JP4721858B2 - Method for producing retardation film - Google Patents

Description

  The present invention relates to a method for producing a retardation film.

  Various retardation films are used in liquid crystal display devices in order to improve viewing angle characteristics. However, a liquid crystal display device using a conventional retardation film has a contrast ratio that decreases in an oblique direction, and coloration of an image that changes with a viewing angle (also referred to as an oblique color shift) occurs. The problem is that the display is non-uniform across the entire screen of the liquid crystal panel. In addition, since the absolute value of the photoelastic coefficient of the retardation film is large, when the backlight of the liquid crystal display device is turned on for a long time, the retardation value is applied to the retardation film due to the contraction stress of the polarizer and the heat of the backlight. Displacement and unevenness occur and the display uniformity of the screen deteriorates.

Conventionally, as one of the retardation films, a stretched polymer film has been proposed (Patent Documents 1 and 2) that exhibits a characteristic that the retardation value is smaller as the wavelength is shorter (also referred to as reverse wavelength dispersion characteristic). Examples thereof include a stretched polymer film (Patent Document 1) mainly composed of a polycarbonate copolymer having a fluorene skeleton, and a stretched film (Patent Document 2) composed mainly of a cellulose ester. . However, since the stretched film of the polymer film has a large absolute value of the photoelastic coefficient, it is easy to cause a shift or unevenness in the retardation value due to strain, and a uniform display can be obtained when used in a liquid crystal display device. There was no problem. In addition, the polymer film is generally formed by a solvent casting method. However, since the solubility of the resin used is poor, there is a limit to the solvent that can be used. Halogenated aliphatic hydrocarbons have been used. However, since these solvents have extremely high volatility with a boiling point of around 40 ° C., the moldability and workability were poor. In addition, since the solvent dissolving power is too strong, usable substrates are limited in, for example, metal belts and glass plates, and productivity is poor. Therefore, it has been desired to develop a method for producing a retardation film that exhibits reverse wavelength dispersion characteristics, has a small absolute value of photoelastic coefficient, and is excellent in molding processability and productivity.
JP 2002-221622 A JP 2001-091743 A

  The present invention has been made in order to solve such problems, and the object thereof is a method for producing a retardation film exhibiting reverse wavelength dispersion characteristics, which is a retardation film excellent in molding processability and productivity. It is to provide a manufacturing method.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above object can be achieved by the following method for producing a retardation film, and have completed the present invention.

The present invention is a method for producing a retardation film satisfying the following formulas (1) and (2), and comprising at least one selected from toluene, ethyl acetate, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, and cyclohexanone. A step of casting a solution prepared by dissolving a resin composition containing a polyvinyl acetal resin as a main component in a solvent, and casting the solution on a surface of a base material to evaporate the solvent to obtain a polymer film; As well as stretching the polymer film:
Re [450] <Re [550] <Re [650] (1)
20 nm ≦ Re [550] ≦ 400 nm (2)
However, Re [450], Re [550], and Re [650] are in-plane retardation values measured with light having wavelengths of 450 nm, 550 nm, and 650 nm at 23 ° C., respectively.

  In a preferred embodiment, the resin composition is mainly composed of a polyvinyl acetal resin having a structure represented by the following general formula (I):

(In general formula (I), R1 has a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a phenyl group which may have a substituent, or a substituent. Represents an optionally substituted naphthyl group, an optionally substituted anthranyl group, or an optionally substituted phenanthrenyl group, R2, R3 and R4 each independently represent a hydrogen atom, a carbon number; 1 to 4 linear, branched or cyclic alkyl group, 1 to 4 linear or branched alkoxyl group, halogen atom, halogenated alkyl group, nitro group, amino group, hydroxyl group, A cyano group or a thiol group, provided that R2 and R3 are not hydrogen atoms at the same time. L represents an integer of 2 or more).

  In a preferred embodiment, the polyvinyl acetal resin has a structure represented by the following general formula (II):

(In general formula (II), R 1, R 5 and R 6 may each independently have a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or a substituent. A phenyl group, an optionally substituted naphthyl group, an optionally substituted anthranyl group, or an optionally substituted phenanthrenyl group, each of R2, R3 and R4 represents Independently, a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxyl group having 1 to 4 carbon atoms, a halogen atom, a halogenated alkyl group, A nitro group, an amino group, a hydroxyl group, a cyano group or a thiol group, wherein R2 and R3 are not hydrogen atoms at the same time, R7 is a hydrogen atom, linear, branched or cyclic with 1 to 8 carbon atoms; Alkyl group Jill group, a silyl group, a phosphate group, an acyl group, .l showing a benzoyl group or a sulfonyl group,, m, and n is an integer of 2 or more.).

  In a preferred embodiment, the resin composition contains more than 0 and 20 (weight ratio) of liquid crystal compounds with respect to the polyvinyl acetal resin 100.

  In preferable embodiment, the thickness of the said polymer film is 20 micrometers-300 micrometers.

  The method for producing a retardation film of the present invention comprises a resin composition comprising a polyvinyl acetal resin as a main component in a solvent containing at least one selected from toluene, ethyl acetate, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, and cyclohexanone. A solution prepared by dissolving the product is cast into a sheet on the surface of the substrate, and the solvent is evaporated to obtain a polymer film, and the polymer film is stretched. According to this manufacturing method, it is excellent in moldability and productivity, and a retardation film can be manufactured without using a conventional halogenated aliphatic hydrocarbon. In addition, the retardation film obtained by this production method has a small absolute value of the photoelastic coefficient and exhibits reverse wavelength dispersion characteristics, so that the display characteristics of the liquid crystal display can be improved.

<< A. Outline of production method of retardation film >>
The method for producing a retardation film of the present invention is a method for producing a retardation film satisfying the following formulas (1) and (2), and includes toluene, ethyl acetate, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, and cyclohexanone. A solution prepared by dissolving a resin composition containing a polyvinyl acetal resin as a main component in a solvent containing at least one kind selected from the following is cast into a sheet on the surface of a substrate, and the solvent is evaporated: Including obtaining a polymer film, and stretching the polymer film:
Re [450] <Re [550] <Re [650] (1)
20 nm ≦ Re [550] ≦ 400 nm (2)
However, Re [450], Re [550], and Re [650] are in-plane retardation values measured with light having wavelengths of 450 nm, 550 nm, and 650 nm at 23 ° C., respectively.

  The retardation film obtained by the production method of the present invention is typically disposed on at least one side of the liquid crystal cell, and reduces the light leakage that occurs in the oblique direction of the liquid crystal display device, thereby increasing the contrast ratio in the oblique direction. It is used to increase the color shift amount in the oblique direction. Further, with respect to the wavelength of light (usually in the visible light region), a λ / 4 plate having an in-plane retardation value of about ¼, or a λ / plate having an in-plane retardation value of about ½. It is also used as a wave plate such as two plates. In addition, the said retardation film is not limited to these uses, It can be used for the use for which a conventionally well-known retardation film is used. Hereinafter, the details of the production method of the present invention and the details of the retardation film obtained by the production method of the present invention will be described.

<< B. Resin composition >>
The resin composition used in the present invention contains a polyvinyl acetal resin as a main component. More preferably, the resin composition used in the present invention is mainly composed of a polyvinyl acetal resin having a structure represented by the following general formula (I). The polyvinyl acetal resin can be obtained, for example, by a condensation reaction (also referred to as acetalization) between a polyvinyl alcohol resin and an aldehyde or ketone. The polymer film containing the polyvinyl acetal resin as a main component has a small photoelastic coefficient and can be a retardation film exhibiting reverse wavelength dispersion characteristics by stretching.

