TW201406843A - Resin composition for reverse wavelength dispersion film, and reverse wavelength dispersion film and reverse wavelength dispersion sheet which comprise same - Google Patents

Abstract

The purpose of the present invention is to provide a novel resin composition which is for use in producing a reverse wavelength dispersion film and which exhibits excellent saponification resistance, transparency, positive birefringence and reverse wavelength dispersion properties. This resin composition contains a modified polysaccharide (A) which is obtained by chemically modifying a polysaccharide to convert at least one of the hydroxyl, carboxyl and amino groups of the polysaccharide into at least one kind of functional group selected from the group consisting of ether group, urethane group, urea group, amido group and imido group. Further, the resin composition is characterized in that: the average molecular dispersion of all the monosaccharide units constituting the modified polysaccharide (A) is 0.50 to 20.0; and a film formed from the resin composition and having a thickness of 80mum exhibits an absolute value of reflection chromaticity b* of 0 to 1.0 as determined according to JIS-Z8729.

Description

Resin composition for reverse wavelength dispersion film, and reverse wavelength dispersion film composed thereof, and reverse wavelength dispersion sheet

The present invention relates to a resin composition for a reverse wavelength dispersion film, a reverse wavelength dispersion film composed of the same, and a reverse wavelength dispersion sheet.

Ethylene cellulose is excellent in non-combustibility, transparency, surface appearance and electrical insulation, and thus can be used in various fields.

As a reverse-wavelength dispersion film (retardation film) which is one of the uses of the acetaminophen film, a resin which satisfies both the positive birefringence and the reverse wavelength dispersion is required, and an acetamethylene fiber having an ethyl ruthenium substitution degree of less than 2.5 can be used. Prime. However, the ethyl phthalocyanine having an ethyl hydrazide substitution degree of less than 2.5 has a problem of elution in the saponification treatment for improving the adhesion, and it is proposed to cover the acetamidine with an ethyl hydrazine having a degree of substitution of 2.5 or more. The surface of the acetamidine cellulose having a base substitution degree of less than 2.5 (for example, Patent Document 1). However, there is a limit to the film thickness of the reverse wavelength dispersion film, and it is difficult to cover it so that the saponification resistance can be completely provided. As a solution to the above problem, a resin having positive birefringence other than acetonitrile cellulose is required. Further, although the reverse wavelength dispersibility can be achieved by using a composite with other resins, it is extremely difficult to select from the viewpoint of transparency (compatibility).

Patent Document 1: Japanese Laid-Open Patent Publication No. 2012-088408

An object of the present invention is to provide a resin composition for a novel reverse wavelength dispersion film which is excellent in saponification resistance, transparency, positive birefringence and reverse wavelength dispersion.

The present inventors have made an effort to achieve the above object, and as a result, have achieved the present invention. That is, the present invention is a resin composition for a reverse wavelength dispersion film; a reverse wavelength dispersion film or a reverse wavelength dispersion sheet formed of the resin composition for the reverse wavelength dispersion film; and a phase formed by the resin composition for the reverse wavelength dispersion film a differential film or a retardation film; and a circularly polarizing film or a circular polarizer formed of the resin composition for the reverse wavelength dispersion film; and the resin composition for the reverse wavelength dispersion film contains a modified polysaccharide (A), the modified polysaccharide ( A) chemically modifying at least one functional group of the polysaccharide selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group to be selected from the group consisting of an ether group, a urethane group, a urea group, a guanyl group and an imine group. At least one functional group of the group consisting of the groups, and the average molecular dispersion of all the monosaccharide units constituting the modified polysaccharide (A) is 0.50 to 20.0, and the resin composition for the reverse wavelength dispersion film is formed into a film thickness of 80 μm. The absolute value of the reflection chromaticity b* obtained from JIS-Z8729 of the film is 0 to 1.0.

The film and sheet formed from the resin composition for a reverse wavelength dispersion film of the present invention are excellent in transparency, saponification resistance, positive birefringence, and reverse wavelength dispersibility.

The resin composition for a reverse wavelength dispersion film of the present invention contains a modified polysaccharide (A) which has at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group. Chemically modifying at least one functional group selected from the group consisting of an ether group, a urethane group, a urea group, a guanamine group, and an imine group, and constituting all the monosaccharides of the modified polysaccharide (A) The average molecular dispersion of the unit is 0.50 to 20.0, and the absolute value of the reflection chromaticity b* (physical property indicating transparency) determined by JIS-Z8729 is obtained by molding the resin composition for a reverse wavelength dispersion film into a film having a film thickness of 80 μm. 0~1.0.

The reverse wavelength dispersion film has a function of a function of increasing the phase difference as the wavelength is longer.

Further, the ether group is preferably an α or β-hydroxy ether group from the viewpoint of saponification resistance, transparency, positive birefringence, and reverse wavelength dispersibility.

In the present invention, the modified polysaccharide (A) constitutes the average molecular dispersion of all the monosaccharide units constituting the modified polysaccharide (A) of 0.50 to 20.0.

The molecular dispersion of the monosaccharide unit is a value obtained by adding the total value of the atomic dispersion described in "Advances in Physical Organic Chemistry, 3, 1, 1965" to each of the bonds in the monosaccharide unit.

Molecular dispersion of monosaccharide units = Σ _i (atomic dispersion of the i-th bond) (Equation 1)

Further, the average molecular dispersion of the monosaccharide unit is such that, as shown by the following formula 2, the molecular dispersion values of the monosaccharide units constituting the modified polysaccharide (A) are all added together, and divided by the modified polysaccharide (A). The average of the number of monosaccharide units.

The average molecular dispersion of the monosaccharide unit = {Σ _n (molecular dispersion of the n-th monosaccharide unit)} / (the number of monosaccharide units in (A)) (Equation 2)

The modified polysaccharide (A) is a case where the polysaccharide (a) is chemically modified by at least one compound selected from the group consisting of the following (y1) to (y5), and the average molecular dispersion of the monosaccharide unit is used by The modification rate of the modified polysaccharide (A) determined by ¹ H-NMR (Nuclear Magnetic Resonance) and the value calculated by the following formula 3 was defined as the average molecular dispersion of the monosaccharide unit.

The average molecular dispersion of the monosaccharide unit = {molecular dispersion of the skeleton of the monosaccharide unit} + [Molecular dispersion of the functional group introduced by the chemical modification of Σ _i { yi] × {Using the modification rate of (yi)}] -[{Molecular dispersion of hydroxyl (OH)}×{Modification rate of hydroxyl}}-[{Molecular dispersion of carboxyl (C(=O)-OH)}×{Modification rate of carboxyl group}]-[{Amino group ( Molecular dispersion of NH ₂ )}×{Modification rate of amine group}] (Expression 3) In the formula 3, (yi) represents (y1) to (y5).

Here, when the polysaccharide (a) is a substituted polysaccharide (for example, (a1) to (a3) below), a substituent introduction ratio (DS) provided by each raw material manufacturer is used, by the following formula The molecular dispersion of the skeleton of the monosaccharide unit was calculated.

Molecular dispersion of the skeleton of the monosaccharide unit = {Molecular dispersion of the skeleton of the monosaccharide unit constituting the polysaccharide before substitution} + [Molecular dispersion of the functional group introduced by substitution) × DS] - [(Chemical by substitution) Molecular dispersion of functional groups before modification) ×DS]

The modification ratio of the use of the hydroxyl group, the carboxyl group, and the amine group (y1) to (y5) was determined by the following measurement.

<Method for measuring the modification rate of the use of hydroxyl group, carboxyl group and amine group (y1) to (y5)

The ¹ H-NMR measurement of the modified polysaccharide (A) was carried out under the following conditions, and was based on the reaction of the polysaccharide (a) and (y1) to (y5) added by the preparation of the modified polysaccharide (A). The peak integrated value of the functional group introduced by the chemical modification and the peak integrated value derived from the hydroxyl group, the carboxyl group and the amine group in the polysaccharide (a), respectively, were used to calculate the modification ratio using (y1) to (y5).

For example, when cellulose is used as the polysaccharide (a) and reacted with methyl isocyanate (y1), the functional group in which the hydroxyl group (-OH) in the cellulose is chemically modified is (-O). -CO-NH-CH ₃ ). By the following formula, the integral value of the hydrogen atom of the urethane group in the modified polysaccharide (A) and the integral value of the hydrogen atom derived from the hydroxyl group in the cellulose (each monosaccharide unit 3H) Calculate the modification rate.

Modification rate = (integral value of hydrogen atom of urethane group) / {(integral value of hydrogen atom of urethane group) + (integral value of hydrogen atom derived from hydroxyl group in cellulose) / 3)

Solvent: Deuterated dimethyl hydrazine

Device: AVANCE300 (made by Japan Bruker Co., Ltd.)

Frequency: 300MHz

In the present invention, the average molecular dispersion of all the monosaccharide units constituting (A) is (A) is from 0.50 to 20.0, but from the viewpoint of reverse wavelength dispersibility, it is preferably from 0.5 to 15.0, more preferably 0.5. ~10.0, and more preferably 0.5~2.0.

The average molecular dispersion of all the monosaccharide units constituting (A) is made low by introducing a substituent having a bond having a smaller absorption maximum wavelength, by introducing a substituent having a bond having a larger absorption maximum wavelength. And make it higher.

In the present invention, the absolute value of the reflection chromaticity b* obtained by molding the resin composition for a reverse wavelength dispersion film into a film having a film thickness of 80 μm in accordance with JIS-Z8729 is 0 to 1.0, but from the viewpoint of transparency Preferably, it is 0 to 0.5, more preferably 0 to 0.25, and particularly preferably 0 to 0.2.

The absolute value of the reflected chromaticity b* is reduced by the production of aromatic isocyanine in the production of (A) below. The amount of the acid ester (aromatic polyisocyanate and aromatic monoisocyanate) is lowered, and the amount of the aromatic isocyanate used is increased to increase the amount of the aromatic isocyanate. Further, in the aromatic polyisocyanate and the aromatic monoisocyanate, the reflection chromaticity b* may be lowered by introducing a hydrocarbon group between the isocyanate group and the aromatic ring.

A film system in which a resin composition for a reverse wavelength dispersion film was formed into a film thickness of 80 μm was obtained from a resin composition for a reverse wavelength dispersion film by the following method.

