions. An excellent optical film can be obtained.

(7) Drying process:
After peeling, generally, the web 206 is used by using a roll drying device 208 that alternately conveys the web 206 through vertically arranged rolls 209 and / or a tenter device 207 that grips and conveys both ends of the web 206 with a clip or the like. To dry. In FIG. 6, a roll drying device 208 is disposed after the tenter device 207. As a drying means, hot air is generally blown on both sides of the web, but there is also a means for heating by applying a microwave instead of the wind. Too rapid drying tends to impair the flatness of the finished film. Throughout, the drying temperature is usually in the range of 40 to 250 ° C., preferably 110 to 160 ° C. The drying temperature, the amount of drying air, and the drying time differ depending on the solvent used, and the drying conditions may be appropriately selected according to the type and combination of the solvents used. 210 is winding of the completed cellulose ester film. In the step of drying the cellulose ester film, the amount of residual solvent is preferably 1% by mass or less, and more preferably 0.1% by mass or less.

  In order to produce the cellulose ester film for a hard coat film of the present invention, the web is stretched in the conveying direction where the residual solvent amount of the web immediately after peeling from the metal support 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 stretching ratios in the machine direction and the transverse direction is less than 1.05, the flatness deterioration due to ultraviolet irradiation when forming the hard coat layer is not preferable. Moreover, when the draw ratio exceeds 1.3 times, the haze tends to increase.

[Actinic radiation curable resin layer]
In the present invention, a hard coat layer is coated on the cellulose ester film. A method for producing an actinic radiation curable resin layer used as a hard coat layer will be described.

  In the hard coat film of the present invention, an actinic radiation curable resin layer is preferably used as the hard coat layer.

  The actinic radiation curable resin layer refers to a layer mainly composed of a resin that cures through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. As the actinic radiation curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and a hard coat layer is formed by curing by irradiation with actinic radiation such as ultraviolet rays or electron beams. Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin curable by ultraviolet irradiation is preferable.

  As the ultraviolet curable resin, for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates) in products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used.

  For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.

  Examples of UV curable polyester acrylate resins include those that are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added thereto, and reacted to form an oligomer. The thing as described in 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. I can list them.

  Specific examples of the photoreaction initiator of these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer. The photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photoinitiator, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.

  Examples of the resin monomer include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  Examples of commercially available ultraviolet curable resins that can be used in the present invention include ADEKA OPTMER KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka ( Co., Ltd.); Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS -101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP -10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.) KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by Daicel UCB Corporation); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120 RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries); SP -1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), etc. Can be selected as appropriate.

  Specific examples of compounds include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like. .

  These actinic ray curable resin layers can be coated by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or an ink jet method.

As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured film layer, any light source that generates ultraviolet rays can be used without any limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is preferably 5 to 150 mJ / cm ² , particularly preferably 20 to 100 mJ / cm ² .

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

  Examples of the organic solvent for the UV curable resin layer composition coating solution include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl). Ketone), esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, other organic solvents, or a mixture thereof. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%.

  In addition, it is particularly preferable to add a silicon compound to the ultraviolet curable resin layer composition coating solution. For example, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1,000 to 100,000, preferably 2,000 to 50,000. When the number average molecular weight is less than 1,000, the coating film is dried. On the contrary, when the number average molecular weight exceeds 100,000, it tends to be difficult to bleed out on the surface of the coating film.

  Commercially available silicon compounds include DKQ8-779 (trade name, manufactured by Dow Corning), SF3771, SF8410, SF8411, SF8419, SF8421, SF8428, SH200, SH510, SH1107, SH3749, SH3771, BX16-034, SH3746, SH3749, SH8400, SH3771M, SH3772M, SH3773M, SH3775M, BY-16-837, BY-16-839, BY-16-869, BY-16-870, BY-16-004, BY-16-891, BY-16 872, BY-16-874, BY22-008M, BY22-012M, FS-1265 (above, product names manufactured by Toray Dow Corning Silicone), KF-101, KF-100T, KF351, KF3 2, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, Silicone X-22-945, X22-160AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), XF3940, XF3949 (trade name, manufactured by Toshiba Silicone Co., Ltd.) ), Disparon LS-009 (manufactured by Enomoto Kasei Co., Ltd.), Granol 410 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone), BYK-306, BYK- 330, BYK-307, BYK-341, BYK-344, BYK-361 (manufactured by BYK-Japan) L series (for example, L7001, L-7006, L-7604, L-9000) manufactured by Nippon Unicar Co., Ltd. Y Over's, FZ series (FZ-2203, FZ-2206, FZ-2207) and the like, are preferably used.

  These components enhance the applicability to the substrate and the lower layer. When added to the outermost surface layer of the laminate, it not only improves the water repellency, oil repellency and antifouling properties of the coating film, but also exhibits an effect on the scratch resistance of the surface. These components are preferably added in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.

  As a coating method of the ultraviolet curable resin composition coating solution, the above-described methods can be used. The coating amount is suitably 0.1 to 30 μm, preferably 0.5 to 15 μm, as the wet film thickness. The dry film thickness is 0.1 to 20 μm, preferably 1 to 10 μm.

  More preferably, when the film thickness of the cellulose ester film is 10 to 80 μm and the ratio (d / H) of the film thickness (H) of the layer to the film thickness (d) of the cellulose ester film is 4 to 10, It has excellent hardness and scratch resistance. This is because the hardness and scratch resistance are inferior when the hard coat layer is thinner than the film thickness of the cellulose ester, and the flatness is deteriorated when the hard coat layer is thicker than the film thickness of the cellulose ester.

The ultraviolet curable resin composition is preferably irradiated with ultraviolet rays during or after coating and drying, and the irradiation time for obtaining the active ray irradiation amount of 5 to 150 mJ / cm ² is from 0.1 second to 5 seconds. Minutes are good, and 0.1 to 10 seconds is more preferable from the viewpoint of curing efficiency or work efficiency of the ultraviolet curable resin.

Moreover, it is preferable that the illuminance of these active ray irradiation parts is 50-150 mW / m < ² >.

  In order to prevent blocking, to improve scratch resistance, to give antiglare property or light diffusibility, and to adjust the refractive index in the cured resin layer thus obtained, fine particles of an inorganic compound or an organic compound Can also be added.

  Inorganic fine particles used in the hard coat layer include silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, silicic acid Mention may be made of aluminum, magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

  The organic fine particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, and melamine resin powder. Polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluoroethylene resin powder can be added to the ultraviolet curable resin composition. Particularly preferred are cross-linked polystyrene particles (for example, SX-130H, SX-200H, SX-350H, manufactured by Soken Chemical) and polymethyl methacrylate-based particles (for example, MX150, MX300, manufactured by Soken Chemical).

  The average particle diameter of these fine particle powders is preferably 0.005 to 5 μm, and particularly preferably 0.01 to 1 μm. As for the ratio of a ultraviolet curable resin composition and fine particle powder, it is desirable to mix | blend so that it may be 0.1-30 mass parts with respect to 100 mass parts of resin compositions.