  In general formula (I), R1 has a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an optionally substituted phenyl group, or a substituent. It represents an naphthyl group which may be substituted, an anthranyl group which may have a substituent, or a phenanthrenyl group which may have a substituent. R2, R3 and R4 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxyl group having 1 to 4 carbon atoms, Represents a halogen atom, a halogenated alkyl group, a nitro group, an amino group, a hydroxyl group, a cyano group or a thiol group; However, R2 and R3 are not hydrogen atoms at the same time. l represents an integer of 2 or more.

  The acetalization is, for example, a method in which a polyvinyl alcohol resin and an aldehyde or ketone are reacted in the presence of a strong inorganic acid catalyst or a strong organic acid catalyst. Specific examples of the acid catalyst include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid and the like. The reaction temperature for acetalization is usually above 0 ° C. and below the boiling point of the solvent used, preferably 10 ° C. to 100 ° C., most preferably 20 ° C. to 80 ° C. With the above reaction temperature, a high yield can be obtained. Solvents used for acetalization include alcohols such as methanol, ethanol, propanol and butanol, cyclic ethers such as 4-dioxane, aprotic such as N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide. A polar solvent or the like is preferably used. These solvents are used alone or in combination of two or more. Moreover, you may mix and use water and the said solvent.

  In the general formula (I), the substituents R2, R3, and R4 are used to control the conformation of the benzene ring to which the substituent is bonded. More specifically, when a polymer film containing as a main component a polyvinyl acetal resin having a structure represented by the above general formula (I) is stretched, the substituent is sterically hindered to cause the above general formula (I ), It is presumed that it becomes easier to conform between two oxygen atoms. As a result, the planar structure of the benzene ring can be oriented substantially orthogonal to the virtual line connecting the two oxygen atoms. The wavelength dispersion characteristic of the retardation film of the present invention is based on the interaction between the wavelength dispersion characteristic of the benzene ring oriented in a direction substantially perpendicular to the virtual line connecting the two oxygen atoms and the wavelength dispersion characteristic of the main chain structure. It is considered to be obtained.

  R1, R2, R3 and R4 in the general formula (I) are, for example, an aldehyde (typically benzaldehyde) or a ketone (typically acetophenone) which is reacted with an alcohol when obtaining the polyacetal resin. And benzophenones) can be selected as appropriate. When a hydrogen atom is substituted for R1, an aldehyde may be used, and when a substituent other than a hydrogen atom is introduced, a ketone may be used.

  Specific examples of benzaldehydes include 2-methylbenzaldehyde, 2-chlorobenzaldehyde, 2-nitrobenzaldehyde, 2-ethoxybenzaldehyde, 2- (trifluoromethyl) benzaldehyde, 2,4-dichlorobenzaldehyde, 2,4-dihydroxybenzaldehyde. 2,4-disulfobenzaldehyde sodium, o-sulfobenzaldehyde disodium, p-dimethylaminobenzaldehyde, 2,6-dimethylbenzaldehyde, 2,6-dichlorobenzaldehyde, 2,6-dimethoxybenzaldehyde, 2,4 , 6-trimethylbenzaldehyde (mesitaldehyde), 2,4,6-triethylbenzaldehyde, 2,4,6-trichlorobenzaldehyde and the like. Specific examples of acetophenones include 2-methylacetophenone, 2-aminoacetophenone, 2-chloroacetophenone, 2-nitroacetophenone, 2-hydroxyacetophenone, 2,4-dimethylacetophenone, 4′-phenoxy-2,2-dichloro. Examples include acetophenone 2-bromo-4′-chloroacetophenone. Examples of benzophenones include 2-methylbenzophenone, 2-aminobenzophenone, 2-hydroxybenzophenone, 4-nitrobenzophenone, 2,4′-dichlorobenzophenone, 2,4′-dichlorobenzophenone, 4,4′-dichlorobenzophenone, 4 4, 4'-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-chloro-4'-dichlorobenzophenone, and the like. In addition, 1-naphthaldehyde, 2-naphthaldehyde having a substituent, 9-anthraldehyde, 9-anthraldehyde having a substituent, acetonaphthone, fluorene-9-aldehyde, 2,4,7-trinitrofluorene-9- ON etc. are mentioned. These aldehydes or ketones can be used alone or in combination of two or more. The aldehyde or ketone may be used after any appropriate modification.

  R1 in the general formula (I) is preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom. Preferably, R2 and R3 in the general formula (I) are each independently at least one substituent selected from a methyl group, an ethyl group, a halogen atom, and a halogenated alkyl group, and most preferably a methyl group. is there. R4 in the general formula (I) is preferably at least one substituent selected from a hydrogen atom, a methyl group, an ethyl group, a halogen atom, and a halogenated alkyl group, and most preferably a methyl group. By introducing such a substituent, a retardation film having excellent optical properties can be obtained.

  As a polyvinyl alcohol resin used as a raw material for the polyvinyl acetal resin, a vinyl ester polymer obtained by polymerizing a vinyl ester monomer may be saponified to use a vinyl ester unit as a vinyl alcohol unit. it can. Examples of the vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, vinyl versatate, and the like. Of these, vinyl acetate is preferable.

  Any appropriate average degree of polymerization can be adopted as the average degree of polymerization of the polyvinyl alcohol-type resin that is a raw material of the polyvinyl acetal-type resin. The average degree of polymerization is preferably 800 to 3600, more preferably 1000 to 3200, and most preferably 1500 to 3000. The average degree of polymerization of the polyvinyl alcohol-based resin can be measured by a method according to JIS K 6726 (: 1994).

  The degree of acetalization of the polyvinyl acetal resin is preferably 40 mol% to 99 mol%, more preferably 50 mol% to 95 mol%, and most preferably 60 mol% to 90 mol%. By setting it as said range, the polymer film excellent in transparency is obtained, and the retardation film excellent in the optical characteristic can be obtained by extending | stretching this polymer film.

The degree of acetalization indicates the proportion of units that are actually acetalized to vinyl alcohol units among the units that can be converted to acetal units by acetalization. Incidentally, acetalization degree of the polyvinyl alcohol-based resin can be determined by nuclear magnetic resonance spectra ⁽¹ H-NMR).

  Particularly preferably, the resin composition used in the present invention is mainly composed of a polyvinyl acetal resin having a structure represented by the following general formula (II). The polyvinyl acetal resin is obtained by a condensation reaction (also called acetalization) using a polyvinyl alcohol resin and two or more aldehydes, two or more ketones, or at least one aldehyde and at least one ketone. Obtainable. A polymer film mainly composed of a polyvinyl acetal resin having a structure represented by the following general formula (II) has a small photoelastic coefficient, exhibits reverse wavelength dispersion characteristics when stretched, and has a retardation value. A retardation film having excellent stability can be obtained. Moreover, since it is also excellent in stretch orientation, the thickness of the retardation film can be reduced.

  In general formula (II), R 1, R 5 and R 6 are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and optionally substituted phenyl. A naphthyl group which may have a group, a substituent, an anthranyl group which may have a substituent, or a phenanthrenyl group which may have a substituent. R2, R3 and R4 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxyl group having 1 to 4 carbon atoms, A halogen atom, a halogenated alkyl group, a nitro group, an amino group, a hydroxyl group, a cyano group or a thiol group is shown. However, R2 and R3 are not hydrogen atoms at the same time. R7 represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a benzyl group, a silyl group, a phosphate group, an acyl group, a benzoyl group, or a sulfonyl group. l, m, and n represent an integer of 2 or more.