First, the resin composition for a reverse wavelength dispersion film is dissolved in 1,3-dioxolane as an organic solvent so that the solid content is about 10%. By using an applicator, a resin composition for a reverse wavelength dispersion film dissolved in an organic solvent is applied to a PET (polyethylene terephthalate) film having a surface thickness of 120 μm so that the film thickness is 80 μm [for example, "COSMOSHINE" manufactured by Toyobo Co., Ltd.]. The coating was dried at 80 ° C for 2 hours. After drying, it was peeled off from the PET film and used for reflection chromaticity b* measurement.

The modified polysaccharide (A) in the present invention chemically modifies at least one functional group of the polysaccharide selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group to be selected from the group consisting of an ether group, an urethane group, and a urea. At least one functional group of a group consisting of a sulfhydryl group and an imido group.

From the viewpoint of reverse wavelength dispersibility, the modified polysaccharide (A) preferably does not have a (meth) acrylonitrile group.

As the polysaccharide, a previously known polysaccharide may be contained and may be used without particular limitation. Specifically, the following polysaccharide (a) may be included.

As the polysaccharide (a), it may comprise a starch selected from the group consisting of starch (including amylose and amylopectin), glycogen, cellulose, chitin, polyglucosamine, agarose, carrageenan, Heparin, hyaluronic acid, pectin, xyloglucan and sinica, and a group of such functional groups substituted with a urethane group, a ureido group and a guanamine group At least one polysaccharide.

One type of the polysaccharide may be used alone or two or more types may be used in combination.

As the substituted polysaccharide, a known polysaccharide which is substituted may be contained. As the substituted polysaccharide, a known cellulose which is substituted is preferred from the viewpoint of birefringence, reverse wavelength dispersibility, and water resistance. As the substituted cellulose, a cellulose (a1), an etherified cellulose (a2), and an etherified cellulose (a3) can be contained.

The deuterated cellulose (a1) may include deuterated cellulose substituted with a fluorenyl group having a carbon number of 2 to 19 which may be partially substituted by a hydroxyl group, and examples thereof include a reaction product of cellulose with a carboxylic acid or a lactone.

The carboxylic acid may include a carbon number of 2 to 19, and examples thereof include acetic acid, butyric acid, 2-ethylhexanoic acid, n-octanoic acid, neodecanoic acid, dodecanoic acid, stearic acid, and oleic acid. , linoleic acid, linoleic acid, benzoic acid and phthalic acid. The carboxylic acid may also be a ruthenium halide such as ruthenium chloride {as a halogen, such as F, Cl, Br, etc.}. Further, these may be used alone or in combination of two or more.

The lactone may include a carbon number of 2 to 19, and examples thereof include β-lactone (β-propiolactone, etc.), γ-lactone (γ-butyrolactone, etc.), and δ-lactone (δ-pentyl). Lactones, etc., ε-lactone (ε-caprolactone, etc.), macrolide (enantholactone, undecanolactone, dodecanoate, etc.) and aromatic lactones (3 , 4-dihydrocoumarin) and the like. These may be used alone or in combination of two or more.

Examples of the fluorenyl group having a carbon number of 2 to 19 which may be partially substituted by a hydroxyl group include an ethyl group, a propyl group, a butyl group, a pentamidine group, a benzamidine group, and a 6-hydroxyhexyl group (HO-C). ₅ H ₁₀ -CO-) and 3-(2-hydroxyphenyl)propanyl group and the like.

Specific examples of (a1) include triethyl hydrazine cellulose, diethyl hydrazine cellulose, acetaminophen cellulose, acetamidine cellulose, and acetyl 3-(2-hydroxyphenyl) propyl group. Cellulose and the like.

In (a1), from the viewpoint of water resistance, it is preferably a cellulose which is substituted with a thiol group having a carbon number of 2 to 19 which is partially substituted by a hydroxyl group, and further preferably has an alkyl group selected from the group consisting of a group consisting of propyl sulfhydryl, butyl sulfhydryl, pentamidine, benzhydryl, 6-hydroxyhexyl (HO-C ₅ H ₁₀ -CO-) and 3-(2-hydroxyphenyl)propanyl At least one functional group of deuterated cellulose, and more preferably diethylated cellulose, acetamidine 6-hydroxyhexylcellulose, and ethyl 3-(2-hydroxyphenyl)propene cellulose, preferably It is diacetyl cellulose, acetamidine cellulose, acetamidine 6-hydroxyhexylcellulose, and ethyl 3-(2-hydroxyphenyl)propene cellulose.

The etherified cellulose (a2) may include etherified cellulose substituted with an alkyl ether group having 1 to 18 carbon atoms which may be partially substituted with a hydroxyl group or a carboxyl group.

The alkyl ether group may include an alkyl ether group having 1 to 18 carbon atoms which may be partially substituted with a hydroxyl group or a carboxyl group, and may, for example, contain a group selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group, and a hydroxyl group. At least one functional group consisting of a group consisting of a methoxy group, a hydroxyethoxy group, a 1-phenylethoxy group, a 2-phenylethoxy group, and a carboxymethoxy group.

The alkyl ether group is preferably an alkyl ether group having 1 to 18 carbon atoms which may be partially substituted with a hydroxyl group or a carboxyl group, and more preferably selected from a methoxy group, from the viewpoint of water resistance. At least one functional group of the group consisting of ethoxy, propoxy, hydroxymethoxy, 1-phenylethoxy, 2-phenylethoxy and hydroxyethoxy.

Specific examples of (a2) include methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and hydroxyethylmethylcellulose. 1-phenylethylcellulose, 2-phenylethylcellulose, carboxymethylcellulose, and the like.

In (a2), from the viewpoint of water resistance, an alkyl etherified cellulose having an alkyl group having 1 to 18 carbon atoms and an oxyalkyl etherified fiber having an alkyl group having 1 to 18 carbon atoms are preferred. More preferably, it is ethyl cellulose, (1-phenylethyl)ethyl cellulose, (2-phenylethyl)ethyl cellulose, and methyl cellulose, and most preferably ethyl cellulose. (1-Phenylethyl)ethylcellulose and (2-phenylethyl)ethylcellulose.

The etherified cellulose (a3) may include an alkyl ether group having a carbon number of 1 to 18 which may be partially substituted with a hydroxyl group or a carboxyl group, and a carbon number of 2 to 19 which may be partially substituted by a hydroxyl group. The cellulose of the thiol group, specifically, hydroxypropylmethylcellulose hexahydrophthalate or hydroxypropyl methylcellulose acetate phthalate And hydroxypropyl methylcellulose acetate succinate and the like.

Preferred examples of the ether group and the fluorenyl group are the same as (a1) and (a2).

In (a3), from the viewpoint of water resistance, 1-phenylethylcellulose acetate, 2-phenylethylcellulose acetate, ethylcellulose benzoate, and B are preferable. Cellulose 6-hydroxycaproate and ethyl cellulose 3-(2-hydroxyphenyl)propionate.

Among the polysaccharides, from the viewpoints of transparency, saponification resistance, positive birefringence, and reverse wavelength dispersibility, polysaccharide (a), more preferably cellulose and substituted cellulose, is further preferred. It is cellulose, cellulose deuterated (a1), etherified cellulose (a2), and etherified cellulose (a3).

In the modified polysaccharide (A), at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group of the polysaccharide is chemically modified to be selected from the group consisting of an ether group, a urethane group, and a urea group. When at least one functional group of the group consisting of a guanamine group and an imine group, at least one monosaccharide unit in the monosaccharide unit constituting the polysaccharide includes at least one selected from the group consisting of hydroxy groups At least one functional group of the group consisting of a base group, a carboxyl group and an amine group is selected from the group consisting of an isocyanate compound (y1), an amine compound (y2), an acid halide compound (y3), an acid anhydride (y4), and an epoxy group. At least one compound of the group consisting of the compound (y5) is chemically modified.

The isocyanate compound (y1) may be a polyisocyanate compound (y11) having two or more isocyanate groups in the molecule of the compound 1, and a monoisocyanate compound (y12) having one isocyanate group in the molecule of the compound 1.

(y11) may include an organic polyisocyanate which is generally used for producing a urethane resin, and examples thereof include an aromatic polyisocyanate, a chain aliphatic polyisocyanate, an alicyclic polyisocyanate, and an aromatic aliphatic polyisocyanate. Such modified substances (containing a urethane group, a carbodiimide group, a urea group, a urea group, a biuret group, an isocyanurate group, and A modified substance of an oxazolone group, etc.). (y11) may be used alone or in combination of two or more.

Examples of the aromatic polyisocyanate include a carbon number (excluding carbon in the NCO group; the following polyisocyanate is also the same): an aromatic diisocyanate of 6 to 16 and an aromatic triisocyanate having 6 to 20 carbon atoms; and the isocyanate. Crude goods, etc. Specific examples thereof include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-toluene diisocyanate (TDI, tolylene diisocyanate), crude TDI, and 2,4'-diphenyl group. Methane diisocyanate, 4,4'-diphenyl-methane-diisocyanate, polymethylene polyphenyl polyisocyanate (crude MDI), naphthalene-1,5-diisocyanate and triphenyl Methane-4,4',4"-triisocyanate, and the like.

Examples of the chain aliphatic polyisocyanate include a chain aliphatic diisocyanate having 1 to 10 carbon atoms of an aliphatic group (1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexaylene). Methyl diisocyanate, lysine diisocyanate, etc.).

Examples of the alicyclic polyisocyanate include an alicyclic diisocyanate having 6 to 16 carbon atoms (isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,4-cyclohexane diisocyanate). ,drop Norbornane diisocyanate, bis(2-isocyanateethyl)-4-cyclohexene-1,2-dicarboxylate, etc.).

Examples of the aromatic aliphatic polyisocyanate include aromatic aliphatic diisocyanates having 8 to 12 carbon atoms (benzoyl diisocyanate and α,α,α',α'-tetramethylbenzenedimethyl diisocyanate, etc.). Wait.

Specific examples of the modified polyisocyanate include carbodiimide modified MDI and the like.

(y11) is a chain aliphatic polyisocyanate from the viewpoint of saponification resistance, transparency, positive birefringence, and reverse wavelength dispersibility.