  The ultraviolet curable resin layer is a clear hard coat layer having a center line average roughness (Ra) defined by JIS B 0601 of 1 to 50 nm or an antiglare layer having an Ra of about 0.1 to 1 μm. Is preferred. The center line average roughness (Ra) is preferably measured with an optical interference type surface roughness measuring instrument, and can be measured using, for example, RST / PLUS manufactured by WYKO.

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

  As fine particles added to the back coat layer, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, and indium oxide. Zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low haze, and silicon dioxide is particularly preferable.

  These fine particles are commercially available under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, and TT600 (manufactured by Nippon Aerosil Co., Ltd.). . Zirconium oxide fine particles are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used. Examples of the polymer fine particles 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 anti-blocking effect while keeping haze low. The hard coat film used in the present invention preferably has a coefficient of dynamic friction on the back side of the hard coat layer of 0.9 or less, particularly 0.1 to 0.9.

  The fine particles contained in the backcoat layer are 0.1 to 50% by weight, preferably 0.1 to 10% by weight, based on the binder. When the back coat layer is provided, the increase in haze is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.0 to 0.1%.

  Specifically, the back coat layer is formed by applying a composition containing a solvent for dissolving or swelling a cellulose ester film. The solvent to be used may include a solvent to be dissolved and / or a solvent to be swollen in addition to a solvent to be swelled, a composition in which these are mixed at an appropriate ratio depending on the degree of curl of the transparent resin film and the type of resin, This is done using the coating amount.

  In order to enhance the curl prevention function, it is effective to increase the mixing ratio of the solvent for dissolving the solvent composition to be used and / or the solvent for swelling, and to decrease the ratio of the solvent not to be dissolved. This mixing ratio is preferably (solvent to be dissolved and / or solvent to be swollen) :( solvent to be dissolved) = 10: 0 to 1: 9. Examples of the solvent for dissolving or swelling the transparent resin film contained in such a mixed composition include dioxane, acetone, methyl ethyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, and ethylene chloride. , Tetrachloroethane, trichloroethane, chloroform and the like. Examples of the solvent that does not dissolve include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, and hydrocarbons (toluene, xylene, cyclohexanol).

  These coating compositions are preferably applied to the surface of the transparent resin film with a gravure coater, dip coater, reverse coater, wire bar coater, die coater, etc., with a wet film thickness of 1 to 100 μm, particularly 5 to 30 μm. Preferably there is. Examples of the resin used as the binder of the backcoat layer include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate-vinyl alcohol copolymer, partially hydrolyzed vinyl chloride-vinyl acetate copolymer. Polymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. Vinyl polymer or copolymer, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8-2.3, propionyl group substitution degree 0.1-1.0), diacetyl cellulose, cellulose Cellulose derivatives such as acetate butyrate resin, maleic acid and / or Or acrylic acid copolymer, acrylic ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin Rubber resins such as polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butadiene resin, butadiene-acrylonitrile resin, Examples thereof include, but are not limited to, silicone resins and fluorine resins. For example, as an acrylic resin, Acrypet MD, VH, MF, V (manufactured by Mitsubishi Rayon Co., Ltd.), Hyperl M-4003, M-4005, M-4006, M-4202, M-5000, M-5001, M-4501 (manufactured by Negami Kogyo Co., Ltd.), Dialnal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR-79, BR -80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105 BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (Mitsubishi Rayon Co., Ltd.) acrylic and The methacrylic monomers such as various homopolymers and copolymers were prepared as raw materials are commercially available, can also be selected preferred mono from this appropriate.

  Particularly preferred are cellulose resin layers such as diacetylcellulose and cellulose acetate propionate.

  The order of coating the backcoat layer may be before or after coating the cellulose ester film on the opposite side of the backcoat layer (clear hard coat layer or other layer such as an antistatic layer). When the back coat layer also serves as an anti-blocking layer, it is desirable to coat it first. Alternatively, the back coat layer can be applied twice or more before and after the hard coat layer is applied.

(Antireflection layer)
In the hard coat film of the present invention, it is preferable to form a thin metal compound layer uniformly by coating or plasma CVD, particularly atmospheric pressure plasma treatment, and these are useful as an antireflection layer.

  As an atmospheric pressure plasma treatment method, for example, an atmospheric pressure plasma discharge treatment method for applying a high-frequency pulse voltage described in JP-A-11-181573, JP-A-2000-26632, JP-A-2002-110397, or the like can be used. Alternatively, the conductive layer can be provided by an atmospheric pressure plasma discharge processing method described in JP-A-2001-337201. Alternatively, the antireflection layer can be provided by the methods described in JP-A No. 2002-228803, Japanese Patent Application No. 2002-369679, Japanese Patent Application No. 2002-317883, and Japanese Patent Application No. 2003-50823. Alternatively, the antifouling layer can be provided by the method described in Japanese Patent Application No. 2003-50823. Alternatively, the antireflection layer can be applied by the method described in JP-A-2003-93963 and Japanese Patent Application No. 2002-49724.

On the hard coat film of the present invention, metal compounds (for example, SiO _x , SiO _x N _y , TiO _x N _y , SiO _x C _z (x = 1 to 2, y = It is preferable to form a thin film such as a metal oxide among metal oxides such as 0.1-1 and z = 0.1-2), metal nitrides, metal oxynitrides, metal carbides). The nitrogen gas contained in the gas is 60 to 99.9% by volume, preferably 75 to 99.9% by volume, and more preferably 90 to 99.9% by volume. In addition to nitrogen gas, a rare gas such as argon or helium may be contained, a gas of a metal compound for forming a thin film is contained, and further a gas (addition gas) for promoting a reaction such as oxygen and hydrogen. Or an auxiliary gas). By these, a low refractive index layer, a high refractive index layer, a medium refractive index layer, a transparent conductive layer, an antistatic layer, an antifouling layer and the like containing a metal compound can be formed.

  Next, the antireflection layer formed on these hard coat layers will be described.

(Antireflection layer)
In the present invention, the method for providing the antireflection layer is not particularly limited, and the antireflection layer can be formed by coating, sputtering, vapor deposition, CVD (Chemical Vapor Deposition), or a combination thereof.

  As a method of forming the antireflection layer by coating, a method of dispersing a metal oxide powder in a binder resin dissolved in a solvent, coating and drying, a method of using a polymer having a crosslinked structure as a binder resin, ethylenic unsaturated Examples of the method include a method of forming a layer by containing a monomer and a photopolymerization initiator and irradiating actinic rays.

  In the present invention, an antireflection layer can be provided on the hard coat film provided with the hard coat layer. A metal oxide layer with a low refractive index is formed on the uppermost layer of the hard coat film, and a metal oxide layer with a high refractive index layer is formed between them, and further between the hard coat film and the high refractive index layer. It is preferable to provide a refractive index layer (a metal oxide layer in which the refractive index is adjusted by changing the metal oxide content or the ratio to the resin binder and the type of metal) in order to reduce the reflectance. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the medium refractive index layer is adjusted so as to be an intermediate value between the refractive index (about 1.5) of the cellulose ester film as the substrate and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80. The thickness of each layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and most preferably 30 nm to 0.2 μm. The haze of the metal oxide layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the metal oxide layer is preferably 3H or more, and most preferably 4H or more, with a pencil hardness of 1 kg. When the metal oxide layer is formed by coating, it is preferable to include inorganic fine particles and a binder polymer.