  In the general formula (II), the R5 and R6 substituents are wavelengths of a retardation film obtained by stretching a polymer film mainly composed of a polyacetal resin having a structure represented by the general formula (II). Used to control the dispersion characteristics more precisely. More specifically, by introducing a substituent into R5 and R6, when the polymer film is stretched, the substituent can be oriented substantially parallel to the stretching direction. The chromatic dispersion characteristics of the retardation film of the present invention are as follows: the chromatic dispersion characteristics of the benzene ring oriented in the direction substantially perpendicular to the imaginary line connecting the two oxygen atoms, and the chromatic dispersion characteristics of the main chain structure. Further, it is considered to be obtained by the interaction with the wavelength dispersion characteristic of the substituent introduced into R5 and R6. Moreover, the moldability and stretch orientation of the polymer film can be further improved.

  R5 and R6 are appropriately selected depending on, for example, the type of aldehyde (typically benzaldehydes) or ketone (typically acetophenones or benzophenones) to be reacted with alcohol when the polyvinyl acetal resin is obtained. Can be selected. Specific examples of the aldehyde and ketone are as described above.

  R5 is preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom. R6 is preferably a methyl group or an ethyl group, and most preferably a methyl group. By introducing such a substituent, a retardation film having excellent solubility, molding processability, and stretch orientation can be obtained.

  In the above general formula (II), the substituent of R7 adjusts the water absorption rate to an appropriate value by protecting the remaining hydroxyl group (also referred to as end cap treatment), forming processability, and stability of retardation value. Used to increase Therefore, depending on the water absorption rate and optical characteristics of the obtained retardation film and the application in which the retardation film of the present invention is used, R7 may not be end-capped and may remain a hydrogen atom.

  The above R7 is, for example, obtained by obtaining a polyvinyl acetal resin having a hydroxyl group remaining thereon, and then using a conventionally known one that forms a substituent by reacting with a hydroxyl group (typically a protecting group), and is subjected to an end cap treatment. Can be obtained. Specific examples of the protecting group include benzyl group, 4-methoxyphenylmethyl group, methoxymethyl group, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, acetyl group, benzoyl group, methanesulfonyl group, bis-4 -Nitrophenyl phosphite etc. are mentioned. As the reaction conditions for the end cap treatment, appropriate reaction conditions may be employed as appropriate depending on the type of substituent to be reacted with a hydroxyl group. For example, a reaction such as alkylation, benzyl group, silylation, phosphorylation, sulfonylation can be performed by converting a polyvinyl acetal resin having a hydroxyl group remaining and a chloride of a desired substituent into 4 (N, N-dimethylamino). In the presence of a catalyst such as pyridine, the reaction can be performed by stirring at 25 ° C to 100 ° C for 1 hour to 20 hours. R7 is preferably one silyl group selected from a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group. By using these substituents, a retardation film having high transparency and excellent retardation value stability can be obtained even in an environment such as high temperature and high humidity.

  In the general formula (II), the ratio of l, m, and n can be appropriately selected according to the type and purpose of the substituent. Preferably, when the sum of l, m, and n is 100 (mol%), l is 5 to 30 (mol%), m is 20 to 80 (mol%), and n is 1 to 70 (mol%). Particularly preferably, l is 10 to 28 (mol%), m is 30 to 75 (mol%), n is 1 to 50 (mol%), and most preferably, l is 15 to 25 (mol%). Mol%), m is 40 to 70 (mol%), and n is 10 to 40 (mol%). By setting it as the above range, it is possible to obtain a retardation film that exhibits reverse wavelength dispersion characteristics and is extremely excellent in solubility, molding processability, and stretch orientation.

  The glass transition temperature (Tg) of the polyvinyl acetal resin used in the present invention is preferably 90 ° C to 185 ° C, more preferably 90 ° C to 150 ° C, and most preferably 100 ° C to 140 ° C. The glass transition temperature (Tg) can be determined by a DSC method according to JIS K 7121 (: 1987).

  The resin composition used in the present invention may contain any appropriate additive. Specific examples of the additives include plasticizers, heat stabilizers, light stabilizers, lubricants, antioxidants, ultraviolet absorbers, flame retardants, colorants, antistatic agents, compatibilizers, crosslinking agents, thickeners. , And a phase difference adjusting agent. In addition, other conventionally known thermoplastic resins may be mixed and used within a range that satisfies the object of the present invention. The kind and amount of the additive used can be appropriately selected depending on the purpose. For example, the content of the additive is preferably 0.01 (weight ratio) to 20 (weight ratio), more preferably 0.05 (weight ratio) to the polyvinyl acetal resin 100 used. 10 (weight ratio), most preferably 0.1 (weight ratio) to 5 (weight ratio).

  Further, the resin composition may further contain any appropriate liquid crystal compound. When the resin composition contains a liquid crystal compound, the resin composition may exhibit a liquid crystal phase and exhibit liquid crystallinity, or may not exhibit liquid crystallinity. In the present specification, the “liquid crystal compound” refers to a molecule having a mesogenic group in the molecular structure and forming a liquid crystal phase by a temperature change such as heating and cooling or by the action of a certain amount of solvent. The “mesogen group” means a structural portion necessary for forming a liquid crystal phase, and usually contains a cyclic unit. Specific examples of the mesogenic group include a biphenyl group, a phenylbenzoate group, a phenylcyclohexane group, an azoxybenzene group, an azomethine group, an azobenzene group, a phenylpyrimidine group, a diphenylacetylene group, a diphenylbenzoate group, a bicyclohexane group, and a cyclohexylbenzene group. And terphenyl group. In addition, the terminal of these cyclic units may have substituents, such as a cyano group, an alkyl group, an alkoxy group, a halogen group, for example. Especially, as a mesogenic group which consists of a cyclic unit etc., what has a biphenyl group and a phenylbenzoate group is used preferably.

  When the resin composition contains a liquid crystal compound, the resin composition preferably contains more than 0 to 20 (weight ratio) of the liquid crystal compound with respect to the polyvinyl acetal resin 100, and more preferably, the liquid crystal compound. 1 to 15 parts by weight, particularly preferably 2 to 10 parts by weight of a liquid crystal compound. By including a liquid crystal compound in the above-mentioned range in the resin composition, transparency is excellent, and a large retardation value can be obtained by stretching, so that the retardation film thickness can be reduced.

  The liquid crystal compound may be either a temperature transition type (thermotropic) liquid crystal in which a liquid crystal phase develops due to a temperature change, or a concentration transition type (lyotropic) liquid crystal in which a liquid crystal phase develops depending on the concentration of a solute in a solution state. Note that the above-described temperature transition type liquid crystal has a phase transition from a crystalline phase (or glass state) to a liquid crystal phase, a reversible tautomatic (enantotropic) phase transition liquid crystal, or a single change in which a liquid crystal phase appears only in a temperature lowering process ( Monotropic) phase transition liquid crystals. Preferably, the liquid crystal compound is a temperature transition type (thermotropic) liquid crystal. It is because it is excellent in productivity, workability, and quality of film forming.

  The liquid crystal compound may be a high molecular substance (polymer liquid crystal) having a mesogenic group in the main chain and / or side chain, or a low molecular substance (low molecular liquid crystal) having a mesogenic group in a part of the molecular structure. There may be. Preferred is a low molecular liquid crystal. This is because the low-molecular liquid crystal is excellent in compatibility with the polyvinyl acetal resin used in the present invention, so that a highly transparent film can be obtained.

  The liquid crystal compound is preferably a low molecular substance (low molecular liquid crystal) each having at least one mesogenic group and a polymerizable functional group in a part of the molecular structure. More preferably, it is a low molecular liquid crystal having one or more mesogenic groups and two or more polymerizable functional groups in a part of the molecular structure. This is because a retardation film having excellent orientation and extremely high optical uniformity and transparency can be obtained. Moreover, if the polymerizable functional group is crosslinked by a polymerization reaction, the mechanical strength of the retardation film is increased, and a retardation film having excellent durability and dimensional stability can be obtained. Specific examples of the low-molecular liquid crystal having one or more mesogenic groups and two or more polymerizable functional groups in a part of the molecular structure include a product name “Paliocolor LC242” manufactured by BASF and a product name “manufactured by HUNTSMAN” CB483 "etc. are mentioned.