When the modified polysaccharide (A) is produced by using (y11), the compound (z) having at least one active hydrogen group can also be used.

As (z), a compound having at least one active hydrogen group having 4 to 100 carbon atoms may be contained.

The active hydrogen group may include a hydroxyl group, an amine group, a carboxyl group, a thiol group, a phosphoric acid group or the like.

Specific examples of (z) include those having a hydroxyl group (methanol, ethanol, n-propanol, n-butanol, n-octanol, phenol, etc.), those having an amine group {ethylamine, etc.), and those having a carboxyl group. {formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, stearic acid and behenic acid, etc.}, having a mercaptan The base {octyl thiol, etc.} and the phosphoric acid group {the above-mentioned hydroxyl group (methanol, etc.) and phosphoric anhydride reaction product, etc.} and the like.

(z) One type may be used alone or two or more types may be used in combination.

In the case of (z), from the viewpoints of surface hardness, resin strength, elongation at break, flexibility, and positive birefringence, a compound having a hydroxyl group having 4 to 100 carbon atoms is preferable, and further preferably having carbon. A compound of 4 to 10 hydroxy groups.

Examples of (y12) include a reaction product of an aromatic monoisocyanate, an alkyl monoisocyanate, an alicyclic monoisocyanate, and a diisocyanate compound and a compound having one active hydrogen group at a molar ratio of 1:1.

The aromatic monoisocyanate may include an aromatic monoisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter), and specific examples thereof include phenyl isocyanate, toluene isocyanate, and benzodimethylisocyanate. α,α,α',α'-tetramethylbenzenedimethylisocyanate, naphthalene isocyanate, and the like.

The alkyl monoisocyanate may include an alkyl (straight or branched) monoisocyanate having 1 to 100 carbon atoms, and specific examples thereof include a carbon number of 1 to 18 (methyl isocyanate or ethyl isocyanate). , n-propyl isocyanate, n-butyl isocyanate, second butyl isocyanate, tert-butyl isocyanate, n-hexyl isocyanate, 2-ethylhexyl isocyanate, isocyanic acid N-octyl ester, n-dodecyl isocyanate, n-octadecyl isocyanate, etc. The alkyl monoisocyanate is preferably one having a carbon number of from 1 to 18 in terms of transparency, saponification resistance, positive birefringence, and reverse wavelength dispersibility.

The alicyclic monoisocyanate may contain an alicyclic monoisocyanate having 4 to 15 carbon atoms, and specific examples thereof include cyclobutyl isocyanate, cyclohexyl isocyanate, cyclooctyl isocyanate, and the like. Cyclodecyl cyanate, cyclododecyl isocyanate, cyclotetradecyl isocyanate, cyclotetradecyl isocyanate, isophorone isocyanate, dicyclohexylmethane-4-isocyanate , cyclohexyl isocyanate, methylcyclohexyl isocyanate and Alkyl isocyanate and the like.

In the reaction product in which the molar ratio of the diisocyanate compound to the compound having one active hydrogen group is 1:1, the diisocyanate compound may include the diisocyanate compound having two isocyanate groups in the above (y11), specifically In other words, aromatic diisocyanate {1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-toluene diisocyanate (TDI), crude TDI, 2,4'-diphenyl Methane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI) and naphthalene-1,5-diisocyanate, etc., alkyl (linear or branched) diisocyanate {1,6-hexamethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and isocyanate diisocyanate, etc., alicyclic diisocyanate {isophorone diisocyanate, 4,4'-dicyclohexylmethane Isocyanate, 1,4-cyclohexane diisocyanate and lower An alkane diisocyanate or the like and an aromatic aliphatic diisocyanate {benzodimethyl diisocyanate and α,α,α',α'-tetramethylbenzenedimethyl diisocyanate, etc.

In addition, examples of the compound having one active hydrogen group include one active hydrogen group in the above compound (z), and specific examples thereof include monohydric alcohols having a carbon number of from 1 to 100 (methanol, ethanol, and n-propyl). The alcohol, n-butanol, n-octanol, phenol, etc. are preferably a monohydric alcohol having 1 to 10 carbon atoms from the viewpoints of surface hardness, resin strength, elongation at break, flexibility, and positive birefringence. Monoamines having a carbon number of 1 to 100, such as ethylamine, etc., and monocarboxylic acids having a carbon number of 1 to 100, {formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, Tannic acid, lauric acid, myristic acid, stearic acid, and behenic acid, etc.

(y12), in terms of saponification resistance, transparency, surface hardness, resin strength, elongation at break, flexibility, and positive birefringence, alkyl monoisocyanate and alicyclic monoisocyanate are preferred. Further, it is preferably an alkyl monoisocyanate having 1 to 18 carbon atoms of an alkyl group and an alicyclic monoisocyanate having 4 to 15 carbon atoms, particularly preferably methyl isocyanate, ethyl isocyanate or isocyanate. Propyl ester, n-butyl isocyanate, second butyl isocyanate, tert-butyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate N-octyl cyanate, n-dodecyl isocyanate and stearyl isocyanate.

(y1) may be used alone or in combination of two or more.

(y1) is preferably a monoisocyanate compound (y12) from the viewpoints of saponification resistance, transparency, surface hardness, resin strength, elongation at break, flexibility, and positive birefringence. It is an alkyl monoisocyanate and an alicyclic monoisocyanate, more preferably an alkyl group of an alkyl monoisocyanate having 1 to 18 carbon atoms and an alicyclic monoisocyanate having 4 to 15 carbon atoms, particularly preferably methyl isocyanate. , ethyl isocyanate, n-propyl isocyanate, n-butyl isocyanate, second butyl isocyanate, tert-butyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate, n-octyl isocyanate, n-dodecyl isocyanate and n-octadecyl isocyanate.

As the amino group compound (y2), ammonia, a primary amine, and a secondary amine may be contained.

As the primary amine, it may contain a monoamine having 1 to 20 carbon atoms (alkyl (linear or branched) monoamine, alicyclic monoamine, aromatic aliphatic monoamine, aromatic monoamine and alkanolamine} and carbon A number of 1 to 20 polyamines {diamines and triamines, etc.}.

Examples of the monoamine include an alkyl monoamine {monoalkyl (alkyl group having 1 to 20 carbon atoms) amine (for example, methylamine, ethylamine, n-butylamine, octylamine, etc.), etc. Alicyclic monoamines {e.g., cyclohexylamine, etc.}, aromatic aliphatic amines (e.g., benzylamine, etc.), aromatic amines {e.g., aniline, toluidine, and naphthylamine, etc.) and alkanolamines {monoalkanolamines (including hydroxy groups) The number of carbon atoms of the alkyl group is 1 to 20, such as ethanolamine, etc.).

The secondary amine may include an amine having a hydrocarbon group of 1 to 20 carbon atoms and/or a hydroxyalkyl group having 1 to 20 carbon atoms.

Examples of the hydrocarbon group include an alkyl group (linear or branched) (such as a methyl group, an ethyl group, and a propyl group), an alicyclic group (such as a cyclohexyl group), and an aromatic hydrocarbon (such as a phenyl group or a naphthyl group).

The secondary amine may specifically contain dimethylamine, diethylamine, ethylmethylamine, diethanolamine or the like.

(y2) may be used alone or in combination of two or more.

(y2), in terms of saponification resistance, transparency, surface hardness, resin strength, elongation at break, flexibility, and positive birefringence, an alkyl monoamine and an alicyclic monoamine are preferred. .

The acid halide compound (y3) may include a halide of a carboxylic acid having 1 to 20 carbon atoms (fluorenyl halide), and as the carboxylic acid, specifically, an aliphatic monocarboxylic acid having 1 to 20 carbon atoms is exemplified. (formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, etc.), aromatics with a carbon number of 7-20 Monocarboxylic acids (benzoic acid, cinnamic acid, naphthoic acid, etc.), aliphatic polycarboxylic acids having 3 to 20 carbons (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, bisphenol) Acid, azelaic acid and sebacic acid, and aromatic polycarboxylic acids having a carbon number of 8 to 20 (phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) )Wait.

Examples of the halide include fluoride, chloride, bromide, and iodide.

(y3) may be used alone or in combination of two or more.

(y3), in terms of saponification resistance, transparency, surface hardness, resin strength, elongation at break, flexibility, and positive birefringence, an aliphatic monocarboxylic acid having 1 to 20 carbon atoms is preferred. Acid halide.

As the acid anhydride (y4), a compound having a carbon number of 3 to 20 having a 1,3-dioxy-2-oxooxyalkylene group may be contained, and a dicarboxylic acid (aliphatic dicarboxylic acid) may be contained. An acid anhydride such as succinic acid, adipic acid, sebacic acid, sebacic acid or maleic acid, or an aromatic dicarboxylic acid (such as phthalic acid).

(y4) may be used alone or in combination of two or more.

(y4), saponification resistance, transparency, surface hardness, resin strength, elongation at break From the viewpoint of the rate, flexibility, and positive birefringence, an acid anhydride of an aliphatic dicarboxylic acid is preferred.

The epoxy compound (y5) may include an aromatic compound (y51) having an epoxy group and another epoxy compound (y52).

The epoxy compound (y5) is chemically modified, whereby the epoxy compound (y5) is bonded to the polysaccharide (a) with an α or β-hydroxy ether bond, and the branches are arranged neatly due to the influence of the hydroxyl group, and thus The etherified polysaccharide (the above (a2) to (a3) and the like) is extremely excellent in positive birefringence and reverse wavelength dispersibility, and is excellent in saponification resistance and transparency. Further, in the usually etherified polysaccharide (the above (a2) to (a3), etc.), the average molecular dispersion of the monosaccharide unit cannot be set within the above range, but by the α or β-hydroxy ether bond. By performing bonding, the average molecular dispersion of the monosaccharide unit can be set within the above range.

As (y51), the following aromatic compound (B) may be contained. When the following aromatic compound (B) is used, the branches are regularly aligned by the interaction of the branched aromatic rings, and thus the positive birefringence and the reverse wavelength dispersibility are further excellent.