The inorganic fine particles used for the metal oxide layer such as the middle refractive index layer or the high refractive index layer preferably have a refractive index of 1.80 to 2.80, more preferably 1.90 to 2.80. . The mass average diameter of the primary particles of the inorganic fine particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The mass average diameter of the inorganic fine particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and most preferably 10 to 80 nm. . The average particle diameter of the inorganic fine particles is measured by a light scattering method if it is 20-30 nm or more and by an electron micrograph if it is 20-30 nm or less. The specific surface area of the inorganic fine particles, a measured value by the BET method, is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, a 30 to 150 m ² / g Is most preferred.

  The inorganic fine particles are particles formed from a metal oxide. Examples of metal oxides or sulfides include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, and the like. Of these, titanium dioxide, tin oxide, and indium oxide are particularly preferable. The inorganic fine particles are mainly composed of oxides 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, and S.

  The inorganic fine 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, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, a silane coupling agent is most preferable. It may be processed by combining two or more types of surface treatments.

  The shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a layer shape, a spindle shape, or an indefinite shape. Two or more kinds of inorganic fine particles may be used in combination in the metal oxide layer.

  The proportion of the inorganic fine particles in the metal oxide layer is preferably 5 to 90% by volume, more preferably 10 to 65% by volume, and still more preferably 20 to 55% by volume.

  The inorganic fine particles are supplied to a coating liquid for forming a metal oxide layer in a dispersion state dispersed in a medium. As the dispersion medium for the inorganic fine particles, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, Examples include dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), and ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

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

  The metal oxide layer preferably uses a polymer having a crosslinked structure (hereinafter also referred to as “crosslinked polymer”) as a binder polymer. Examples of the crosslinked polymer include polymers having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as “polyolefin”), crosslinked products such as polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. Among them, a crosslinked product of polyolefin, polyether and polyurethane is preferred, a crosslinked product of polyolefin and polyether is more preferred, and a crosslinked product of polyolefin is most preferred. Moreover, it is more preferable that the crosslinked polymer has an anionic group. The anionic group has a function of maintaining the dispersion state of the inorganic fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but is bonded to the main chain as a side chain via the linking group. Is preferred.

  The refractive index of the low refractive index layer used in the antireflective layer of the present invention is preferably 1.46 or less, and particularly preferably 1.3 to 1.45, by silicon alkoxide as a coating composition by a sol-gel method. A low refractive index layer can be formed. Alternatively, a low refractive index layer can be formed using a fluororesin. In particular, it is preferably composed of a cured product of thermosetting or ionizing radiation curable fluorine-containing resin and the cured product and ultrafine particles of silicon oxide.

  The dynamic friction coefficient of the cured product is preferably 0.02 to 0.2, and the pure water contact angle is preferably 90 to 130 °. Examples of the curable fluorine-containing resin include perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane) and fluorine-containing copolymers (crosslinkable groups). Monomer and fluorine-containing monomer as structural units). Specific examples of the fluorine-containing monomer unit include, for example, hexafluoroethylene, hexafluoropropylene, tetrafluoroethylene, and fluoroolefins (for example, vinylidene fluoride perfluoro-2,2-dimethyl-1,3-dioxole, fluoroethylene, etc.) , Fluorinated alkyl ester derivatives of (meth) acrylic acid (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fluorinated vinyl ethers, and the like. As a monomer having a crosslinkable group, a (meth) acrylate monomer having a crosslinkable functional group in the molecule in advance such as glycidyl methacrylate, and a (meth) acrylate having a carboxyl group, an amino group, a hydroxyl group, a sulfonic acid group, etc. And monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.). It is described in JP-A-10-25388 and JP-A-10-147739 that a crosslinked structure can be introduced after copolymerization.

  Moreover, not only the polymer which uses the said fluorine-containing monomer as a structural unit but the copolymer with the monomer which does not contain a fluorine atom can be used. There are no particular limitations on the monomer units that can be used in combination, for example, acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate), methacrylate esters (methyl methacrylate, ethyl methacrylate, Butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, α-methylstyrene, vinyltoluene, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, acrylonitrile Derivatives, olefins (ethylene, propylene, isoprene, vinylidene chloride, vinyl chloride, etc.), vinyl ethers (methyl vinyl ether, etc.), vinyl esters (vinyl acetate, propionic acid) Alkenyl, vinyl cinnamate) may be mentioned.

  In order to improve the scratch resistance, it is preferable to add silicon oxide fine particles to the fluorine-containing resin used for forming the low refractive index layer. The addition amount is adjusted in consideration of the refractive index and scratch resistance. As the silicon oxide fine particles, silica sol dispersed in a commercially available organic solvent can be added to the coating composition as it is, or various commercially available silica powders can be dispersed in an organic solvent and used.

  The coating composition for forming a low refractive index layer of the antireflection film of the present invention preferably contains a solvent having a low boiling point mainly. Specifically, the solvent having a boiling point of 100 ° C. or less is preferably 50% by mass or more of the total solvent. As a result, even when coated on the surface of a substrate having irregularities such as an antiglare layer, it can be dried quickly, fine film thickness unevenness due to the flow of the coating liquid is reduced, and an increase in reflectance is suppressed. The In addition, it is preferable that a solvent having a boiling point of 100 ° C. or higher is included because drying unevenness and white turbidity unevenness are suppressed.

  Low boiling point solvents used in coating compositions for the low refractive index layer include ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, ether alcohols such as methyl cellosolve, methanol, ethanol, and isopropanol. Among such alcohols, those having a high solubility of the solid content contained in the coating composition are preferably used. Coating solvents having a boiling point exceeding 100 ° C. include ketones such as cyclohexanone, cyclopentanone and methyl-isobutyl ketone, ether alcohols such as diacetone alcohol and propylene glycol monomethyl ether, and alcohols such as 1-butanol and 2-butanol. Etc. are used.

  Each layer of the antireflection film can be formed by coating by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a micro gravure coating method or an extrusion coating method. I can do it.

  In the present invention, a method of forming a metal oxide layer by plasma discharge treatment can be used.

  A method for forming a metal oxide layer by plasma discharge treatment will be described below with reference to FIGS.

  Plasma discharge treatment under atmospheric pressure or a pressure in the vicinity thereof as a method for forming a metal oxide layer on the hard coat film of the present invention is performed by using a plasma discharge treatment apparatus as described below.

  FIG. 7 is a view showing an example of a plasma discharge treatment apparatus used for forming a metal oxide layer on the hard coat film of the present invention.

  In FIG. 7, this apparatus has a pair of rotating electrodes 10A and 10B. A power supply 80 to which a voltage for generating plasma discharge can be applied is connected to the rotating electrodes 10A and 10B. Connected to ground, 82 is connected to ground.

  Rotating electrodes 10A and 10B are conveyed while winding a hard coat film, and are preferably roll electrodes or belt-like electrodes, and FIG. 7 shows roll electrodes.

  A gap (electrode gap) between these rotating electrodes is a place where electric discharge is performed, and is set to an interval at which the hard coat film F can be conveyed. The gap between the electrodes becomes the discharge part 50.

