Method for producing β-diketone derivatives, method for producing pyrazole derivatives, and phase difference film

Abstract

The object of the present invention is to provide a method for producing β-diketone derivatives with high yield. [Solution] The present invention provides a method for producing a β-diketone derivative, in which a ketone compound having a structure represented by general formula (1) and a carboxylic acid ester compound having a structure represented by general formula (2) are reacted in the presence of a base under reduced pressure of 15 kPa or less to produce a β-diketone derivative having a structure represented by general formula (3).

Description

[Technical Field]

[0001] The present invention relates to a method for producing β-diketone derivatives, a method for producing pyrazole derivatives, and a phase difference film. [Background technology]

[0002] β-diketone derivatives are useful as precursors for pyrazole compounds used in pharmaceuticals, functional materials, and the like. Furthermore, β-diketone derivatives are useful as intermediates for metal complexes, ionic liquids, supramolecules, and other materials. Therefore, there is a need for a simple method for producing β-diketone derivatives. In particular, pyrazole derivatives with two pyrazole cores, used as additives in pharmaceuticals, electronic materials, and optical applications, require high purity, and the precursor β-diketone derivatives also require high purity. Additionally, to improve productivity, there is a need to increase the yield in the production methods for β-diketone derivatives.

[0003] Conventional methods for producing β-diketone derivatives involve reacting a ketone with a carboxylic acid ester in tetrahydrofuran (THF) or ethylene glycol dimethyl ether in the presence of a base (Patent Document 1, Non-Patent Document 1, and Non-Patent Document 2). However, in this reaction, the α-hydrogen of the β-diketone is further abstracted by the base, and the β-diketone reacts with the starting material or intermediate to produce 3-4 mers. The solubility of these polymers is close to that of the β-diketone, and if the polymers are to be removed by purification, it is necessary to repeat recrystallization or suspension purification several times. Therefore, there has been a problem in that the productivity is extremely low when obtaining high-purity β-diketone derivatives.

[0004] To address these challenges, a manufacturing method has been disclosed in which a solvent is used in the reaction in which the number of donors is in the range of 25.0 to 35.0 (Patent Document 2).

[0005] While this manufacturing method has enabled the production of high-purity β-diketone derivatives, further improvement in yield was desired. Furthermore, conventional methods for producing β-diketone derivatives, such as the method using sodium hydride as a base to react dimethyl isophthalate with acetophenone (Non-Patent Literature 2), also yielded only 64% of the desired β-diketone derivative, and further improvement in yield was desired. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] U.S. Patent No. 5191121 [Patent Document 2] Japanese Patent Publication No. 2015-86170 [Non-patent literature]

[0007] [Non-Patent Document 1] Spectrochimica Acta,Part A:Molecular and Biomolecular Spectroscopy;vol.70;(2008);p.1203-1207 [Non-Patent Document 2] European Journal of Chemistry,vol.2 No.3;(2011);p.289-294 [Overview of the project] [Problems that the invention aims to solve]

[0008] This invention has been made in view of the above-mentioned problems and circumstances. The problem to be solved is to provide a method for producing β-diketone derivatives with high yield. [Means for solving the problem]

[0009] The inventors of the present invention investigated the causes of the above problems in order to solve them. As a result, they discovered that the yield of the synthesized β-diketone derivative is improved by reacting a ketone with a carboxylic acid ester in the presence of a base under reduced pressure, which led to the present invention. In other words, the above-mentioned problems according to the present invention are solved by the following means.

[0010] 1. A ketone compound having the structure represented by the following general formula (1), A carboxylic acid ester compound having the structure represented by the following general formula (2) is used. The reaction is carried out in the presence of a base under reduced pressure of 15 kPa or less. A method for producing a β-diketone derivative having a structure represented by the following general formula (3).

[0011] [ka]

[0012] In the formula, R 1 R represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or a tertiary alkyl group. 2 This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0013] [ka]

[0014] In the formula, Ar 1 R represents an aromatic hydrocarbon group or an aromatic heterocyclic group that may be substituted. 3 and R 4 Each of these independently represents an alkyl group having 1 to 6 carbon atoms. n represents an integer from 0 to 2. When n is 2, R 3 They may be the same or different.

[0015] [ka]

[0016] In the formula, R 1 represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or a tertiary alkyl group. Ar 1 represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group. R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. n represents an integer from 0 to 2. When n is 2, R 1 may be the same or different. When n is 2, R 2 may be the same or different.