  Any appropriate functional group can be selected as the polymerizable functional group. For example, acryloyl group, methacryloyl group, epoxy group, vinyl ether group and the like can be mentioned. Of these, an acryloyl group and a methacryloyl group are preferably used. This is because, in addition to excellent reactivity, a highly transparent retardation film can be obtained.

<< C. Polymer Film Molding Method >>
Solvent casting is used as a method for obtaining a polymer film containing the polyvinyl acetal resin as a main component. Specifically, the solvent casting method used in the present invention is obtained by dissolving a resin composition in a solvent containing at least one selected from toluene, ethyl acetate, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, and cyclohexanone. In this method, the prepared solution is cast in the form of a sheet on the surface of the substrate, and the solvent is evaporated to obtain a polymer film. With the above production method, a polymer film having good smoothness and optical uniformity (for example, a film having a uniform retardation value both in the plane and in the thickness direction) can be obtained, and economical and mass-productive. Also excellent.

  An example of a method for producing a polymer film by the solvent casting method of the present invention will be described with reference to FIG. FIG. 1 is a schematic view showing the concept of a process for forming the polymer film of the present invention. In this step, the base material 202 is supplied from the feeding unit 201 and conveyed by the guide roll 203, and in the coater unit 204, a solution in which the resin composition is dissolved is cast (coated) on the surface of the base material 202. ) The base material coated with the resin composition is sent to drying means 205 to 207 and dried while gradually raising the temperature from a low temperature to a high temperature, thereby evaporating the solvent and forming a polymer film 208. The The polymer film 208 is wound up by the winding unit 209 and used for the next stretching step.

  As described above, the solvent includes at least one selected from toluene, ethyl acetate, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, and cyclohexanone. These solvents can be used alone or in admixture of two or more. More preferably, it contains at least one selected from toluene, ethyl acetate, methyl isobutyl ketone, and cyclopentanone. Particularly preferably, it contains at least one selected from toluene, methyl isobutyl ketone, and cyclopentanone. If it is said solvent (or mixed solvent), the restriction | limiting of the conventional base material can be improved significantly, without eroding which has a practically bad influence with respect to a base material. In addition, since the boiling point is moderately higher than that of halogenated aliphatic hydrocarbons, the molding processability is excellent, and the workability and environmental performance are also excellent.

  The boiling point of the solvent is preferably 60 ° C to 160 ° C, more preferably 70 ° C to 150 ° C, and most preferably 80 ° C to 140 ° C. If it is said temperature range, a solvent will not evaporate rapidly but the polymer film which has favorable surface uniformity can be obtained.

  Moreover, you may use said solvent mixed with another organic solvent. As other organic solvents, alcohols, ketones, ethers, esters, aliphatic and aromatic hydrocarbons, cellosolves and the like are used. When another organic solvent is used, preferably, the total amount Y of the solvent used is selected from toluene, ethyl acetate, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, and cyclohexanone with respect to the total amount X of the other organic solvent. The ratio (X / Y) is 6/4 (volume / volume) to 1/9 (volume / volume), more preferably 5/5 (volume / volume) to 1/9 (volume / volume). Most preferably, it is 4/6 (volume / volume) to 1/9 (volume / volume). In addition, it is preferable that said mixed solvent is also adjusted and used for the temperature range of the boiling point mentioned above.

  The total solid content concentration of the solution is appropriately selected depending on the solubility, the type of coater used, the thickness after coating, and the like. Usually, the solid content (typically resin and additive) is 5 (weight ratio) to 100 (weight ratio), more preferably 10 (weight ratio) to 60 (weight ratio), particularly preferably with respect to the solvent 100. Is 10 (weight ratio) to 40 (weight ratio). If it is said range, the polymer film excellent in surface uniformity can be obtained.

  As a method of casting (coating) the above solution on the surface of the substrate in a sheet form, a coating method using an appropriate coater can be appropriately selected and used. Specific examples of the above coater include reverse roll coater, forward rotation roll coater, gravure coater, knife coater, rod coater, slot orifice coater, curtain coater, fountain coater, air doctor coater, kiss coater, dip coater, bead coater, blade coater, cast Examples include a coater, a spray coater, a spin coater, an extrusion coater, and a hot melt coater. Among these, as a coater, a reverse roll coater, a normal rotation roll coater, a gravure coater, a rod coater, a slot orifice coater, a curtain coater, a fountain coater, and a spin coater are preferable. If it is the coating method using said coater, the polymer film excellent in surface uniformity can be obtained.

  As the substrate on which the solution is applied, an appropriate one can be selected as appropriate. Specific examples include glass substrates such as glass plates and quartz substrates, polymer substrates such as films and plastics substrates, metal substrates such as aluminum and iron, inorganic substrates such as ceramic substrates, and semiconductors such as silicon wafers. Examples include base materials. Preferably, the substrate is a polymer substrate. This is because the surface uniformity of the base material is excellent, continuous production using a roll is possible, and productivity can be greatly improved.

  When a polymer substrate is used for the substrate, the material for forming the polymer substrate is appropriately selected according to the dissolving power, smoothness, wettability, and the like of the solvent used. Specific examples of the material forming the polymer substrate include thermosetting resins, ultraviolet curable resins, thermoplastic resins, thermoplastic elastomers, biodegradable plastics, and the like. A thermoplastic resin is preferable. Specific examples of the thermoplastic resin include polynorbornene, cellulose ester, ABS resin, AS resin, polymethyl methacrylate, polyvinyl acetate, polyvinylidene chloride, polyamide, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polysulfone. , Polyethersulfone, polyetheretherketone, polyarylate, liquid crystal polymer, polyamideimide, polyimide, polytetrafluoroethylene and the like. Among these, polynorbornene, cellulose ester, polymethyl methacrylate, and polyethylene terephthalate are particularly preferable. It is because it is excellent in smoothness, mechanical strength, and solvent resistance. In addition, you may give wet surface treatments, such as dry-type surface treatments, such as a corona treatment and a plasma treatment, an anchor coat layer, etc. previously at the side by which the solution of the said base material is coated. Further, the substrate is usually peeled off before the obtained polymer film is stretched. For example, the retardation value of the substrate is very small, and the liquid crystal remains as a laminate of the polymer film and the substrate. Even if it is used for a display device, the substrate may be left as it is without peeling if it does not have a practically adverse effect.

  Moreover, a commercially available polymer film can also be used for the said polymer base material. For example, the product name “Fujitac” manufactured by Fuji Photo Film Co., Ltd., the product name “Zeonor” manufactured by Nippon Zeon Co., Ltd., and the product name “Arton” manufactured by JSR Co., Ltd. may be used.

  Examples of the method for evaporating the solvent (drying method) include, for example, an air circulation type constant temperature oven in which hot air or cold air circulates, a heater using microwaves or far infrared rays, a roll heated for temperature control, a heat pipe roll Alternatively, a drying means such as a metal belt is used.

  The temperature employed for the drying means (drying temperature) is preferably equal to or lower than the glass transition temperature of the resin composition, and is preferably dried by gradually raising the temperature from a low temperature to a high temperature. Specifically, it is preferably 50 ° C to 130 ° C, more preferably 80 ° C to 120 ° C, and most preferably 90 ° C to 110 ° C. If it is said temperature range, a polymer film with high surface uniformity can be obtained.