Aromatic compound (B): an aromatic compound (b1) selected from one hydrogen atom in an aromatic ring substituted by an epoxy group, and one hydrogen atom in an aromatic ring having a carbon number of 3 to 8 via an alkyl group The oxyalkyl-substituted aromatic compound (b2) and one hydrogen atom in the aromatic ring are substituted with at least one carbon atom of the alkyl group into an oxygen atom through an alkylene group having an alkyl group having 3 to 8 carbon atoms. At least one compound of the group consisting of the functional group-substituted aromatic compound (b3).

In the aromatic compound (B), the aromatic ring may include a ring structure composed of only carbon (a benzene ring, a naphthalene ring, etc.) and a heterocyclic ring containing an element other than carbon in the ring structure (furan, thiophene, pyrrole, and imidazole). Wait}.

In the aromatic ring, from the viewpoints of birefringence, reverse wavelength dispersion, and water resistance, it is preferably The ring structure is only an aromatic ring composed of carbon, and more preferably a benzene ring.

Further, in (B), one hydrogen atom in the aromatic ring may be an epoxy group such as an epoxy group, an alkylene group having an alkyl group having 3 to 8 carbon atoms, and a ring having a carbon number of 3 to 8. The oxyalkyl ether group may be substituted, and the other hydrogen atom may be substituted with another functional group (x) other than the epoxy group or the like.

Examples of the other functional group (x) include a halogen group (such as F, Cl, Br, and I), a hydroxyl group, an amine group, and an alkyl group having an alkyl group having an alkyl group having 1 to 8 carbon atoms or an alkyl group. It is an alkylamine group of 1-8.

Further, in (B), a plurality of aromatic rings may be bonded to an epoxy group or an epoxy group.

Specific examples of the aromatic compound (b1) in which one hydrogen atom in the aromatic ring is substituted with an epoxy group include styrene oxide, 2-(4-chlorophenyl)ethylene oxide, and 2 -(4-Fluorophenyl)oxirane, 2-(4-bromophenyl)oxirane, 2,3-diphenylethylene oxide, and the like.

The aromatic compound (b2) in which one hydrogen atom in the aromatic ring is substituted with an epoxy group having 3 to 8 carbon atoms in the alkyl group, specifically, 2-benzyl oxirane or the like can be mentioned.

An aromatic compound (b3) substituted with a functional group in which at least one carbon atom of the alkyl group is substituted with an oxygen atom in an alkylene group having 1 to 6 carbon atoms in the aromatic ring; Specific examples thereof include benzyl glycidyl ether, trityl glycidyl ether, glycidyl-4-methoxyphenyl ether, 1-naphthyl-2-oxiranyl methyl ether, and 2- [(2-Naphthyloxy)methyl]oxirane, 4-chlorophenyl-2-oxiranemethylether, 2-[(4-ethylphenoxy)methyl]epoxy Ethane, 2-[(3-methylphenoxy)methyl]oxirane, 2-[(2-methylphenoxy)methyl]oxirane, 2-{[4-( Benzyloxy)phenoxy]methyl}oxirane, 2-[(4-mercaptophenoxy)methyl]oxirane, 2-[(4-bromophenoxy)methyl] Ethylene oxide, 4-chloro-3-methylphenyl-2-oxirane methyl ether, 2-(2-oxiranylmethoxy)benzonitrile and 2-[(benzyloxy) Base) methyl]oxirane and the like.

(y51) is preferably an aromatic compound (B) from the viewpoint of transparency, saponification resistance, positive birefringence, and reverse wavelength dispersibility, and further preferably one hydrogen atom in the aromatic ring. The epoxy group-substituted aromatic compound (b1) is particularly preferably styrene oxide.

(y52) may include an epoxy compound having an epoxy group and having an aromatic ring and having 2 to 20 carbon atoms, and specific examples thereof include ethylene oxide and a non-cyclic aliphatic having 3 to 20 carbon atoms. Epoxy compound {1,2-epoxypropane and 1,2-butylene oxide, etc., alicyclic epoxy compound {manganese dioxide, bis(3,4-epoxycyclohexyl) adipate, (3,4-epoxycyclohexyl)methyl-3',4'-epoxycyclohexanecarboxylate, (3,4-epoxy-6-methylcyclohexyl)methyl-3', 4'-Epoxy-6-methylcyclohexanecarboxylate and ethyl-1,2-bis(3,4-epoxycyclohexanecarboxylic acid) ester, etc.

(y5) may be used alone or in combination of two or more.

In the epoxy compound (y5), from the viewpoints of transparency, saponification resistance, positive birefringence, and reverse wavelength dispersibility, an aromatic compound (y51) having an epoxy group is preferred, and further preferably The aromatic compound (B), more preferably an aromatic compound (b1) in which one hydrogen atom in the aromatic ring is substituted with an epoxy group, is preferably an epoxy phenylethane.

The modified polysaccharide (A) can be obtained by using the above polysaccharide (a) and selected from the group consisting of an isocyanate compound (y1), an amine compound (y2), an acid halide compound (y3), an acid anhydride (y4), and an epoxy compound (y5). It is produced by at least one compound of the group.

When the modified polysaccharide (A) is produced by using the polysaccharide (a) and the isocyanate compound (y1), a compound having at least one selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group can be reacted with an isocyanate compound. A well-known method.

Further, when the modified polysaccharide (A) is produced by using the polysaccharide (a) and the amine compound (y2), a compound having a carboxyl group can be reacted with an amine compound to obtain a guanamine compound. A well-known method of things.

Further, when the modified polysaccharide (A) is produced by using the polysaccharide (a) and the acid halogen compound (y3), a known method of obtaining a quinone imine compound by reacting a compound having an amine group with an acid halogen compound can be used. .

Further, when the modified polysaccharide (A) is produced by using the polysaccharide (a) and the acid anhydride (y4), it is known to obtain a guanamine compound and/or a ruthenium compound by reacting a compound having an amine group with an acid anhydride. The method.

Further, when the modified polysaccharide (A) is produced by using the polysaccharide (a) and the epoxy compound (y5), a compound having a hydroxyl group and an epoxy compound can be used to obtain an α- and/or β-hydroxyether group. A known method of the compound.

In the modified polysaccharide (A), from the viewpoints of transparency, saponification resistance, positive birefringence, and reverse wavelength dispersibility, it is preferred to modify the polysaccharide (A1) and the modified polysaccharide (A2). The polysaccharide (A1)-based polysaccharide is the above-mentioned polysaccharide (a), and at least one of the monosaccharide units constituting the polysaccharide is at least one selected from the group consisting of the following general formulae (1) to (6). And at least one of the substituents represented by the following formula (7); the modified polysaccharide (A2)-based polysaccharide is the above-mentioned polysaccharide (a), and at least one hydroxyl group in (a) has an epoxy group The above aromatic compound (B) is chemically modified.

In the above formula, X ¹ to X ¹³ are each independently a hydrogen atom or a substituent represented by the following formula (7); and at least one of X ¹ to X ³ is represented by the following formula (7). a substituent; at least one of X ⁴ to X ⁶ is a substituent represented by the following formula (7); and at least one of X ⁷ and X ⁸ is a substituent represented by the following formula (7); At least one of X ¹⁰ and X ¹¹ is a substituent represented by the following formula (7); and at least one of X ¹² and X ¹³ is a substituent represented by the following formula (7); Is an oxygen atom or an NH group, and Z is a hydroxyl group or a substituent represented by (8).

In the above formula, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms; * represents a substituent represented by the formula (7) and the above formula (1) to (by a bond attached thereto); 6) is bonded to an oxygen atom and/or a nitrogen atom adjacent to X.

*-HN-R ² (8)

In the above formula, R ² is a monovalent hydrocarbon group having 1 to 18 carbon atoms or an alkyl polyoxyalkylene group; * represents a substituent represented by the formula (8) and the above formula by a bond attached thereto (5) A carbon atom bond adjacent to Z.

In the structure of the general formulae (1) to (6), (A1), from the viewpoints of surface hardness, adhesion, and flexibility, the formula (1) or (6) is preferred, and further preferably. It is of the formula (1).

In the general formulae (7) and (8), from the viewpoints of surface hardness, adhesion, and flexibility, R ¹ and R ² are preferably a hydrocarbon group having 1 to 18 carbon atoms, particularly preferably R ¹ and R ^{2 is} independently methyl, ethyl, n-propyl, n-butyl, t-butyl, t-butyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-octyl, n-dodecyl And n-octadecyl.

The modified polysaccharide (A1) is preferably an aminocarboxylic acid obtained by the following formula (1) from the viewpoints of coloring property, transparency, saponification resistance, positive birefringence, and reverse wavelength dispersibility. The total introduction ratio of the ester group, the urea group, the guanamine group and the imine group is 0.01 to 3, and the total introduction rate is preferably 0.04 to 3, more preferably 0.06 to 2, and particularly preferably 0.11 to 1.4. .

Total introduction rate of urethane group, urea group, guanamine group and imine group = P/T' (1)

P: NMR integral value (P ₁ ) of a hydrogen atom of a urethane group chemically modified to constitute a hydroxyl group, a carboxyl group and an amine group of a monosaccharide unit of the modified polysaccharide (A1), a urea group The NMR integrated value (P ₂ ) of the hydrogen atom, the NMR integrated value (P ₃ ) of the hydrogen atom of the guanamine group, and the NMR integrated value (P ₄ ) of the hydrogen atom of the imine group are applied to the following formula (2). The total integrated value P = P ₁ + P ₂ / 2 + P ₃ + P ₄ (2)

Further, in the case where the amidino group is not {-C(=O)-NH-R (R is a hydrogen atom)} and is (-C(=O)-NH ₂ ), P _{3 is} set to P. ₃ /2.

T': NMR integral value of a hydrogen atom directly bonded to a carbon atom at the 4-position of the monosaccharide unit constituting the modified polysaccharide (A1)

<Method for Measuring Total Introduction Rate of Carbamate Group, Urea Group, Amidino Group and Imine Group>

Solvent: Deuterated dimethyl hydrazine

Device: AVANCE300 (made by Japan Bruker Co., Ltd.)

Frequency: 300MHz

When the introduction ratio is more than 0.01, the transparency, the saponification resistance, and the reverse wavelength dispersibility are further improved. When the introduction ratio is 3 or less, the positive birefringence is further improved.