  The gap between the electrodes is maintained at atmospheric pressure or a pressure close to atmospheric pressure. The reaction gas G is supplied from the reaction gas supply unit 30 and the surface of the hard coat film F is subjected to plasma discharge treatment.

  Here, the hard coat film F unwound from the original winding roll or the hard coat film F conveyed from the previous process is first transferred through the guide roll 20 while being in contact with the rotating electrode 10A rotating in the transfer direction, A thin film is formed on the surface of the hard coat film F through the discharge part 50.

  The hard coat film F that has once exited from the discharge section 50 is U-turned by the U-turn rolls 11A to 11D, and this time, the hard coat film F contacts the rotating electrode 10B rotating in the opposite direction to the rotating electrode 10A. The thin film is further formed by plasma discharge treatment on the surface of the hard coat film F on which the thin film has been formed. The U-turn is usually performed in about 0.1 seconds to 1 minute.

  The reaction gas G used for the treatment is discharged from the gas discharge port 40 as exhaust gas G ′ after the reaction. It is preferable that the reaction gas G is heated to room temperature to 250 ° C., preferably 50 to 150 ° C., more preferably 80 to 120 ° C., and then fed into the discharge part 50.

  In addition, it is preferable that the discharge part 50 is provided with the rectification | straightening board 51, and while making the flow of the reaction gas G and waste gas G 'smooth, the discharge part 50 spreads and unnecessary discharge is made between electrodes 10A and 10B. The rectifying plate 51 is preferably made of an insulating member.

  In the figure, the thin film formed on the hard coat film F is omitted. The hard coat film F having a thin film formed on the surface is conveyed in the direction of the next process or a take-up roll (not shown) via the guide roller 21.

  Therefore, the hard coat film F is subjected to plasma discharge treatment by reciprocating the discharge portion 50 in a state of being in close contact with the rotary electrodes 10A and 10B.

  Although not shown in the drawing, the devices such as the rotating electrodes 10A and 10B, the guide rolls 20 and 21, the U-turn rolls 11A to 11D, the reactive gas supply unit 30, and the gas discharge port 40 are in a plasma discharge processing vessel that is shielded from the outside. It is preferable that it is enclosed and enclosed.

  Although not shown, a temperature control medium for controlling the temperature of the rotating electrodes 10A and 10B is circulated as necessary to control the surface temperature of each electrode to a predetermined value. . The diameters of the rotating electrodes 10A and 10B are 10 to 1000 mm, preferably 50 to 500 mm, and those having different diameters may be used in combination.

  FIG. 8 is a view showing an example of a plasma discharge treatment apparatus having a rotating electrode and a fixed electrode useful for forming a metal oxide thin film layer on the hard coat film of the present invention.

  A rotating electrode 110 and a plurality of fixed electrodes 111 arranged opposite to the rotating electrode 110 and a hard coat film F conveyed from a not-shown original winding roll or a previous process pass through a guide roll 120 and a nip roll 122 to rotate the rotating electrode 110, the hard coat film F is transferred in synchronization with the rotation of the rotating electrode 110 while being in contact with the rotating electrode 110, and is supplied to the discharge unit 150 under the atmospheric pressure or in the vicinity thereof by the reaction gas generator 131. The prepared reaction gas G is supplied from the supply pipe 130, and a thin film is formed on the hard coat film surface facing the fixed electrode 111.

  A power supply 180 capable of applying a voltage for generating plasma discharge is connected to the voltage supply means 181 between the rotating electrode 110 and the fixed electrode, one of which is connected to the ground, and 182 is connected to the ground.

  Further, the rotating electrode 110, the fixed electrode 111, and the discharge unit 150 are covered with a plasma discharge processing vessel 190 and are shielded from the outside. The treated exhaust gas G ′ is discharged from a gas exhaust port 140 at the lower part of the processing chamber.

  The hard coat film F subjected to the plasma discharge treatment is conveyed to the next process or a winding roll (not shown) through the nip roll 123 and the guide roll 121.

  Partition plates 124 and 125 with the outside world are provided at the nip rolls 122 and 123 at the entrance and exit of the plasma discharge processing container, and air accompanying the hard coat film F from the outside world together with the nip rolls 122 is provided. At the outlet, the reaction gas G or the exhaust gas G ′ is prevented from leaking to the outside. Although not shown, the rotating electrode 110 and the fixed electrode 111 may be temperature controlled as required. A temperature-controlled medium is circulated in the interior.

  Thus, in the present invention, the hard coat film on which the thin film is formed is preferably subjected to plasma discharge treatment while being transferred on the rotating electrode.

  The surface where the rotating electrode is in contact with the hard coat film is required to have high smoothness, and the surface roughness of the surface of the rotating electrode is the maximum surface roughness (Rmax) defined by JIS-B-0601 of 10 μm or less. More preferably, it is 8 micrometers or less, Most preferably, it is 7 micrometers or less. Moreover, it is necessary to prevent dust and foreign matter from adhering to the electrode for uniform film formation.

The surface of the electrode used for the plasma discharge treatment is preferably coated with a solid dielectric, and in particular, a conductive base material such as a metal is preferably coated with the solid dielectric. Examples of the solid dielectric include plastics such as polytetrafluoroethylene and polyethylene terephthalate, metal oxides such as glass, silicon dioxide, aluminum oxide (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ), and titanium oxide (TiO ₂ ). Examples thereof include double oxides such as barium titanate.

  It is particularly preferable that the dielectric material is a ceramic-coated dielectric that has been thermally sprayed with ceramics and then sealed with an inorganic material. Here, examples of the conductive base material such as metal include metals such as silver, platinum, stainless steel, aluminum, and iron. Stainless steel is preferable from the viewpoint of processing.

  As the lining material, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass and the like are preferably used. However, among these, borate glass is more preferably used because it is easy to process.

  The electrode used for the plasma discharge treatment can be heated or cooled as necessary from the back side (inside). When the electrode is a belt, it can be cooled with gas from the back side, but it is preferable to control the temperature of the electrode surface and the temperature of the hard coat film by supplying a medium inside the rotating electrode using a roll. .

  As the medium, an insulating material such as distilled water, oil, particularly silicon oil is preferably used.

  The temperature of the hard coat film during the discharge treatment varies depending on the treatment conditions, but is preferably room temperature to 200 ° C. or less, more preferably room temperature to 120 ° C. or less, and further preferably 50 to 110 ° C.

  In addition, the curling may be caused by the discharge due to the rise of the film surface temperature or the like, but according to the present invention, the curling can be remarkably generated.

  It is desirable to prevent temperature unevenness particularly in the width direction of the hard coat film surface during the discharge treatment, preferably within ± 5 ° C, more preferably within ± 1 ° C, and particularly preferably. Within ± 0.1 ° C.

  In the present invention, the electrode gap is determined in consideration of the thickness of the solid dielectric, the applied voltage and frequency, the purpose of using plasma, and the like. The shortest distance between the solid dielectric and the electrode when a solid dielectric is placed on one of the electrodes, and the distance between the solid dielectrics when a solid dielectric is placed on both of the electrodes is uniform in any case From the viewpoint of generating discharge plasma, 0.5 mm to 20 mm is preferable, and 1 mm ± 0.5 mm is particularly preferable.