  The time required for the drying means (drying time) is not particularly limited, but in order to obtain a polymer film having good display uniformity and low residual volatile components, it is, for example, 1 minute to 60 minutes, Preferably, it is 10 minutes to 40 minutes.

<< D. Polymer film stretching method >>
As a stretching method of the polymer film used in the present invention, any suitable stretching method can be adopted depending on the purpose. Specific examples include a longitudinal uniaxial stretching method, a transverse uniaxial stretching method, a longitudinal and transverse simultaneous biaxial stretching method, a longitudinal and transverse sequential biaxial stretching method, and the like. For example, a heat uniaxial stretching method may be used. As the stretching means, any suitable stretching machine such as a roll stretching machine, a tenter stretching machine, or a biaxial stretching machine can be used. Preferably, the stretching machine includes a temperature control unit. When extending | stretching by heating, the temperature inside an extending | stretching machine may be changed continuously and may be changed in steps. Further, the stretching step may be divided into two or more times. The stretching direction may be the film longitudinal direction (MD direction) or the width direction (TD direction). Moreover, you may extend | stretch in the diagonal direction (diagonal extending | stretching) using the extending | stretching method of FIG. 1 of Unexamined-Japanese-Patent No. 2003-262721.

  Preferably, the method for stretching the polymer film used in the present invention is a method in which a shrinkable film is bonded to both surfaces of the polymer film and heated and stretched by a longitudinal uniaxial stretching method using a roll stretching machine. The shrinkable film is used for imparting a shrinkage force in a direction perpendicular to the stretching direction at the time of heat stretching and increasing a refractive index (nz) in the thickness direction. According to said extending | stretching method, the retardation film which shows the refractive index distribution of nx> nz> ny can be obtained. A retardation film exhibiting a refractive index distribution of nx> nz> ny is suitable for increasing the contrast ratio in the oblique direction of the liquid crystal display device and reducing the amount of color shift in the oblique direction.

  The method for attaching the shrinkable film on both sides of the polymer film is not particularly limited, but an acrylic pressure-sensitive adhesive layer having an acrylic polymer as a base polymer between the polymer film and the shrinkable film. The method of providing and bonding is preferable from the viewpoint of excellent workability and economical efficiency.

  An example of the method for stretching the polymer film of the present invention will be described with reference to FIG. FIG. 2 is a schematic view showing the concept of a step of stretching the polymer film of the present invention. The polymer film 302 is fed out from the first feeding unit 301, and a shrinkable film having two pressure-sensitive adhesive layers is bonded to both surfaces of the polymer film by the laminate rolls 307 and 308. One shrinkable film 304 is drawn out from the second drawing-out portion 303, and the other shrinkable film 306 is drawn out from the third drawing-out portion 305. The polymer film having the shrinkable film attached on both sides is given a tension in the film longitudinal direction by rolls 310, 311, 312 and 313 having different speed ratios while being held at a constant temperature by the temperature control means 309. (At the same time, when the shrinkable film shrinks, tension is also applied to the polymer film in the thickness direction), and the film is subjected to a stretching treatment. After the stretching treatment, the shrinkable films 315 and 317 having the pressure-sensitive adhesive layer are wound up by the first winding unit 314 and the second winding unit 316, and the obtained retardation film 318 is the third winding. It is wound up by the take-up part 319.

  The shrinkable film has a shrinkage ratio in the film longitudinal direction at 140 ° C .: S (MD) of 2.7% to 9.4%, and a shrinkage ratio in the width direction: S (TD) of 4.6. What is% to 15.8% is preferably used. Preferably, the shrinkable film has a difference between the shrinkage in the width direction and the shrinkage in the longitudinal direction: ΔS = S (TD) −S (MD) in the range of 3.2% to 9.6%. There is something. Within the above range, a retardation film excellent in optical uniformity and satisfying desired optical characteristics can be obtained. The optical properties of the retardation film will be described later in Section E.

  The shrinkage rates S (MD) and S (TD) can be determined according to the method of heating shrinkage rate A of JIS Z 1712 (: 1997) (however, the heating temperature is set to 140 ° C. instead of 120 ° C. The difference is that a load of 3 g was applied to the piece). Specifically, five test pieces each having a width of 20 mm and a length of 150 mm were taken from the vertical (MD) and horizontal (TD) directions, and a test piece with a mark at a distance of about 100 mm at the center was prepared. To do. The test piece is suspended vertically in an air circulation drying oven maintained at a temperature of 140 ° C. ± 3 ° C. under a load of 3 g, heated for 15 minutes, taken out, and left in a standard state (room temperature) for 30 minutes. Then, using a caliper specified in JIS B 7507, the distance between the gauge points was measured to obtain an average value of five measured values, and S (%) = [[distance between gauge points before heating ( mm) −distance between gauge points after heating (mm)] / distance between gauge points before heating (mm)] × 100.

  The shrinkable film is preferably a stretched film such as a biaxially stretched film or a uniaxially stretched film. The shrinkable film can be obtained, for example, by stretching an unstretched film formed into a sheet by an extrusion method in the longitudinal and / or transverse direction at a predetermined magnification with a simultaneous biaxial stretching machine or the like. The molding and stretching conditions can be appropriately selected depending on the composition, type and purpose of the resin used.

  Examples of the material for forming the shrinkable film include polyester, polystyrene, polyethylene, polypropylene, polyvinyl chloride, and polyvinylidene chloride. Among these, as the shrinkable film used in the present invention, a biaxially stretched polypropylene film is preferably used in view of excellent mechanical strength, thermal stability, surface uniformity and the like.

  In addition, the shrinkable film can be used for general packaging, food packaging, pallet packaging, shrinkage label, cap seal, and electrical insulation as long as the object of the present invention is satisfied. A commercially available shrinkable film can be appropriately selected and used. These commercially available shrinkable films may be used as they are, or after being subjected to secondary processing such as stretching treatment or shrinkage treatment. Specific examples of commercially available shrinkable films include Oji Paper Co., Ltd. product name “Alphan Series”, Gunze Co., Ltd. product name “Fancy Top Series”, and Toray Industries, Inc. product name “Trephan Series”. , Santox Co., Ltd., trade name “Santox-OP Series”, Tosero Co., Ltd., trade name “Tosero OP Series”, and the like.

  The temperature in the temperature control means (also referred to as the stretching temperature) when heating and stretching the laminate of the polymer film and the shrinkable film depends on the target retardation value, the type and thickness of the polymer film used, etc. Can be appropriately selected. Preferably, it is performed in the range of Tg + 1 ° C. to Tg + 30 ° C. with respect to the glass transition point (Tg) of the polymer film. This is because the retardation value tends to be uniform, and the film is difficult to crystallize (white turbidity). More specifically, the stretching temperature is preferably 90 ° C to 150 ° C, more preferably 100 ° C to 140 ° C, and most preferably 110 ° C to 135 ° C. The glass transition temperature (Tg) can be determined by a DSC method according to JIS K 7121 (: 1987).

  The temperature control means is not particularly limited, but is an air circulation type constant temperature oven in which hot air or cold air circulates, a heater using microwaves or far infrared rays, a roll heated for temperature control, a heat pipe roll, or a metal. A known heating method and temperature control method using a belt or the like can be given.