The modified polysaccharide (A2) is a polysaccharide obtained by chemically modifying the above polysaccharide (a), and at least one hydroxyl group in the (a) is chemically modified by the following aromatic compound (B) having an epoxy group. Modified polysaccharides.

Aromatic compound (B): an aromatic compound (b1) selected from one hydrogen atom in an aromatic ring substituted by an epoxy group, and one hydrogen atom in an aromatic ring having a carbon number of 3 to 8 via an alkyl group The oxyalkyl-substituted aromatic compound (b2) and one hydrogen atom in the aromatic ring are substituted with at least one carbon atom of the alkyl group into an oxygen atom through an alkylene group having an alkyl group having 3 to 8 carbon atoms. At least one compound of the group consisting of the functional group-substituted aromatic compound (b3).

The preferred ones of the aromatic compound (B) are as described above.

From the viewpoint of reverse wavelength dispersibility and water resistance, in the modified polysaccharide (A2), the ratio of the functional group chemically modified by the aromatic compound (B) in the hydroxyl group of the polysaccharide (a) is the hydroxyl group in the polysaccharide (a) The number is based on the reference, preferably 30 to 100%, and more preferably 60 to 100%.

The ratio of the chemically modified functional groups can be determined by ¹ H-NMR. Specifically, the measurement was carried out by the following measurement method.

<Method for Measuring the Ratio of Functional Groups Modified by (B)>

The ¹ H-NMR measurement of the polysaccharide (a) and the modified polysaccharide (A2) before modification was carried out. The following integral value obtained by the respective measurement results was applied to the following formula (3), whereby the ratio (%) of the functional group modified by (B) was calculated.

The ratio (%) of the functional group modified by (B) = {(T-S) / T} × 100 (3)

S = the integral value of the hydrogen atom of the hydroxyl group of the modified polysaccharide (A2)

T = hydrogen atom integral value of the hydroxyl group of polysaccharide (a)

Solvent: Deuterated dimethyl hydrazine

Device: AVANCE300 (made by Japan Bruker Co., Ltd.)

Frequency: 300MHz

Further, the aromatic ring concentration in the modified polysaccharide (A2) is preferably from 20 to 80% by weight, and more preferably from 25 to 70% by weight, from the viewpoints of coloring property, high birefringence, and reverse wavelength dispersibility. More preferably, it is 30 to 65% by weight.

The aromatic ring concentration was measured by the following measurement method.

<Measurement of aromatic ring concentration>

The ¹ H-NMR measurement of the polysaccharide (a) and the modified polysaccharide (A2) before modification was carried out. The following integrated value obtained by the respective measurement results was applied to the following formula (4), whereby the aromatic ring concentration (% by weight) of the modified polysaccharide (A2) was calculated.

Aromatic ring concentration (% by weight) = {U × W / (U × W + V)} × 100 (4)

U = (integral value of one hydrogen atom in the structure of the aromatic compound (B)) × (number of aromatic rings in the aromatic compound (B)) × 5 / (in the monosaccharide constituting the modified polysaccharide (A2), The total of the integrated values of the hydrogen atoms bonded to the carbon in the 1st to 5th positions)

V = molecular weight of the monosaccharide constituting the polysaccharide (a)

W = molecular weight of aromatic compound (B)

Solvent: Deuterated dimethyl hydrazine

Device: AVANCE300 (made by Japan Bruker Co., Ltd.)

Frequency: 300MHz

The molecular weight (quantitative average molecular weight (Mn) of the modified polysaccharide (A), the molecular weight in the case of a single compound, in terms of the solvent solubility of (A), the heat resistance and adhesion of the reverse wavelength dispersion film and the sheet It is preferably 3,000 to 7 million, and more preferably 3,500 to 6 million, and particularly preferably 4,000 to 5 million.

The number average molecular weight (Mn) in the present invention is measured by the following conditions.

Device: gel permeation chromatography

Solvent: N,N-dimethylformamide

Reference material: polystyrene

Sample concentration: 3mg/ml

Column stationary phase: PLgel MIXED-B

Column temperature: 40 ° C

The resin composition for a reverse wavelength dispersion film of the present invention may contain esterified cellulose (C). Since the modified polysaccharide (A) has a very high reverse wavelength dispersibility, the reverse wavelength dispersibility can be appropriately adjusted by containing (C) having a low reverse wavelength dispersibility.

The esterified cellulose (C) in the present invention may contain a known esterified cellulose, and examples thereof include an alkyl esterified cellulose (carbon number of the alkyl group: 1 to 18), and the like, and an alkyl ester group. For example, an acetate group, a propionate group, a butyrate group, etc. are mentioned. (C) may be used alone or in combination of two or more.

Esterification rate of esterified cellulose (C) from the viewpoints of transparency, saponification resistance, positive birefringence, and reverse wavelength dispersion (each monosaccharide unit is directly bonded to the hydroxyl group of cellulose) The average number of ester group substitutions is preferably from 0.1 to 3.

The esterification ratio of the esterified cellulose was determined by NMR.

The Mn of the esterified cellulose (C) is preferably from 3 to 10,000,000, and more preferably from 5 to 8,000,000, from the viewpoints of transparency, saponification resistance, positive birefringence, and reverse wavelength dispersion.

In the above (C), from the viewpoint of reverse wavelength dispersibility, an alkyl esterified cellulose having 1 to 18 carbon atoms is preferred, and further preferably having an alkyl ester group, a propionate group and An esterified cellulose having at least one ester group of a group consisting of butyrate groups, and more preferably cellulose acetate, cellulose butyrate, cellulose propionate, cellulose acetate propionate, and cellulose acetate butyrate .

The resin composition for reverse wavelength dispersion film of the present invention contains esterified cellulose In the case of (C), the content of the modified polysaccharide (A) in the resin composition for a reverse wavelength dispersion film is (from the viewpoints of transparency, saponification resistance, positive birefringence, and reverse wavelength dispersibility) The total weight of A) and (C) is preferably from 1 to 99.9% by weight, and more preferably from 3 to 95% by weight.

When the resin composition for a reverse wavelength dispersion film of the present invention contains the esterified cellulose (C), the reverse wavelength is used in terms of transparency, saponification resistance, positive birefringence, and reverse wavelength dispersion. The content of the esterified cellulose (C) in the resin composition for a dispersion film is preferably from 0.1 to 99% by weight, and more preferably from 5 to 97% by weight, based on the total weight of the (A) and (C).

The resin composition for a reverse wavelength dispersion film of the present invention may be added with an organic solvent, a leveling agent or the like as needed.

Examples of the organic solvent include glycol ethers (such as ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone). Ester (ethyl acetate, butyl acetate, ethylene glycol alkyl ether acetate, methyl lactate, propylene glycol alkyl ether acetate, etc.), aromatic hydrocarbons (toluene, xylene, mesitylene, etc.), alcohol (methanol, ethanol, n-propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.), decylamine (N,N-dimethylacetamide and N,N-dimethyl Myramine, etc.), hydrazine (dimethyl hydrazine) and ether (tetrahydrofuran, 1,3-two Alkane, 1,4-two Alkane, 1,3-dioxolane, 1,8-anthracene, etc.). These may be used alone or in combination of two or more.

The amount of the organic solvent to be added is preferably from 0 to 400% by weight, more preferably from 0 to 400% by weight, based on the weight of the resin composition for the reverse wavelength dispersion film, from the viewpoint of the moldability and the viscosity of the resin composition for a reverse wavelength dispersion film. 3 to 350% by weight, particularly preferably 5 to 300% by weight.

Examples of the leveling agent include a fluorine-based leveling agent (perfluoroalkyl ethylene oxide adduct, etc.) and a polyfluorene-based leveling agent (amine-based polyether modified poly-oxygen, methoxy) The base is modified by polyoxyl and polyether modified polyfluorene, etc.). The addition amount of the leveling agent is preferably 0 to 20% by weight, more preferably 0 to 20% by weight, based on the weight of the resin composition for the reverse wavelength dispersion film, from the viewpoint of the effect of addition and transparency. It is 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight.

The resin composition for a reverse wavelength dispersion film of the present invention may further contain inorganic fine particles, a dispersant, an antifoaming agent, a thixotripy imparting agent, a slip agent, a flame retardant, an antistatic agent, an antioxidant, and the like according to the purpose of use. A known additive such as an ultraviolet absorber or the like which can be added to the composition of the reverse wavelength dispersion film. Specifically, those described in the publicly known documents (JP-A-2012-088408, etc.) and the like can be cited.

The resin composition for a reverse wavelength dispersion film of the present invention can be obtained by mixing a group selected from an ether group, a urethane group, a urea group, a guanamine group and an imine group by a disperser or the like. At least one modified polysaccharide (A), and other components such as esterified cellulose (C) and an organic solvent are mixed as needed. The mixing temperature is usually from 10 ° C to 40 ° C, preferably from 20 ° C to 30 ° C.

The resin composition for a reverse wavelength dispersion film of the present invention may be added to a pigment previously used for paints, inks, and the like. The amount of the pigment to be added is preferably from 0 to 300% by weight, and more preferably from 0 to 200% by weight, based on the weight of the resin composition for the reverse wavelength dispersion film.

Examples of the pigment include chrome yellow, zinc yellow, iron blue, barium sulfate, cadmium red, titanium oxide, zinc white, red iron oxide, aluminum oxide, calcium carbonate, ultramarine blue, carbon black, graphite, and titanium black. Wait.

In order to improve the dispersibility of the pigment and the storage stability of the resin composition for a reverse wavelength dispersion film in the case of using a pigment, a pigment dispersant may be added to the resin composition for a reverse wavelength dispersion film of the present invention.

As the pigment dispersant, a pigment dispersant (Anti-Terra-U, Disperbyk-101, 103, 106, 110, 161, 162, 164, 166, 167, 168, 170, 174, manufactured by BYK-Chemie Co., Ltd.) may be mentioned. 182, 184, and 2020, etc., pigment dispersing agents (Ajisper PB711, PB821, PB814, PN411, and PA111) manufactured by Ajinomoto Fine-Techno Co., Ltd., and pigment dispersing agents manufactured by Lubrizol (Solsperse 5000, 12000, 32000, 33000, and 39000, etc.) ).

These pigment dispersing agents may be used alone or in combination of two or more.