  In the present invention, the flow rate of the mixed gas generated by the gas generator is controlled in the discharge portion of the electrode gap and introduced into the plasma discharge portion from the reaction gas supply port. The concentration and flow rate of the reaction gas are appropriately adjusted, but it is preferable to supply the processing gas to the electrode gap at a speed sufficient for the transport speed of the hard coat film. In the discharge section, it is desirable to set the flow rate and discharge conditions so that most of the supplied reaction gas reacts and is used for thin film formation.

  In order to prevent the atmosphere from being mixed into the discharge part and the reaction gas from leaking out of the apparatus, it is preferable that the electrode and the hard coat film being transferred are surrounded and shielded from the outside. In the present invention, the atmospheric pressure of the discharge part is maintained at atmospheric pressure or a pressure in the vicinity thereof. In addition, the reaction gas may be decomposed in the gas phase to generate metal oxide fine powder, and it is desirable to set the flow rate and discharge conditions so as to reduce the generation.

  Here, the vicinity of atmospheric pressure represents a pressure of 20 to 200 kPa, but 93 to 110 kPa is preferable in order to preferably obtain the effects described in the present invention. The discharge part is preferably slightly positive with respect to the atmospheric pressure outside the apparatus, more preferably atmospheric pressure outside the plasma apparatus +0.1 kPa to 5 kPa.

  In the plasma discharge treatment apparatus useful for the present invention, it is preferable that one electrode is connected to a power source to apply a voltage, and the other electrode is grounded to generate a discharge plasma to generate a stable plasma. .

  The value of the voltage applied to the electrode from the high frequency power source used in the present invention is appropriately determined. For example, the voltage is about 0.5 to 10 kV, the applied frequency is adjusted to 1 kHz to 150 MHz, and the waveform is a pulse wave. Or a sine wave. In particular, it is preferable to apply a high frequency of 50 MHz or less over a frequency exceeding 100 kHz because a discharge part (discharge space) is obtained. Alternatively, a method of simultaneously applying high-frequency voltages having two frequencies of 1 kHz to 200 kHz and 800 kHz to 150 MHz is also preferably used.

Preferably the discharge density in the discharge portion are 5~1000W · min / m ^2, in particular it is desirable that 50~500W · min / m ^2.

  It is desirable that the plasma discharge processing section is appropriately surrounded by a Pyrex (R) glass processing container or the like, and it is also possible to use a metal as long as it is insulated from the electrodes. For example, polyimide resin or the like may be affixed to the inner surface of an aluminum or stainless steel frame, and the metal frame may be subjected to ceramic spraying to achieve insulation. In addition, the reaction gas and the exhaust gas can be appropriately supplied to the discharge unit or exhausted by surrounding the discharge unit, the side surface of the rotating electrode, the side surface of the cellulose ester film transport unit and the like.

  The reaction gas used in the method for forming a metal oxide thin film layer of the present invention will be described.

  The reaction gas for forming the thin film layer preferably contains nitrogen or a rare gas.

  That is, the reactive gas is preferably a mixed gas of nitrogen or a rare gas and a reactive gas described later.

  Here, the noble gas is a group 18 element of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc., and in the present invention, helium or argon is preferably used. I can do it. These may be used as a mixture, for example, in a ratio of helium 3: argon 7 or the like.

  The concentration of the rare gas or nitrogen in the reaction gas is preferably 90% or more in order to generate a stable plasma discharge, and desirably 90 to 99.99% by volume.

  A rare gas or nitrogen is used to generate a stable plasma discharge. In the plasma, the reactive gas is ionized or radicalized, and is deposited or adhered to the substrate surface to form a thin film.

  The reactive gas useful in the present invention can form thin films having various functions on a hard coat film by using a reactive gas added with reactive gases of various substances.

  For example, the low refractive index layer or the antifouling layer of the antireflection layer can be formed using a fluorine-containing organic compound or a silicon compound as the reactive gas.

  Further, these metal oxide layers (metal oxide nitride layers) using organometallic compounds, metal hydrides, and metal halides containing Ti, Zr, In, Sn, Zn, Ge, Si or other metals. Or a metal nitride layer or the like. These layers may be a middle refractive index layer or a high refractive index layer of the antireflection layer, or may be a conductive layer or an antistatic layer.

  Further, the antifouling layer and the low refractive index layer can be formed with a fluorine-containing organic compound, and the gas barrier layer and the low refractive index layer can be formed with a silicon compound. The present invention is particularly preferably used for forming an antireflection layer formed by alternately laminating high, medium refractive index layers and low refractive index layers.

  The film thickness of the formed metal oxide layer is preferably in the range of 1 nm to 1000 nm.

  In the atmospheric pressure plasma treatment, a fluorine compound-containing layer can be formed by using a fluorine-containing organic compound as a raw material gas.

  As the fluorine-containing organic compound, a fluorocarbon gas, a fluorinated hydrocarbon gas, or the like is preferable.

Specifically, as the fluorine-containing organic compound, for example, a fluorocarbon compound such as carbon tetrafluoride, carbon hexafluoride, tetrafluoroethylene, hexafluoropropylene, and octafluorocyclobutane;
Fluorinated hydrocarbon compounds such as difluoromethane, tetrafluoroethane, propylene tetrafluoride, propylene trifluoride, and cyclobutane octafluoride;
Further, halides of fluorinated hydrocarbon compounds such as trichloromethane trichloride, methane monochloride difluoride methane, and cyclobutane tetrachloride difluoride, and fluorine-substituted products of organic compounds such as alcohols, acids, and ketones. I can do it.

  These may be used alone or in combination. Examples of the fluorinated hydrocarbon gas include gases such as difluoromethane, tetrafluoroethane, propylene tetrafluoride, and propylene trifluoride.

  Furthermore, it is possible to use halides of fluorinated hydrocarbon compounds such as monochlorotrifluoride methane, monochlorodifluoride methane, and dichloride tetrafluorocyclobutane, and fluorine-substituted products of organic compounds such as alcohols, acids, and ketones. However, the present invention is not limited to these.

  Moreover, these compounds may have an ethylenically unsaturated group in the molecule. In addition, the above compounds may be used as a mixture.

  When a fluorine-containing organic compound is used as the reactive gas, the content of the fluorine-containing organic compound as the reactive gas in the reactive gas is from the viewpoint of forming a uniform thin film on the cellulose ester film by plasma discharge treatment. It is preferable that it is 01-10 volume%, More preferably, it is 0.1-5 volume%.

  Further, when the fluorine-containing organic compound that is preferably used is a gas at normal temperature and pressure, it can be used as it is as a component of the reactive gas.

  Further, when the fluorine-containing organic compound is liquid or solid at normal temperature and normal pressure, it may be used after being vaporized by vaporization means, for example, by heating, reduced pressure, or the like, and may be used after being dissolved in an appropriate organic solvent. .

  Examples of silicon compounds useful as reactive gases include organometallic compounds such as dimethylsilane and tetramethylsilane, metal hydrides such as monosilane and disilane, metal halogens such as silane dichloride, silane trichloride, and silicon tetrafluoride. Compounds, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, hexamethyldisiloxane and other alkoxysilanes, organosilanes, etc. are preferably used. It is not limited.