Further, the stretching ratio (stretching ratio) when stretching the laminate of the polymer film and the shrinkable film is appropriately selected according to the target retardation value, the type and thickness of the polymer film to be used, and the like. obtain. The draw ratio is preferably 1.1 to 2.5 times, more preferably 1.2 to 2.0 times. The feed rate during stretching is not particularly limited, but is preferably 0.5 m / min to 30 m / min, more preferably 1 m / min to 20 m / min from the mechanical accuracy and stability of the stretching apparatus. If it is said extending | stretching conditions, not only the target optical characteristic can be satisfied, but the retardation film excellent in optical uniformity can be obtained.
E. Various properties of the retardation film obtained by the production method of the present invention The transmittance of the retardation film obtained by the production method of the present invention measured with light having a wavelength of 550 nm at 23 ° C. is preferably 80% or more, and more preferably Is 85% or more, particularly preferably 90% or more. Moreover, it is preferable that the polymer film mentioned above also has the same transmittance | permeability.

  The thickness of the retardation film can be appropriately selected according to the purpose. The thickness range of the retardation film is preferably 20 μm to 300 μm, and more preferably 30 μm to 200 μm. When used as a λ / 4 plate, the thickness is preferably 40 μm to 140 μm, and particularly preferably 60 μm to 120 μm. When used as a λ / 2 plate, it is preferably 130 μm to 230 μm, particularly preferably 150 μm to 210 μm. If it is said range, the retardation film which is excellent in mechanical strength and optical uniformity, and satisfies the optical characteristic mentioned later can be obtained.

The absolute value of the photoelastic coefficient measured with light having a wavelength of 550 nm at 23 ° C. of the retardation film; C [550] (m ² / N) is 50 × 10 ⁻¹² or less. By reducing the absolute value of the photoelastic coefficient of the retardation film, the shrinkage stress of the polarizer and the shift and unevenness of the retardation value caused by the heat of the backlight of the liquid crystal panel are prevented, resulting in good display uniformity. An image display device having the characteristics can be obtained. Preferably, C [550] of the retardation film is 1 × 10 ⁻¹² to 40 × 10 ⁻¹² , particularly preferably 3 × 10 ⁻¹² to 30 × 10 ⁻¹² or less, and most preferably 5 ×. 10 ^{−12 to} 25 × 10 ⁻¹² . By setting C [550] in the above range, a target phase difference value can be obtained, and deviation or unevenness of the phase difference value can be reduced.

  The water absorption of the retardation film is preferably 0.01% to 5%, more preferably 0.05% to 4%, particularly preferably 0.1% to 3%, most preferably. 0.2% to 2%. By setting it as said range, the retardation film which shows stability of favorable retardation value can be obtained. In addition, the water absorption rate of the said retardation film can be calculated | required by the method according to JISK7209 (: 2000). In addition, the water absorption rate of the said retardation film is suitably adjusted with the kind of substituent of the polyvinyl acetal type resin used for this invention, and the residual amount of a hydroxyl group.

  The retardation film obtained by the production method of the present invention is stretched so as to satisfy various refractive index distributions according to purposes. As specific examples of the refractive index distribution, those satisfying the relationship of nx> ny = nz (Re> 10 nm, Re [550] = Rth [550]), nx> ny> nz (10 nm <Re [550] <Rth [550]), nx = ny> nz (Rth [550]> 10 nm, Re [550] = 0 nm), nx = nz> ny (Re [550]> 10 nm, Rth [550] = 0), nx> nz> ny (0 nm <Rth [550] <Re [550]), nz> nx> ny (Rth [550] <0 nm <Re And those satisfying the relationship [550]). The nx, ny, and nz represent the refractive indexes in the slow axis direction, the fast axis direction, and the thickness direction of the retardation film, respectively. Among these, the retardation film obtained by the production method of the present invention is preferably stretched so as to satisfy the relationship of nx> nz> ny (0 nm <Rth [550] <Re [550]).

  In this specification, Re [550] refers to an in-plane retardation value measured with light having a wavelength of 550 nm at 23 ° C. Re [550] is expressed by the formula: Re when the refractive index in the slow axis direction and the fast axis direction of the retardation film at a wavelength of 550 nm is nx and ny, and d (nm) is the thickness of the retardation film. [550] = (nx−ny) × d. The slow axis refers to the direction in which the in-plane refractive index is maximum. Re [450] and Re [650] indicate in-plane retardation values measured with light having a wavelength of 450 nm and 650 nm at 23 ° C., respectively.

  Re [550] of the retardation film obtained by the production method of the present invention is 20 nm to 400 nm, preferably 80 nm to 350 nm. When used as a λ / 4 plate, it is preferably 100 nm to 180 nm, more preferably 110 nm to 170 nm, particularly preferably 120 nm to 160 nm, and most preferably 130 to 150 nm. When used as a λ / 2 plate, it is preferably 220 nm to 300 nm, more preferably 230 nm to 290 nm, particularly preferably 240 nm to 280 nm, and most preferably 250 nm to 270 nm. By setting Re [550] in the above range, the contrast ratio in the oblique direction of the liquid crystal display device can be increased. The above Re [550] is adjusted to an appropriate value depending on the draw ratio and the draw temperature.

  Generally, the retardation value of the retardation film may vary depending on the wavelength. This is called the wavelength dispersion characteristic of the retardation film. The retardation film obtained by the production method of the present invention exhibits a characteristic that the retardation value becomes smaller as the wavelength is shorter (also referred to as reverse wavelength dispersion characteristic), and the formula: Re [450] <Re [550] <Re [650] Satisfied. In the present specification, the chromatic dispersion characteristic can be obtained by a ratio of in-plane retardation values measured with light having a wavelength of 450 nm and 550 nm at 23 ° C .: Re [450] / Re [550].

  Re [450] / Re [550] of the retardation film obtained by the production method of the present invention is smaller than 1. Preferably it is 0.70-0.99, More preferably, it is 0.76-0.92, Especially preferably, it is 0.80-0.88, Most preferably, it is 0.82-0.86 is there. By setting Re [450] / Re [550] in the above range, the retardation value becomes constant in a wide visible light region. Therefore, when used in a liquid crystal display device, the wavelength of light leaked is reduced. Therefore, the color shift amount in the oblique direction of the liquid crystal display device can be further reduced. The above Re [450] / Re [550] is the type of substituent of the polyvinyl acetal resin used and the molar ratio of structural units (for example, in the structure represented by the general formula (II), l, m, and n ratio).

  In this specification, Rth [550] refers to a thickness direction retardation value measured with light having a wavelength of 550 nm at 23 ° C. Rth [550] is expressed by the formula: Rth [550] when the refractive index in the slow axis direction and the thickness direction of the retardation film at a wavelength of 550 nm is nx and nz, and d (nm) is the thickness of the retardation film. = (Nx−nz) × d. The slow axis refers to the direction in which the in-plane refractive index is maximum.

  Preferably, Rth [550] of the retardation film obtained by the production method of the present invention satisfies the formula: Rth [550] <Re [550]. By setting in such a range, the phase difference value in the oblique direction can be made appropriate, so that the contrast ratio in the oblique direction of the liquid crystal display device can be increased. Specifically, an appropriate range of Rth [550] is appropriately selected according to the Nz coefficient of the retardation film described later. For example, when the retardation film obtained by the production method of the present invention is used as a λ / 4 plate having an Nz coefficient of 0.5, Rth [550] is preferably 50 nm to 90 nm, more preferably 55 nm to 85 nm, particularly preferably 60 nm to 80 nm, and most preferably 65 nm to 75 nm. When the retardation film obtained by the production method of the present invention is used as a λ / 2 plate having an Nz coefficient of 0.5, Rth [550] is preferably 110 nm to 150 nm, more preferably 115 nm to 145 nm, particularly preferably 120 nm to 140 nm, and most preferably 125 nm to 135 nm. The Rth [550] is adjusted to an appropriate value depending on the stretching ratio and the stretching temperature, and when a shrinkable film is used, depending on the shrinkage rate of the shrinkable film.