The amount of the pigment dispersant to be added is preferably from 0 to 20% by weight, and more preferably from 0 to 10% by weight, based on the weight of the resin composition for the reverse wavelength dispersion film.

When the resin composition for a reverse wavelength dispersion film of the present invention contains an organic solvent, a coating method to a substrate can be applied to a known coating method such as spin coating, roll coating, or spray coating, and lithography or carton printing. A known printing method such as carton printing, metal printing, offset printing, screen printing, and gravure printing. Further, it is also possible to apply an inkjet method in which fine droplets are continuously ejected.

The coating film thickness is preferably from 0.5 to 300 μm, more preferably from 1 to 250 μm, from the viewpoint of drying property, abrasion resistance, solvent resistance, and stain resistance.

When the resin composition for a reverse wavelength dispersion film of the present invention contains an organic solvent, it is preferably dried after application. Examples of the drying method include hot air drying (such as a dryer). The drying temperature is usually 10 to 200 ° C. The upper limit is preferably 150 ° C from the viewpoint of smoothness and appearance of the coating film, and the lower limit is preferably 30 ° C from the viewpoint of drying speed.

Further, when the resin composition for a reverse wavelength dispersion film does not contain an organic solvent, it may be melt-mixed. Further, examples of the method for forming the film and the sheet include injection molding, compression molding, calender molding, slush moulding, rotary molding, extrusion molding, blow molding, and film molding (casting method, tenter method, and The molding is performed by an expansion method or the like.

The reverse wavelength dispersion film and sheet of the present invention are preferably transparent.

The haze value of the reverse wavelength dispersion film and the sheet is preferably 3% or less from the viewpoint of transparency.

The total light transmittance of the reverse wavelength dispersion film and the sheet is preferably 85% or more from the viewpoint of coloring property and transparency.

The retardation film and sheet of the present invention can be produced by molding a film or sheet composed of the resin composition for a reverse wavelength dispersion film, or by stretching (aligning) after molding. As the film and sheet forming method, the above method can be used.

The retardation film and sheet of the present invention are preferably transparent.

From the viewpoint of transparency, the haze value of the retardation film and the sheet is preferably 3% or less.

The total light transmittance of the retardation film and the sheet is preferably 85% or more from the viewpoint of coloring property and transparency.

The circularly polarizing film and sheet of the present invention can be produced by a known melt film formation method or a cast film formation method.

The circularly polarizing film and sheet of the present invention are preferably transparent.

From the viewpoint of transparency, the haze value of the circular polarizing film and the sheet is preferably 3% or less.

The total light transmittance of the circularly polarizing film and the sheet is preferably 85% or more from the viewpoint of coloring property and transparency.

Example

Hereinafter, the present invention will be further described by way of examples, but the invention is not limited thereto. Hereinafter, unless otherwise specified, % represents % by weight, and parts represents parts by weight.

<Production Examples 1 to 51 and Comparative Production Examples 1 to 32>

[Synthesis of Modified Polysaccharide (A)]

To the reaction vessel equipped with a stirring device, a heating and cooling device, and a thermometer, 150 parts of the polysaccharides and dimethylacetamide described in Tables 1 to 5 or Tables 7 to 9 were added, and the mixture was stirred at 150 ° C for 1 hour. After cooling to 100 ° C, 15 parts of lithium chloride and 0.1 part of dibutyltin laurate were added to the reaction solution, and the mixture was stirred while maintaining the temperature at 100 ± 20 ° C for 24 hours. Thereafter, the mixture was cooled to 0 ° C, and 100 parts of pyridine, as shown in Tables 1 to 5 or Tables 7 to 9 (y1) or (y)', was added to the reaction solution while maintaining the temperature at 0 ± 5 ° C. Stir for 2 hours. The reaction solution was added to 2000 parts of water, and the precipitate was collected by filtration, washed with 2000 parts of water, and dried under reduced pressure at 100 ° C for 20 hours, thereby obtaining modified polysaccharides as described in Tables 1 to 5 or Tables 7 to 9 ( A-1)~(A-51) and comparative modified polysaccharides (A'-1)~(A'-32).

<Manufacturing Examples 52 to 61>

[Synthesis of Modified Polysaccharide (A)]

The polysaccharide (a) and the aromatic compound (B) in the amounts described in Table 6 were added to 150 parts of water, and the mixture was stirred at 80 ° C for 2 hours. Thereafter, 15 parts of sodium hydroxide was added, and the mixture was stirred for 12 hours while maintaining the temperature at 80 ± 10 °C. After adding 20 parts of acetic acid to the obtained reaction solution for neutralization, white precipitates (filter paper: manufactured by ADVANTEC Co., Ltd.; No. 5) were collected by filtration, and washed three times with 200 parts of toluene. The modified polysaccharides (A-52) to (A-61) shown in Table 6 were obtained by drying under reduced pressure at 100 ° C for 3 hours.

In Table 5, (a'1) to (a'8) were used in the following Production Examples 62 to 69.

<Manufacturing Example 62>

[Reactant of benzamidine chloride and acetamidine cellulose (a'1) {acetamidine fiber]}

To 100 parts of toluene, 5 parts of acetonitrile cellulose ("cellulose acetate L-20" manufactured by Daicel Co., Ltd.) was added, and the mixture was stirred at 80 ° C for 1 hour. After cooling to 25 ° C, 3 parts of benzamidine chloride ("B0105" manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.02 parts of triethylamine were added to the reaction solution, and the temperature was maintained while maintaining the temperature at 80 ± 10 ° C. hour. Thereafter, the mixture was cooled to 25 ° C, and the reaction solution was added to 500 parts of acetone, whereby the precipitated reaction product as a white solid was collected by filtration, and washed with 1000 parts of acetone. The mixture was dried under reduced pressure at 40 ° C for 3 hours, whereby a reaction product (a'1) of benzamidine chloride and acetonitrile cellulose was obtained.

<Manufacturing Example 63>

[Reactant of benzamidine chloride and ethyl cellulose (a'2) {ethyl cellulose benzoate}]

In the above-mentioned Production Example 61, "Ethylcellulose ("cellulose acetate L-20" manufactured by Daicel Co., Ltd.) was changed to "ethyl cellulose ("OCOCEL 10cps manufactured by Dow Chemical Co., Ltd." In addition, 3.5 parts of the reaction product (a'2) of benzamidine chloride and ethyl cellulose was obtained by the same method.

<Manufacturing Example 64>

[Reactant of styrene and acetonitrile cellulose (a'3) {1-phenylethyl cellulose acetate and 2-phenylethyl cellulose acetate}]

Five parts of acetonitrile cellulose ("cellulose acetate L-20" manufactured by Daicel Co., Ltd.) was added to 100 parts of toluene, and the mixture was stirred at 80 ° C under nitrogen for 1 hour. After 0.02 parts of azobisisobutyronitrile (AIBN, azobisisobutyronitrile) was added to the reaction solution, 5 parts of styrene was added dropwise over 3 hours, and the mixture was stirred while maintaining the temperature at 80 ° C ± 10 ° C for 12 hours. Thereafter, 500 parts of hexane was added to the reaction solution, whereby a white precipitate was collected by filtration and washed with 1000 parts of hexane. The mixture was dried under reduced pressure at 60 ° C for 3 hours, whereby a reaction product (a'3) of styrene and acetonitrile was obtained.

<Manufacturing Example 65>

[Reactant of styrene and ethyl cellulose (a'4) {(1-phenylethyl)ethylcellulose, (2-phenylethyl)ethylcellulose}]

In the above-mentioned Production Example 63, "Ethylcellulose ("cellulose acetate L-20" manufactured by Daicel Co., Ltd.) 5 parts" was changed to "ethyl cellulose ("OWOCEL (made by Dow Chemical Co., Ltd.)" A reaction product (a'4) of styrene and ethyl cellulose was obtained by the same method except that 10 cps)))).

<Manufacturing Example 66>

[3,4-dihydrocoumarin (3,4-dihydrocoumarin) and acetonitrile cellulose reaction (a'5) {acetonitrile 3-(2-hydroxyphenyl) propylene cellulose}]

5 parts of acetonitrile cellulose ("cellulose acetate L-20" manufactured by Daicel Co., Ltd.) was added to 100 parts of toluene, and dehydration in the reaction system was carried out at 110 ° C under reflux of toluene for 3 hours. After dehydration, 4 parts of 3,4-dihydrocoumarin ("D1223" manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.02 parts of tin (II) 2-ethylhexanoate were added while maintaining 80 °C ± 10 °C. The reaction was carried out for 12 hours. Thereafter, the mixture was cooled to 25 ° C, and the reaction solution was added to 500 parts of acetone, whereby the precipitated reaction product as a white solid was collected by filtration, and washed with 1000 parts of acetone. The mixture was dried under reduced pressure at 40 ° C for 3 hours, whereby a reaction product (a'5) of 3,4-dihydrocoumarin and acetonitrile cellulose was obtained.

<Manufacturing Example 67>

[Reaction of [3,4-dihydrocoumarin with ethyl cellulose (a'6) {ethylcellulose 3-(2-hydroxyphenyl)propionate}]

In the above-mentioned Production Example 65, "Ethylcellulose ("cellulose acetate L-20" manufactured by Daicel Co., Ltd.) was changed to "ethyl cellulose ("OWOCEL (manufactured by Dow Chemical Co., Ltd.)" A reaction product (a'6) of 3,4-dihydrocoumarin and ethyl cellulose was obtained by the same method except that 10 cps)))).

<Manufacturing Example 68>

[Reaction of ε-caprolactone with acetamidine cellulose (a'7) {acetam 6-hydroxyhexanyl cellulose}]

5 parts of acetonitrile cellulose ("cellulose acetate L-20" manufactured by Daicel Co., Ltd.) was added to 100 parts of toluene, and dehydration in the reaction system was carried out at 110 ° C under reflux of toluene for 3 hours. After dehydration, 4 parts of ε-caprolactone ("C0702" manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.02 parts of tin (II) 2-ethylhexanoate were added, and 12 hours were maintained while maintaining at 80 ° C ± 10 ° C. reaction. Thereafter, the mixture was cooled to 25 ° C, and the reaction solution was added to 500 parts of acetone, whereby the precipitated reaction product as a white solid was collected by filtration, and washed with 1000 parts of acetone. The mixture was dried under reduced pressure at 40 ° C for 3 hours, whereby a reaction product (a'7) of ε-caprolactone and acetonitrile cellulose was obtained.