  Moreover, these can be used in combination as appropriate. Alternatively, another organic compound can be added to change or control the physical properties of the film.

  When a silicon compound is used as the reactive gas, the content of the silicon compound as the reactive gas in the reactive gas is 0.01 to 10 volumes from the viewpoint of forming a uniform thin film on the cellulose ester film by plasma discharge treatment. %, Preferably 0.1 to 5% by volume.

  Although it does not specifically limit as an organometallic compound useful as a reactive gas, Al, As, Au, B, Bi, Sb, Ca, Cd, Cr, Co, Cu, Fe, Ga, Ge, Hg, In, Li Preferably, organometallic compounds for forming metal compounds such as Mg, Mn, Mo, Na, Ni, Pb, Pt, Rh, Se, Si, Sn, Ti, Zr, Y, V, W, Zn, etc. I can do it.

  For example, in order to form a high refractive index layer of the antireflection layer, a titanium compound is preferable. Specifically, for example, an organic amino metal compound such as tetradimethylamino titanium, a metal hydrogen compound such as monotitanium and dititanium, Examples thereof include metal halogen compounds such as titanium chloride, titanium trichloride, and titanium tetrachloride, and metal alkoxides such as tetraethoxy titanium, tetraisopropoxy titanium, and tetrabutoxy titanium.

  The above silicon compounds and organometallic compounds are preferably metal hydrides and metal alkoxides from the viewpoint of handling, and are preferably used since metal alkoxides are not corrosive, do not generate harmful gases, and have little contamination in the process. It is done.

  When using an organometallic compound as the reactive gas, from the viewpoint of forming a uniform thin film on the cellulose ester film by plasma discharge treatment, the content of the organometallic compound as the reactive gas in the reactive gas is 0.01 to Although it is preferable that it is 10 volume%, More preferably, it is 0.1-5 volume%.

  Further, in order to introduce a metal compound such as a silicon compound or a titanium compound into the discharge part, both can be used in a gas, liquid or solid state at normal temperature and pressure.

  In the case of gas, it can be introduced into the discharge part as it is, but in the case of liquid or solid, it can be used after being vaporized by means of vaporization such as heating, decompression or ultrasonic irradiation.

  When metal compounds such as silicon compounds and titanium compounds are vaporized by heating, metal alkoxides that are liquid at room temperature and have a boiling point of 200 ° C. or less, such as tetraethoxysilane and tetraisopropoxytitanium, are used in the present invention. It is suitable for a method for forming a metal oxide thin film layer. The metal alkoxide may be used after diluted with an organic solvent. As the organic solvent, an organic solvent such as methanol, ethanol, n-hexane, or a mixed organic solvent thereof can be used.

  Furthermore, physical properties such as hardness and density of the thin film layer can be obtained by adding 0.1 to 10% by volume of oxygen, hydrogen, carbon dioxide, carbon monoxide, nitrogen, nitrogen dioxide, nitrogen monoxide, water, etc. in the reaction gas. Can be controlled.

  By the above method, an amorphous metal oxide layer such as silicon oxide or titanium oxide can be preferably produced.

  The hard coat film of the present invention can be preferably used for, for example, an optical film having an antireflection layer obtained by laminating a low refractive index layer and a high refractive index layer, a conductive layer, an optical film having an antistatic layer, or the like.

  In the present invention, by providing a plurality of plasma discharge devices, a multilayer thin film can be continuously provided, and a multilayer laminate can be formed without unevenness of the thin film.

  For example, when producing an antireflection film having an antireflection layer on a hard coat film, a high refractive index layer having a refractive index of 1.6 to 2.3 and a low refractive index layer having a refractive index of 1.3 to 1.5 are provided. The cellulose ester film can be continuously laminated on the surface and efficiently produced.

  As the low refractive index layer, a fluorine-containing compound layer formed by plasma discharge treatment using a gas containing a fluorine-containing organic compound, or mainly silicon oxide formed by plasma discharge treatment using an organosilicon compound such as alkoxysilane is used. The high refractive index layer is preferably a metal oxide layer formed by plasma discharge treatment with a gas containing an organometallic compound, such as a layer having titanium oxide or zirconium oxide.

  Although there are thinning methods described above, the present invention is not limited to these methods, and the layer structure is not limited thereto. For example, an antifouling layer may be provided on the outermost surface by plasma discharge treatment in the presence of a fluorine-containing organic compound gas in the presence of atmospheric pressure or in the vicinity thereof.

  According to the above method, in the present invention, multilayer thin films can be laminated, and a uniform antireflection film can be obtained without unevenness in the thickness of each layer.

〔Polarizer〕
The hard coat film provided with the antireflection layer of the present invention is used for production of a polarizing plate.

  The polarizing plate can be produced by a general method. The back surface side of the antireflection film of the present invention was subjected to alkali saponification treatment, and the treated antireflection film was immersed and drawn in an iodine solution, and a completely saponified polyvinyl alcohol aqueous solution was used on at least one surface of the following polarizing film. It is preferable to stick them together. The antireflection film may be used on the other surface, or another polarizing plate protective film may be used. With respect to the antireflection film of the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation Ro of 590 nm, a phase difference of 20 to 70 nm, and Rt of 100 to 400 nm. preferable. These can be produced, for example, by the method described in JP-A-2002-71957 and Japanese Patent Application No. 2002-155395. Alternatively, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. Or it can also be set as a circularly-polarizing plate by using (lambda) / 4 board also as a polarizing plate protective film. By using it in combination with the antireflection film of the present invention, a polarizing plate having excellent flatness and a stable viewing angle expansion effect can be obtained.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. On the surface of the polarizing film, one side of the antireflection film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

  A conventional polarizing plate using an antireflection film is inferior in interference unevenness and flatness, and when a reflected image is seen, iridescent unevenness and fine wavy unevenness are recognized, and a pencil hardness of only about 2H is obtained at 60 ° C. As a result of the durability test under the condition of 90% RH, the wavy unevenness increased. On the other hand, the polarizing plate using the antireflection film of the present invention has excellent interference unevenness and flatness, and has a pencil hardness. It was excellent. In addition, unevenness did not increase even in a durability test under the conditions of 60 ° C. and 90% RH.

<Display device>
By incorporating a polarizing plate using the hard coat film according to the present invention into a display device, various display devices having excellent visibility can be manufactured. The hard coat film of the present invention is preferably used in reflective, transmissive, transflective LCDs or LCDs of various drive systems such as TN, STN, OCB, HAN, VA, and IPS. In addition, the antireflection film in which the antireflection layer is formed on the hard coat film of the present invention has significantly less color unevenness in the reflected light of the antireflection layer, and is excellent in flatness, plasma display, field emission display, organic EL display, It is also preferably used for various display devices such as inorganic EL displays and electronic paper. Especially for large-screen display devices with a screen size of 30 or more, the reflected images of fluorescent lamps appear to be distorted due to uneven color and wavy unevenness, so there is no distortion like the reflection of mirrors. But there was an effect that eyes were not tired.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1
[Production of cellulose ester film]
Using the cellulose ester, additive 1, additive 2, fine particles, and solvent described in Table 1, a cellulose ester solution was prepared so as to have a dope composition as shown in Table 2.