Re [550] and Rth [550] can also be obtained using a spectroscopic ellipsometer [manufactured by JASCO Corporation, product name “M-220”]. In-plane retardation value (Re) at a wavelength of 550 nm at 23 ° C., retardation value (R40) measured by tilting the slow axis by 40 degrees with respect to the tilt axis, thickness of optical element (or retardation film) (d ) And the average refractive index (n0) of the optical element (or retardation film), nx, ny and nz are obtained by computer numerical calculation from the following formulas (i) to (iv), and then the formula (iv) Rth can be calculated by Here, φ and ny ′ are represented by the following equations (v) and (vi), respectively.
Re = (nx−ny) × d (i)
R40 = (nx−ny ′) × d / cos (φ) (ii)
(Nx + ny + nz) / 3 = n0 (iii)
Rth = (nx−nz) × d (iv)
φ = sin ⁻¹ [sin (40 °) / n0] (v)
ny ′ = ny × nz [ny ² × sin ² (φ) + nz ² × cos ² (φ)] ^1/2 (vi)

  In this specification, Rth [550] / Re [550] refers to a ratio between a thickness direction retardation value measured with light having a wavelength of 550 nm at 23 ° C. and an in-plane retardation value (also referred to as an Nz coefficient). .

  Preferably, the Nz coefficient of the retardation film obtained by the production method of the present invention is 1.2 or less. More preferably, the Nz coefficient of the retardation film is less than 1. When the Nz coefficient is smaller than 1, the retardation film satisfies the formula: Rth [550] <Re [550]. Preferably, the Nz coefficient of the retardation film is more than 0 and less than 1. When the Nz coefficient exceeds 0 and is smaller than 1, the retardation film satisfies the formula: 0 nm <Rth [550] <Re [550]. More preferably, the Nz coefficient of the retardation film is 0.2 to 0.8, particularly preferably 0.3 to 0.7, and most preferably 0.4 to 0.6. By setting the Nz coefficient in the above range, the phase difference value in the oblique direction is appropriately adjusted (for example, the angle dependency of the phase difference value is reduced), and the contrast ratio in the oblique direction of the liquid crystal display device can be increased. it can.

The present invention will be further described using the above examples and comparative examples. In addition, this invention is not limited only to these Examples. In addition, each analysis method used in the Example is as follows.
(1) Measurement of composition ratio:
Nuclear magnetic resonance spectrometer [product name “LA400” manufactured by JEOL Ltd.] (measurement solvent: heavy DMSO solvent, frequency: 400 MHz, observation nucleus: ¹ H, measurement temperature: 25 ° C.), 0.83 ppm, 0 It calculated | required from the peak of .95-2.0 ppm, 3.5-5.0 ppm, and 6.76 ppm.
(2) Measurement of glass transition temperature:
Using a differential scanning calorimeter [manufactured by Seiko Co., Ltd., product name “DSC-6200”], it was determined by a method according to JIS K 7121 (: 1987) (method for measuring the transition temperature of plastics). Specifically, a 10 mg powder sample was heated twice (heating rate: 10 ° C./min) in a nitrogen atmosphere (gas flow rate: 50 ml / min) and measured twice, and the second data was adopted. The calorimeter corrected the temperature using a standard material (indium).
(3) Measuring method of thickness:
When the thickness was less than 10 μm, measurement was performed using a thin film spectrophotometer [manufactured by Otsuka Electronics Co., Ltd., “instant multiphotometry system MCPD-2000”]. When the thickness was 10 μm or more, measurement was performed using an Anritsu digital micrometer “KC-351C type”.
(4) Measuring method of phase difference values (Re, Rth):
Using a spectroscopic ellipsometer [manufactured by JASCO Corporation, product name “M-220”], measurement was performed with light having a wavelength of 550 nm at 23 ° C. For wavelength dispersion measurement, light with wavelengths of 450 nm and 650 nm was also used.
(5) Measuring method of average refractive index of film:
It calculated | required from the refractive index measured with the light of wavelength 589nm in 23 degreeC using the Abbe refractometer [The product name "DR-M4" by Atago Co., Ltd.].
(6) Transmittance measurement method:
It measured with the light of wavelength 550nm in 23 degreeC using the ultraviolet visible spectrophotometer [The product name "V-560" by JASCO Corporation].
(7) Photoelastic coefficient measurement method:
Using a spectroscopic ellipsometer [product name “M-220” manufactured by JASCO Corporation], the sample (size 2 cm × 10 cm) is sandwiched at both ends, and stress (5N to 15N) is applied to the phase difference at the center of the sample. The value (23 ° C./wavelength 550 nm) was measured and calculated from the slope of the function of stress and phase difference value.
(8) Measurement of water absorption:
It was measured by a method according to JIS K 7209 (: 2000) (Testing method for water absorption rate and boiling water absorption rate of plastic). The test sample was 50 mm × 50 mm and the thickness was 40 μm to 100 μm.

[Reference Example 1]
After drying 5.0 g of a polyvinyl alcohol-based resin [manufactured by Nippon Synthetic Chemical Co., Ltd., trade name “NH-18” (polymerization degree: 1800, saponification degree: 99.0%)] at 105 ° C. for 2 hours, Dissolved in 95 ml of dimethyl sulfoxide (DMSO). To this, 2.02 g of 2,4,6-trimethylbenzaldehyde (mesitaldehyde) and 0.44 g of p-toluenesulfonic acid monohydrate were added and stirred at 40 ° C. for 2 hours. To this, 13.41 g of 1,1-diethoxyethane (acetal) was added and further stirred at 40 ° C. for 2 hours. Thereafter, 1.18 g of triethylamine was added to complete the reaction. The obtained reaction product (polymer) was dropped into a methanol solution, and reprecipitation was performed. After the polymer was allowed to settle and the supernatant was removed by decantation, methanol / water = 1/1 (volume / volume) was further added to wash the polymer. The polymer obtained by filtering this was dried to obtain 7.50 g of a white polymer. The white polymer was a polyvinyl acetal resin having a structure (l: m: n = 21: 58: 21) represented by the following chemical structural formula (III) as measured by ¹ H-NMR. Moreover, it was 120 degreeC when the glass transition temperature of this white polymer was measured with the differential scanning calorimeter.

[Reference Example 2]
The polyvinyl acetal resin powder obtained in Reference Example 1 and a solvent were added to a sample bottle, and the solubility of the polyvinyl acetal resin in various solvents at 23 ° C. and 40 ° C. was examined. Table 1 shows the results of the solubility test. All tests were classified into four stages of x, Δ, ○, and ◎ by visual observation. The evaluation criteria are “x” when the resin is dissolved in the solvent 100 from 0 (weight ratio) to less than 5 (weight ratio), and the resin is 5 (weight ratio) to less than 15 (weight ratio) in the solvent 100 “Δ” indicates that the resin is dissolved, and “◯” indicates that the resin is dissolved in the solvent 100 by 15 (weight ratio) or more and less than 25 (weight ratio), and the resin dissolves in the solvent 100 by 25 (weight ratio) or more. The thing was designated as “◎”.