<Manufacturing Example 69>

[Reaction of ε-caprolactone with ethyl cellulose (a'8) {ethylcellulose 6-hydroxyhexanoate}]

In the above-mentioned Production Example 67, "Ethylcellulose ("cellulose acetate L-20" manufactured by Daicel Co., Ltd.) 5 parts" was changed to "ethyl cellulose ("OWOCEL (made by Dow Chemical Co., Ltd.)" A reaction product (a'8) of ε-caprolactone and ethyl cellulose was obtained by the same method except that 10 cps)))).

In Table 2, (y1) is used in the following manufacturing examples 70 to 74.

<Manufacturing Example 70>

[monoisocyanate combination as a reaction product of 1,6-hexamethylene diisocyanate and methanol Object (y141)]

In a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, 32 parts of methanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and hexamethylene diisocyanate [[product name: Duranat HDI, manufactured by Asahi Kasei Chemicals Co., Ltd.] 168 parts, As a catalyst, one part of tris(2-ethylhexanoic acid) hydrazine (2-ethylhexanoic acid 50% solution) was reacted at 70 ° C for 5 hours to obtain a urethane compound (y141).

<Manufacturing Example 71>

[monoisocyanate compound (y142) as a reaction product of isophorone diisocyanate and ethanol]

In Production Example 70, "Ethanol [Tokyo Chemical Industry Co., Ltd.] 46 parts" was used instead of "methanol 32 parts" instead of "hexamethylene diisocyanate 168 parts" and "isophorone diisocyanate" was used. A monoisocyanate compound (y142) was obtained in the same manner except for the product name: 222 parts by the product of Desmodur I and Sumika Bayer Urethane.

<Manufacturing Example 72>

[monoisocyanate compound (y143) as a reaction product of 4,4'-dicyclohexylmethane diisocyanate and n-butanol]

In Production Example 70, "n-butanol [manufactured by Tokyo Chemical Industry Co., Ltd.] 74 parts" was used instead of "32 parts of methanol" instead of "hexamethylene diisocyanate 168 parts" and "dicyclohexylmethane" was used. A monoisocyanate compound (y143) was obtained in the same manner except that 4,4'-diisocyanate (trade name: manufactured by Desmodur W, manufactured by Sumika Bayer Urethane) was 262 parts.

<Manufacturing Example 73>

[monoisocyanate compound (y144) as a reaction product of toluene diisocyanate and n-octanol]

In the production example 70, instead of "32 parts of methanol", "100 parts of octanol [manufactured by Tokyo Chemical Industry Co., Ltd.]" was used instead of "168 parts of hexamethylene diisocyanate", and "toluene diisocyanate" was used. A monoisocyanate compound (y144) was obtained in the same manner except that: Desmodur T-80, manufactured by Sumika Bayer Urethane, 174 parts.

<Manufacturing Example 74>

[Mono Isocyanate Compound (y145) as a Reaction Product of Benzyl Diisocyanate and Phenol]

In Production Example 70, "Phenol [Tokyo Chemical Industry Co., Ltd.] 94 parts" was used instead of "methanol 32 parts" instead of "hexamethylene diisocyanate 168 parts" and "benzodimethyl diisocyanate" was used. A monoisocyanate compound (y145) was obtained in the same manner except for the product name: "Desmodur 15, manufactured by Sumika Bayer Urethane].

In addition, the components of Tables 1 to 9 are as follows.

○ polysaccharide

Cellulose: Made by Nippon Paper Chemical Co., Ltd., "KC FLOCK W-50GK"

Diacetyl cellulose-1: manufactured by Daicel, "cellulose acetate L-20"

Diacetyl cellulose-2: manufactured by Daicel, "cellulose acetate L-50"

Diacetyl cellulose-3: manufactured by Eastman Chemical, "CA-394"

Acetin cellulose-1: manufactured by Eastman Chemical, "CAB551-0.2"

Acetone cellulose-2: manufactured by Eastman Chemical, "CAB381-0.5"

Acetylpyrene Cellulose-1: manufactured by Eastman Chemical, "CAP482-0.5"

Acetylpyrene Cellulose-2: Made by Eastman Chemical, "CAP482-2.0"

Carboxymethylcellulose: manufactured by Nippon Paper Chemical Co., Ltd., "Sunrose F1400MC"

Carboxymethylethylcellulose: Sanyo Chemical Industry Co., Ltd., "CMEC"

Cellulose acetate phthalate: manufactured by Wako Pure Chemical Industries Co., Ltd.

Hydroxypropyl methylcellulose phthalate: manufactured by Shin-Etsu Chemical Co., Ltd., "HPMCP HP-50"

Hydroxypropyl methylcellulose hexahydrophthalate: manufactured by Shin-Etsu Chemical Co., Ltd., "HPMCHHP"

Hydroxypropyl methylcellulose phthalate acetate: Shin-Etsu Chemical Co., Ltd., "HPMCAP"

Hydroxypropylmethylcellulose acetate succinate: manufactured by Shin-Etsu Chemical Co., Ltd., "AQOAT AS-MG"

Hydroxyethyl cellulose-1: manufactured by Daicel, "HEC-SP900"

Hydroxyethyl cellulose-2: manufactured by Sumitomo Seika Co., Ltd., "HEC AX-15"

Hydroxypropyl cellulose: manufactured by Japan's Soda Co., "NISOO HPC"

Low-substituted hydroxypropyl cellulose: Shin-Etsu Chemical Co., Ltd., "LH-31"

Methylcellulose-1: Shin-Etsu Chemical Co., Ltd., "METOLOSE SM-8000"

Methylcellulose-2: manufactured by Matsumoto Oil & Fats Co., Ltd., "Maporose M-4000"

Ethylcellulose-1: manufactured by Dow Chemical, "ETHOCEL"

Ethylcellulose-2: manufactured by Kanto Chemical Co., Ltd., "Ethylcellulose 45CP"

Hydroxypropylmethylcellulose-1: manufactured by Shin-Etsu Chemical Co., Ltd., "METOLOSE 90SH-4000"

Hydroxypropyl methylcellulose-2: manufactured by Matsumoto Oil & Fats Co., Ltd., "Maporose 60MP-4000"

Hydroxyethyl methylcellulose: manufactured by Shin-Etsu Chemical Co., Ltd., "METOLOSE SNB60T"

Starch: manufactured by NIHON-CORNSTARCH, "White Cornstarch"

Amylose: manufactured by Hayashibara, "Amylose EX-I"

Amylopectin: Wako Pure Chemical (Stock) Manufacturing

Hepatic sugar: manufactured by Wako Pure Chemical Co., Ltd., "Hepatic sugar (from oysters)"

Chitin: manufactured by Wako Pure Chemical Co., Ltd.

Polyglucosamine: manufactured by Wako Pure Chemical Co., Ltd., "Polyuramine 1000"

Agarose: manufactured by Wako Pure Chemical Co., Ltd., "Sepharose 1600"

Carrageenan: manufactured by Wako Pure Chemical Co., Ltd., "IRISH MOSS (Carrageenan)"

Heparin: manufactured by Wako Pure Chemical Co., Ltd., "Heparin Sodium"

Hyaluronic acid: manufactured by Kewpie Co., Ltd., "HA-F"

Pectin: manufactured by Wako Pure Chemical Co., Ltd.

Xyloglucan: manufactured by Dainippon Sumitomo Pharmaceutical Co., Ltd., "GLYLOID 6C"

Sanxianjiao: Heguang Pure Medicine Co., Ltd.

Further, the total introduction ratio of the urethane group, the urea group, the guanamine group and the imine group in Tables 1 to 5 and 7 to 9 was determined by the following.

<Method for Calculating Total Introduction Rate of Carbamate Group, Urea Group, Amidoxime Group and Imine Group>

Total introduction rate of urethane group, urea group, guanamine group and imine group = P/T' (1)

P: NMR integral value (P ₁ ) of a hydrogen atom constituting a urethane group in which a hydroxyl group, a carboxyl group and an amine group of a monosaccharide unit of the modified polysaccharide (A) are chemically modified, and a urea group The NMR integrated value (P ₂ ) of the hydrogen atom, the NMR integrated value (P ₃ ) of the hydrogen atom of the guanamine group, and the NMR integrated value (P ₄ ) of the hydrogen atom of the imine group are applied to the following formula (2). The total integrated value obtained is P=P ₁ +P ₂ /2+P ₃ +P ₄ (2)

T': NMR integral value of a hydrogen atom directly bonded to a carbon atom at the 4-position of the monosaccharide unit constituting the modified polysaccharide (A)

<Method for Measuring Total Introduction Rate of Carbamate Group, Urea Group, Amidino Group and Imine Group>

Solvent: Deuterated dimethyl hydrazine

Device: AVANCE300 (made by Japan Bruker Co., Ltd.)

Frequency: 300MHz

In Table 6, the ratio of the functional group (B) chemically modified in (A) was determined by the following measurement method.

<Method for Measuring the Ratio of Functional Groups Modified by (B)>

The ¹ H-NMR measurement of the polysaccharide (a) before modification and the modified polysaccharide (A) was carried out. The following integral value obtained by the respective measurement results was applied to the following formula (3), whereby the ratio (%) of the functional group modified by (B) was calculated.

The ratio (%) of the functional group modified by (B) = {(T-S) / T} × 100 (3)

S = [(the integral value of the hydrogen atom of the hydroxyl group of the modified polysaccharide (A)) + { (the integrated value of the hydrogen atom of the amine group of the modified polysaccharide (A)) / 2}]

T = [(integral value of hydrogen atom of hydroxyl group of polysaccharide (a)) + {(integral value of hydrogen atom of amine group of polysaccharide (a))/2}]

Solvent: Deuterated dimethyl hydrazine

Device: AVANCE300 (made by Japan Bruker Co., Ltd.)

Frequency: 300MHz

In Table 6, the aromatic ring concentration of (A) was determined by the following measurement method.