  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, and then the solution was produced by Azumi Filter Paper No. Filtration using 244 gave each cellulose ester solution.

  The dopes A to U prepared above are combined from the two surface layer dope lines and the base layer dope line to the respective surface layer die or base layer die as shown in Table 3, and the dried layer The film was introduced so that the film thickness was as shown in Table 3, and co-casting was carried out on an endless stainless steel belt having an infinite traveling length of 1.7 m (the surface layer was cast slightly wider than the base layer). The temperature of the stainless steel belt was set to 35 ° C. so that the surface layer 1 was on the belt surface (this surface was designated as B surface) and the surface layer 2 was on the air side surface (this surface was designated as A surface). The solvent was evaporated on the stainless steel belt, and the web was peeled off from the stainless steel belt. The peeled web was cut to 1.5 m width with a slitter at both ends, this web was introduced into a tenter dryer, both ends were gripped with clips and dried at 90 ° C. while stretching 1.05 times in the width direction, and then Drying was terminated while a large number of rolls arranged up and down were alternately passed through a roll drier having each drying zone at 125 ° C., and drying was completed to prepare a multilayered cellulose ester film. Further, both ends of the cellulose ester film are cut off to form a 1.4 m wide film, and both ends of the film are subjected to a knurling process having a width of 10 mm and a height of 8 μm, and the winding length is 3000 m. 1-26 were obtained.

[Production of hard coat film]
<Coating of hard coat layer>
Cellulose ester film No. On the B surface of each of 1 to 26, the following hard coat layer (ultraviolet curable resin layer) coating solution is filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a hard coat layer coating solution. After applying using a gravure coater and drying at 90 ° C., using an ultraviolet lamp, the illuminance of the irradiated part is 100 mW / cm ² , the applied dose is cured at 100 mJ / cm ² , and the hard coat is 3 μm thick. A layer was formed. In this way, the hard coat film No. 1-26 were produced.

<Coating liquid for hard coat layer>
Dipentaerythritol hexaacrylate 100 parts by weight Photoreaction initiator 4 parts by weight (Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.))
Ethyl acetate 75 parts by mass Propylene glycol monomethyl ether 75 parts by mass Silicon compound 0.5 parts by mass (BYK-307 (by Big Chemie Japan))
[Evaluation]
The following evaluation was performed about the obtained hard coat film.

<< Flatness index; Evaluation of minute irregularities >>
Laser displacement meter: Keyence Corporation, 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 hard coat film Evaluated.

  The measuring method is that the film is placed on a flat and horizontal table, both ends of the width are fixed to the table with tape, and the measuring camera is set in parallel with the table on a moving rail made by Sigma Kogyo Co., Ltd. And the sample film were set so that the distance between them was 25 mm, and the measurement was performed by scanning at a moving speed of 5 cm / min. The value obtained by the measurement is the state and size of minute irregularities on the film surface.

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 3.0 μm or more <<Flatness; Visual evaluation >>
Cut each sample into a size of 90cm in width and 100cm in length, and arrange five 50W fluorescent lamps at a height of 1.5m so that the sample stage can be illuminated from a 45 ° angle. Each film sample was placed, and the unevenness that appeared to be reflected on the film surface was visually observed and judged as follows. By this method, it is possible to determine “tsun” and “wrinkle”.

◎: All five fluorescent lamps look straight ○: Some fluorescent lamps appear to be bent slightly △: Fluorescent lamps appear to be slightly bent overall ×: Fluorescent lamps appear to swell largely << Evaluation of interference unevenness >>
Hard coat film No. For samples 1 to 26, the back surface was painted black with black spray, and then the sample was placed on a horizontal table. The degree was visually evaluated.

○: Interference unevenness is not seen at all Δ: Interference unevenness is slightly visible but no problem is observed ×: Interference unevenness is clearly seen XX: Strong interference unevenness is seen The results obtained above are shown in Table 4 below. Indicated.

  From the above table, it was found that the hard coat film of the present invention was excellent in flatness, flatness index, and interference unevenness compared to the comparative example.

Example 2
[Preparation of antireflection film]
An antireflection layer was formed on the hard coat film produced in Example 1.

  Hard coat film No. A coating solution for the refractive index layer shown below is applied onto 1 to 26 using a bar coater, dried at 70 ° C., then irradiated with ultraviolet rays to cure the coating layer, and a medium refractive index layer (refractive index). 1.72 and a film thickness of 80 nm). On top of that, the following coating solution for a high refractive index layer was applied using a bar coater, dried at 70 ° C., then irradiated with ultraviolet rays to cure the coating layer, and a high refractive index layer (refractive index 1.9, A film thickness of 70 nm) was formed. Furthermore, the following coating solution for the low refractive index layer is applied using a bar coater, dried at 70 ° C., and cured by heat treatment to form a low refractive index layer (refractive index 1.45, film thickness 95 nm). And an antireflection film No. having a visible light reflectance of 0.5% or less. 1-26 were produced.

<Preparation of medium refractive index layer / high refractive index layer / low refractive index layer>
(Preparation of titanium dioxide dispersion)
Titanium dioxide (primary particle mass average particle size: 50 nm, refractive index: 2.70) 30 parts by mass, anionic diacrylate monomer (PM21, Nippon Kayaku Co., Ltd.) 4.5 parts by mass, cationic methacrylate monomer ( DMAEA (manufactured by Kojin Co., Ltd.) 0.3 parts by mass and 65.2 parts by mass of methyl ethyl ketone were dispersed with a sand grinder to prepare a titanium dioxide dispersion.

(Preparation of coating solution for medium refractive index layer)
In 151.9 g of cyclohexanone and 37.0 g of methyl ethyl ketone, 0.14 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 0.04 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) were dissolved. Further, 6.1 g of the above titanium dioxide dispersion and 2.4 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) were added and stirred at room temperature for 30 minutes. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for a medium refractive index layer. When this coating solution was applied to a cellulose ester film and dried and the refractive index after UV curing was measured, a medium refractive index layer having a refractive index of 1.72 was obtained.

(Preparation of coating solution for high refractive index layer)
In 1152.8 g of cyclohexanone and 37.2 g of methyl ethyl ketone, 0.06 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 0.02 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) were dissolved. Furthermore, the ratio of the above titanium dioxide dispersion and the titanium dioxide dispersion of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) is increased, and the refractive index of the high refractive index layer is increased. The amount was adjusted so as to be a ratio, and the mixture was stirred at room temperature for 30 minutes, and then filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a high refractive index layer. When this coating solution was applied to a cellulose ester film, dried and the refractive index after UV curing was measured, a high refractive index layer having a refractive index of 1.9 was obtained.