[Example 1]
The polyvinyl acetal resin (30 parts by weight) obtained in Reference Example 1 was dissolved in toluene (100 parts by weight) to prepare a 23% by weight solution. This solution is uniformly cast in the form of a sheet with a comma coater on the surface of a polyethylene terephthalate film [trade name “Lumirror S27-E” manufactured by Toray Industries, Inc.] having a thickness of 75 μm. In the oven (error ± 1 ° C.), the solvent was evaporated while gradually raising the temperature from low temperature to 80 ° C. for 20 minutes, 120 ° C. for 20 minutes, and 140 ° C. for 30 minutes. The polyethylene terephthalate film was peeled off to produce a polymer film having a width of 300 mm and a thickness of 80 μm. This polymer film had a transmittance of 90%, a water absorption of 3%, and a residual volatile component content of 5%. This polymer film (average refractive index = 1.50, Re [550] = 2.0 nm, Rth [550] = 2.0 nm) is roll-stretched in an air circulation drying oven at 130 ° C. ± 1 ° C. The film was stretched uniaxially by 1.5 times in the longitudinal direction of the film. The properties of the obtained retardation film A are shown in Table 2 below together with the film properties of Examples 2-3. A part of the retardation film A was left in an air circulation type drying oven at 80 ° C. ± 1 ° C., and the Re [550] after 100 hours was measured. The change in Re [550] was less than 2%. The retardation film A exhibited excellent stability of the retardation value.

[Example 2]
A resin composition (30 parts by weight) obtained by mixing 1.5 parts by weight of a liquid crystal compound [trade name “Paliocolor LC242” manufactured by BASF Corp.] with 28.5 parts by weight of the polyvinyl acetal resin obtained in Reference Example 1, It was dissolved in 100 parts by weight of isobutyl ketone to prepare a 23% by weight solution. This solution is uniformly cast in the form of a sheet with a comma coater on the surface of an 80 μm thick triacetylcellulose film [trade name “UZ-TAC” manufactured by Fuji Photo Film Co., Ltd.], and multi-chamber air circulation The solvent was evaporated while gradually raising the temperature from a low temperature in an oven drying oven (error ± 1 ° C.) at 80 ° C. for 20 minutes, 120 ° C. for 20 minutes, and 140 ° C. for 30 minutes. The triacetylcellulose film was peeled off to produce a polymer film having a width of 300 mm and a thickness of 92 μm. This polymer film had a transmittance of 90%, a water absorption of 2%, and a residual volatile component amount of 4%. This polymer film (average refractive index = 1.51, Re [550] = 1.8 nm, Rth [550] = 2.1 nm) is roll-stretched in an air circulation drying oven at 130 ° C. ± 1 ° C. The film was stretched uniaxially by 1.5 times in the longitudinal direction of the film. The properties of the obtained retardation film B are shown in Table 2.

[Example 3]
On both sides of a 180 μm-thick polymer film (average refractive index = 1.50, Re [550] = 2.8 nm, Rth [550] = 3.0 nm) obtained by the same method as in Example 1. An axial stretched polypropylene film [trade name “Trefan E60-high shrinkage type” (thickness 60 μm) manufactured by Toray Industries, Inc.] was bonded via an acrylic pressure-sensitive adhesive (thickness 15 μm). Thereafter, the film was uniaxially stretched 1.5 times in the longitudinal direction of the film using a roll stretching machine in an air circulation drying oven at 145 ° C. ± 1 ° C. Table 2 shows the properties of the obtained retardation film C.

  The biaxially stretched polypropylene film used in this example had a shrinkage rate at 140 ° C. of 6.4% in the MD direction and 12.8% in the TD direction. The acrylic pressure-sensitive adhesive uses isononyl acrylate (weight average molecular weight = 550,000) synthesized by solution polymerization as a base polymer, and a polyisocyanate compound cross-linking agent [Nippon Polyurethane (100% by weight). A product obtained by mixing 3 parts by weight of a trade name “Coronate L” manufactured by Co., Ltd. and 10 parts by weight of a catalyst [trade name “OL-1” manufactured by Tokyo Fine Chemical Co., Ltd.] was used.

[Evaluation]
As shown in Examples 1 to 3, the retardation film obtained by the production method of the present invention showed a reverse wavelength dispersion characteristic in which the absolute value of the photoelastic coefficient was small and the retardation value was smaller as the wavelength was shorter. . As shown in Example 2, when a resin composition in which a liquid crystal compound is added to a polyvinyl acetal resin having a specific structure is used, the stretch orientation is further improved, which is significantly higher than that of a conventional retardation film. A retardation value of λ / 2 or λ / 4 could be achieved with a small thickness. Further, as shown in Example 3, a retardation film satisfying nx>nz> ny (0 nm <Rth [550] <Re [550]) was obtained by stretching the polymer film.

  As described above, according to the retardation film obtained by the production method of the present invention, the absolute value of the photoelastic coefficient is small and the inverse wavelength dispersion characteristic is exhibited, so that it is extremely useful for improving the display characteristic of the liquid crystal display device. It can be said that. The liquid crystal panel of the present invention is suitably used for a liquid crystal display device and a liquid crystal television.

It is a schematic diagram which shows the concept of the process which shape | molds the polymer film of this invention. It is a schematic diagram which shows the concept of the process of extending | stretching the polymer film of this invention.

Explanation of symbols

201 Feeding unit 202 Base material 203 Guide roll 204 Coater 205, 206, 207 Drying means 208 Polymer film 209 Winding unit 301 First feeding unit 302 Polymer film 303 Second feeding unit 304 Shrinkable film 305 Third Feeding part 306 Contractive film 307, 308 Laminating roll 309 Temperature control means 310, 311, 312, 313 Roll 314 First winding part 315, 317 Contracting film 316 Second winding part 318 Phase difference film 319 Third Winding part

Claims (4)

A method for producing a retardation film satisfying the following formulas (1) and (2):
A solvent containing at least one selected from toluene, ethyl acetate, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, and cyclohexanone is mainly composed of a polyvinyl acetal resin having a structure represented by the following general formula (I). Including a step of casting a solution prepared by dissolving a resin composition on a surface of a substrate in the form of a sheet and evaporating a solvent to obtain a polymer film, and a step of stretching the polymer film. Production method of retardation film:
Re [450] <Re [550] <Re [650] (1)
20 nm ≦ Re [550] ≦ 400 nm (2)
However, Re [450], Re [550], and Re [650] are in-plane retardation values measured with light having wavelengths of 450 nm, 550 nm, and 650 nm at 23 ° C., respectively.
(In general formula (I), R1 has a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a phenyl group which may have a substituent, or a substituent. Represents an optionally substituted naphthyl group, an optionally substituted anthranyl group, or an optionally substituted phenanthrenyl group, R2, R3 and R4 each independently represent a hydrogen atom, a carbon number; 1 to 4 linear, branched or cyclic alkyl group, 1 to 4 linear or branched alkoxyl group, halogen atom, halogenated alkyl group, nitro group, amino group, hydroxyl group, A cyano group or a thiol group, provided that R2 and R3 are not hydrogen atoms at the same time. L represents an integer of 2 or more). The method for producing a retardation film according to claim 1 , wherein the polyvinyl acetal resin has a structure represented by the following general formula (II):
(In general formula (II), R 1, R 5 and R 6 may each independently have a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or a substituent. A phenyl group, an optionally substituted naphthyl group, an optionally substituted anthranyl group, or an optionally substituted phenanthrenyl group, each of R2, R3 and R4 represents Independently, a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxyl group having 1 to 4 carbon atoms, a halogen atom, a halogenated alkyl group, A nitro group, an amino group, a hydroxyl group, a cyano group or a thiol group, wherein R2 and R3 are not hydrogen atoms at the same time, R7 is a hydrogen atom, linear, branched or cyclic with 1 to 8 carbon atoms; Alkyl group Jill group, a silyl group, a phosphate group, an acyl group, .l showing a benzoyl group or a sulfonyl group,, m, and n is an integer of 2 or more.). The resin composition is, with respect to the polyvinyl acetal resin 100, a liquid crystal compound containing more than 20 (weight ratio) or less 0, method for producing a retardation film according to claim 1 or 2. The polymer film thickness is 20Myuemu～300myuemu, method for producing a retardation film according to any one of claims 1 to 3.