<Measurement of aromatic ring concentration>

Polysaccharides (a) before the modification and modified polysaccharide (A) using ¹ H-NMR measurement, the integral value obtained by following the respective measurement results to the following formula (4), whereby the modified polysaccharide was calculated ( A) Aromatic ring concentration (% by weight).

Aromatic ring concentration (% by weight) = {U × W / (U × W + V)} × 100 (4)

U = (integral value of one hydrogen atom in the structure of the aromatic compound (B)) × (number of aromatic rings in the aromatic compound (B)) × 5 / (in the monosaccharide constituting the modified polysaccharide (A), The total of the integral values of the hydrogen atoms bonded to the carbon of the 1st to 5th positions)

V = molecular weight of the monosaccharide constituting the polysaccharide (a)

W = molecular weight of aromatic compound (B)

Solvent: Deuterated dimethyl hydrazine

Device: AVANCE300 (made by Japan Bruker Co., Ltd.)

Frequency: 300MHz

In Tables 1 to 9, the Mn of the modified polysaccharide (A) was measured under the following conditions.

Device: gel permeation chromatography

["Alliance GPC V2000", Waters (share) manufacturing]

Solvent: N,N-dimethylformamide

Reference material: polystyrene

Sample concentration: 3mg/ml

Column stationary phase: PLgel MIXED-B

[Polymer Laboratories (share) manufacturing]

Column temperature: 40 ° C

Examples 1 to 61 and Comparative Examples 1 to 32

(A-1) to (A-61) manufactured in Production Examples 1 to 61 and 100 parts each of (A'-1) to (A'-32) manufactured in Comparative Production Examples 1 to 32, respectively. 1000 parts of 1,3-dioxolane as an organic solvent was mixed at once, and the resin for reverse wavelength dispersion film of Examples 1 to 61 and Comparative Examples 1 to 32 was prepared by uniformly mixing and stirring with a disperser. Composition.

[Production of reverse wavelength dispersion film]

The resin composition for each reverse wavelength dispersion film obtained in Examples 1 to 61 and Comparative Examples 1 to 32 was applied to a surface-treated PET having a thickness of 120 μm by using an applicator in a thickness of 80 μm. A polyethylene terephthalate film [COSMOSHINE" manufactured by Toyobo Co., Ltd. was dried at 80 ° C for 2 hours. After drying, it was peeled off from the PET film, whereby a reverse wavelength dispersion film was obtained.

[Performance evaluation of membrane]

The following films (1) and (2) were evaluated using the produced film. The results are shown in Tables 10 and 11.

(1) Transmittance and haze (transparency)

According to JIS-K7136, the total light transmittance measuring device [product name "haze-garddual" BYK is used. Transmittance and haze were measured by Gardner. The unit of transmittance and haze is %.

(2) Positive birefringence and reverse wavelength dispersion

In-plane retardation (Re, in-plane retardation) of light having wavelengths of 450 nm, 590 nm, and 630 nm was measured using "RETS-100" manufactured by Otsuka Electronics Co., Ltd.

The positive birefringence means a value obtained by dividing the retardation value at a wavelength of 590 nm by the film thickness. Furthermore, the larger the value, the higher the positive birefringence.

The reverse wavelength dispersibility refers to the values of Re(450)/Re(590) and Re(630)/Re(590). Further, Re (450), Re (590), and Re (630) refer to in-plane retardation at wavelengths of 450 nm, 550 nm, and 630 nm, respectively. Although Re(450)/Re(590)=0.88±0.03 and Re(630)/Re(590)=1.06±0.03, the reverse wavelength dispersion is particularly good, and although the value of Re(450)/Re(590) The difference from the value of Re(630)/Re(590) is large, but the reverse wavelength dispersion is particularly good.

The film for reflection b* measurement was produced by the following production method, and the reflection chromaticity b* was measured in accordance with JIS-Z8729.

<Method for Producing Film for Measuring Reflectance b*>

The resin composition for a reverse wavelength dispersion film was applied to a PET (polyethylene terephthalate) film having a thickness of 120 μm which was surface-treated by the use of an applicator in a thickness of 80 μm [Toyobo Co., Ltd.) "COSMOSHINE"]. The coating was dried at 80 ° C for 2 hours. After drying, it was peeled off from the PET film to prepare a film for measuring reflection b*.

According to the results of Tables 10 and 11, the resin composition for a reverse wavelength dispersion film of Examples 1 to 61 of the present invention has both saponification resistance, transparency, positive birefringence, and reverse wavelength dispersion. According to the above, the resin composition for a reverse wavelength dispersion film of Examples 1 to 61 of the present invention is excellent as a composition for a film and a sheet.

[Industrial availability]

The resin composition for a reverse wavelength dispersion film of the present invention is excellent in saponification resistance, transparency, positive birefringence, and reverse wavelength dispersibility, and therefore is particularly preferably used for a reverse wavelength dispersion film or sheet, a retardation film or a sheet. , and a circular polarizing film or a circular polarizer.

Claims (12)

A resin composition for a reverse wavelength dispersion film comprising a modified polysaccharide (A), wherein the modified polysaccharide (A) is a chemical having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group The modification is carried out by at least one functional group selected from the group consisting of an ether group, a urethane group, a urea group, a guanamine group, and an imine group, and constitutes all monosaccharide units of the modified polysaccharide (A) The average molecular dispersion is 0.50 to 20.0, and the resin composition of the reverse wavelength dispersion film is formed into a film having a film thickness of 80 μm. The absolute value of the reflection chromaticity b* determined in accordance with JIS-Z8729 is 0 to 1.0. The resin composition for a reverse wavelength dispersion film according to the first aspect of the invention, wherein the modified polysaccharide (A) is a polysaccharide obtained by chemically modifying the following polysaccharide (a), and the modified polysaccharide (A) is formed. At least one of the monosaccharide units is at least one selected from the group consisting of the following general formulae (1) to (6), and the polysaccharide (a) is selected from the group consisting of starch, glycogen, cellulose, and chitin. Polyglucosamine, agarose, carrageenan, heparin, hyaluronic acid, pectin, xyloglucan and sinica, and the functional groups substituted for the urethane group, urea group, hydrazine a polysaccharide of at least one of the group consisting of a polysaccharide other than an amine group and an imine group, [wherein, X ¹ to X ¹³ are each independently a hydrogen atom or the following formula (7); and at least one of X ¹ to X ³ is a substituent represented by the following formula (7); X ⁴ to X At least one of ⁶ is a substituent represented by the following formula (7); at least one of X ⁷ and X ⁸ is a substituent represented by the following formula (7); and at least 1 of X ¹⁰ and X ¹¹ One is a substituent represented by the following formula (7); at least one of X ¹² and X ¹³ is a substituent represented by the following formula (7); Y is an oxygen atom or an NH group, and Z is a hydroxyl group or (8) the substituents indicated], Wherein R ¹ is a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms; * represents a substituent represented by the formula (7) and a formula (1) represented by the formula (7) ~(6) is an oxygen atom and/or a nitrogen atom adjacent to X], *-HN-R ² (8) [wherein R ² is a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 12 or The alkyl polyoxyalkylene group; * represents a bond represented by the formula (8) and a carbon atom adjacent to Z in the above formula (5) by a bond to which it is attached]. The resin composition for a reverse wavelength dispersion film according to the second aspect of the invention, wherein R ¹ in the formula (7) is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, and t-butyl groups. A substituent of at least one of the group consisting of a third butyl group, a n-hexyl group, a cyclohexyl group, a 2-ethylhexyl group, an n-octyl group, an n-dodecyl group, and an n-octadecyl group. The resin composition for a reverse wavelength dispersion film according to the first aspect of the invention, wherein the modified polysaccharide (A) is a polysaccharide obtained by chemically modifying the following polysaccharide (a), and at least one of (a) The hydroxyl group is chemically modified by the following aromatic compound (B) having an epoxy group. Carbohydrate, polysaccharide (a): selected from the group consisting of starch, glycogen, cellulose, chitin, polyglucosamine, agarose, carrageenan, heparin, hyaluronic acid, pectin, xyloglucan and sinensis, and The functional group having such a functional group substituted with at least one of a group consisting of a polysaccharide other than a urethane group, a urea group, a guanamine group, and an imine group, and the aromatic compound (B): selected from the group consisting of aromatics An aromatic compound in which one hydrogen atom in the ring is substituted with an epoxy group (b1), and one hydrogen atom in the aromatic ring is substituted with an alkylene group having an alkyl group having 3 to 8 carbon atoms (b2) And an aromatic compound in which one hydrogen atom in the aromatic ring is substituted with a functional group in which at least one carbon atom of the alkyl group is substituted with an oxygen atom through an alkylene group having an alkyl group having 3 to 8 carbon atoms (b3) A compound of at least one of the group consisting of. The resin composition for a reverse wavelength dispersion film according to any one of claims 2 to 4, wherein the polysaccharide (a) is selected from the group consisting of cellulose, cellulose deuterated (a1), and etherified cellulose (a2). And at least one of the group consisting of etherified deuterated cellulose (a3). The resin composition for a reverse wavelength dispersion film according to any one of claims 1 to 5, which contains the esterified cellulose (C). The resin composition for a reverse wavelength dispersion film according to the sixth aspect of the invention, wherein the esterified cellulose (C) is an alkyl esterified cellulose, and the carbon number of the alkyl group is from 1 to 18. The resin composition for a reverse wavelength dispersion film according to claim 6 or 7, wherein the esterified cellulose (C) has a group selected from the group consisting of an acetate group, a propionate group, and a butyrate group. At least one ester-based esterified cellulose. The resin composition for a reverse wavelength dispersion film according to any one of claims 6 to 8, wherein the polysaccharide (A) is modified based on the weight of the resin composition for the reverse wavelength dispersion film. The content is from 1 to 99.9% by weight, and the content of the esterified cellulose (C) is from 0.1 to 99% by weight. A reverse wavelength dispersion film or a reverse wavelength dispersion sheet formed of the resin composition for a reverse wavelength dispersion film according to any one of claims 1 to 9. A retardation film or a retardation film is formed from the resin composition for a reverse wavelength dispersion film according to any one of claims 1 to 9. A circularly polarizing film or a circularly polarizing film is formed from the resin composition for a reverse wavelength dispersion film according to any one of claims 1 to 9.