(Preparation of coating solution for low refractive index layer)
Silane coupling agent (KBM-503, Shin-Etsu Silicone Co., Ltd.) 3 g and 0.1 M / L hydrochloric acid 2 g were added to 200 g of methanol dispersion of silica fine particles with an average particle size of 15 nm (methanol silica sol, manufactured by Nissan Chemical Co., Ltd.). In addition, the mixture was stirred at room temperature for 5 hours and then allowed to stand at room temperature for 3 days to prepare a dispersion of silica fine particles treated with silane coupling. To 35.04 g of the dispersion, 58.35 g of isopropyl alcohol and 39.34 g of diacetone alcohol were added. Further, 1.02 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and a solution obtained by dissolving 0.51 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) in 772.85 g of isopropyl alcohol were added. Furthermore, 25.6 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was added and dissolved. 67.23 g of the resulting solution was added to the above dispersion, a mixture of isopropyl alcohol and diacetone alcohol. The mixture was stirred for 20 minutes at room temperature and filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a low refractive index layer. When this coating solution was applied to a cellulose ester film and dried, and the refractive index after UV curing was measured, the refractive index was 1.45.

  A polarizing plate was prepared using each antireflection film.

[Preparation of polarizing plate]
A polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizing film.

  Subsequently, according to the following processes 1-5, the polarizing film, the said antireflection film, and the polarizing plate protective film on the back side were bonded together, and the polarizing plate was produced. As the polarizing plate protective film on the back surface side, a cellulose ester film having a retardation (measured at 590 nm, in-plane retardation Ro = 43 nm, retardation in the thickness direction Rt = 135 nm) was used as a polarizing plate.

  Step 1: Soaked in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried to obtain a saponified cellulose ester film bonded to the polarizer.

  On the other hand, the surface of the anti-reflection layer side of the hard coat film on which the anti-reflection layer was formed was subjected to the saponification treatment while applying a peelable polyethylene film and protecting it from alkali.

  Step 2: The polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.

  Step 3: Gently wipe off excess adhesive adhered to the polarizing film in Step 2 and place it on the cellulose ester film treated in Step 1 so that the anti-reflection layer of the hard coat film is on the outside Laminated and placed.

Step 4: Excess adhesive and bubbles were removed from the end of the laminate of the antireflection film, the polarizing film and the cellulose ester film sample laminated in Step 3 with a hand roller, and bonded together. The pressure of the hand roller was 20 to 30 N / cm ² and the roller speed was about 2 m / min.

  Process 5: The sample which bonded the polarizing film produced in the process 4, the cellulose-ester film, and the antireflection film in the 80 degreeC dryer was dried for 2 minutes, and the polarizing plate was produced. Antireflection film No. 1 to 26, respectively, polarizing plate No. 1-26 were produced.

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

  The polarizing plates on the both sides of the 15-inch display VL-150SD manufactured by Fujitsu were previously peeled off to remove the polarizing plate No. 1 prepared above. 1-26 were bonded to the glass surface of the liquid crystal cell, respectively.

  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 device no. 1-26 were produced respectively.

[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 antireflection film laminated on the hard coat film of the present invention was excellent in flatness, whereas the comparative polarizing plate had fine wavy unevenness. It was recognized and my eyes were 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 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 △: Color unevenness of reflected light is recognized but practically no problem ×: Reflected light I am worried about the uneven color.

  Liquid crystal display device no. The evaluation results for 1-26 are shown in Table 4 above.

  The liquid crystal display device of the present invention had good visibility and did not cause reflection color unevenness and had no practical problem. However, the comparative liquid crystal display device had poor visibility and caused reflection color unevenness.

[Evaluation of plasma display device]
The produced antireflection film No. 1 to 26 are attached to the forefront of a commercially available panel (PDP-503HD, manufactured by Pioneer Co., Ltd.) with an adhesive. 1-26 were produced. The obtained display device was placed on a desk 75 cm high from the floor, and a Paruk fluorescent lamp (FL40SS / ELW / 37 type, 37 W, manufactured by Matsushita Electric Industrial Co., Ltd.) was placed on the ceiling 3 m high from the floor. Eight sets were arranged at 1.5 m intervals, with two as one set. At this time, when the evaluator is in front of the display device, the fluorescent lamp is arranged so that the fluorescent lamp comes to the ceiling part from the evaluator's overhead to the rear, and the reflection of the fluorescent lamp is ranked as follows. As a result, it was found that in the antireflection film using the hard coat film of the present invention, there was no distortion until the reflection of a nearby fluorescent lamp, and thus eyes did not get tired even during long-time viewing.

The cross section of the film of 3 layer structure is shown typically. It is the figure showing the place which formed the multilayer casting web by casting and a co-casting die. It is a figure showing the web of the sequential casting die and the casted multilayer structure. It is the figure which showed the cross section of another type co-casting die. It is the figure which showed typically the dope preparation process of the solution casting film forming apparatus concerning this invention. It is the figure which showed typically from the casting process to the drying process of the solution casting film forming apparatus concerning this invention. It is a figure which shows an example of the plasma discharge treatment apparatus used in order to form a metal oxide layer on the hard coat film of this invention. It is a figure which shows an example of the plasma discharge processing apparatus which has a rotating electrode useful for forming a metal oxide thin film layer on the hard coat film of this invention, and a fixed electrode.

Explanation of symbols

F hard coat film G reactive gas G ′ exhaust gas 10A, 10B, 110 rotating electrode 11A, 11B, 11C, 11D U-turn roll 20, 21 guide roll 30 reactive gas supply unit 40, 140 gas exhaust port 50, 150 discharge unit 51 rectification Plate 80, 180 Power supply 81, 82, 181, 182 Voltage supply means 111 Fixed electrode 120, 121 Guide roll 122, 123 Nip roll 124, 125 Partition plate 130 Air supply pipe 131 Reactive gas generator 190 Plasma discharge treatment vessel

Claims (8)

At least one surface layer having a cellulose ester having a film thickness of 0.1 to 15 μm and a total acyl group substitution degree of 2.7 or less, a plasticizer, an ultraviolet absorber, and a cellulose ester having a total acyl group substitution degree of 2.8 or more A hard coat film comprising a hard coat layer on the surface layer of a cellulose ester film having a multilayer structure having a base layer having a surface. The hard coat film according to claim 1, wherein the cellulose ester of the base layer is cellulose triacetate, and the cellulose ester of the surface layer is cellulose diacetate or cellulose acetate propionate. The cellulose ester of the base layer is a cellulose ester having a number average molecular weight (Mn) of 80,000 to 200,000 and a weight average molecular weight (Mw) / number average molecular weight (Mn) value of 1.4 to 3.0. The hard coat film according to claim 1 or 2. The hard coat film according to claim 1, wherein the surface layer contains fine particles. The hard coat film according to any one of claims 1 to 4, wherein the surface layer contains a plasticizer. 6. The hard according to claim 1, wherein a plasticizer content of the surface layer adjacent to the hard coat layer is larger than an average plasticizer content of the multilayered cellulose ester film. Coat film. The hard coat film according to claim 1, further comprising an antireflection layer on the hard coat layer. A cellulose ester solution A for forming a base layer having a plasticizer, an ultraviolet absorber and a cellulose ester having a total acyl group substitution degree of 2.8 or more, and a surface layer having a cellulose ester having a total acyl group substitution degree of 2.7 or less. The cellulose ester solution B to be formed is formed by a co-casting method to form a cellulose ester film having a multilayer structure having at least one base layer and a surface layer having a film thickness of 0.1 to 15 μm. A method for producing a hard coat film, comprising: coating an active ray curable resin layer on the top and then irradiating with active rays to form a hard coat layer.

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