[0017] 2. The method for producing a β-diketone derivative according to claim 1, wherein the ketone compound and the carboxylic acid ester compound are reacted in the presence of a dehydrating agent.

[0018] 3. The method for producing a β-diketone derivative according to claim 2, wherein the dehydrating agent is one or more compounds selected from the group consisting of a carbonic ester, a phosphorous ester, an alkoxysilane, and a titanate ester.

[0019] 4. The method for producing a β-diketone derivative according to claim 3, wherein the alkoxysilane includes a compound having a structure represented by the following general formula (4).

[0020]

Chemical formula

[0021] In the formula, R 5 represents an alkyl group having 1 to 4 carbon atoms. R 6 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group having 1 to 10 carbon atoms. p represents an integer from 0 to 3.

[0022] 5. The method for producing a β-diketone derivative according to claim 1, wherein the base is one or more compounds selected from the group consisting of a metal alkoxide, sodium amide, and sodium hydride.

[0023] 6. A method for producing the β-diketone derivative described in paragraph 1, wherein the ketone compound has a structure represented by the following general formula (1a).

[0024] [ka]

[0025] In the formula, R 2 X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 1 m represents a substituent. 1 This represents an integer from 0 to 5.

[0026] 7. A method for producing the β-diketone derivative according to paragraph 1, wherein the carboxylic acid ester compound has a structure represented by the following general formula (2a).

[0027] [ka]

[0028] In the formula, R 3 and R 4 Each of these independently represents an alkyl group having 1 to 6 carbon atoms. 2 m represents a substituent. 2 This represents an integer from 0 to 4.

[0029] 8. A method for producing a β-diketone derivative according to item 6 or 7, comprising reacting the ketone compound with the carboxylic acid ester compound in the presence of a dehydrating agent.

[0030] 9. A method for producing a β-diketone derivative according to paragraph 8, wherein the dehydrating agent is one or more compounds selected from the group including carbonate esters, phosphite esters, alkoxysilanes, and titanate esters.

[0031] 10. A method for producing a β-diketone derivative according to paragraph 9, wherein the alkoxysilane contains a compound having a structure represented by the following general formula (4).

[0032] [ka]

[0033] In the formula, R 5 R represents an alkyl group with 1 to 4 carbon atoms. 6 represents an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms. p represents an integer from 0 to 3.

[0034] 11. A method for producing a β-diketone derivative according to paragraph 6 or 7, wherein the base is one or more compounds selected from the group including metal alkoxides, sodium amides, and sodium hydride.

[0035] 12. A β-diketone derivative is produced using the method for producing a β-diketone derivative described in any one of paragraphs 1 to 7. A method for producing a pyrazole derivative, comprising reacting a manufactured β-diketone derivative with hydrazine to produce a pyrazole derivative having the structure represented by the following general formula (5).

[0036] [ka]

[0037] In the formula, R 1 Ar represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or a tertiary alkyl group. 1 This represents a divalent aromatic hydrocarbon group or an aromatic heterocyclic group.

[0038] 13. A resin containing a pyrazole derivative having a structure represented by the following general formula (5), and a compound having a structure represented by the following general formula (6), A phase difference film in which, when the total amount of the aforementioned resin is 100 parts by mass, the content of a compound having the structure represented by the following general formula (6) is in the range of 0.0001 to 0.1 parts by mass.

[0039] [ka]

[0040] In the formula, R 1 Ar represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or a tertiary alkyl group. 1 This represents a divalent aromatic hydrocarbon group or an aromatic heterocyclic group.

[0041] [ka]

[0042] In the formula, R 7 X represents an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms. 3 , X 4 and X 5 This is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -Si-R 8 (OX 6 ) Represents the group represented by 2. 8 X represents an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms. 6 This is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -Si-R 8 (OX 6 ) represents 2. [Effects of the Invention]

[0043] The above-described means of the present invention can provide a method for producing β-diketone derivatives with high yield.

[0044] Although the mechanism of action or mechanism of the present invention is not yet clear, it is speculated as follows.

[0045] In the reaction between ketones and carboxylic acid esters, alcohols are produced in addition to β-diketones. The accumulation of alcohols hinders the reaction between ketones and carboxylic acid esters. Furthermore, in the reaction between ketones and carboxylic acid esters, water is produced through the self-condensation of the ketone, in addition to the β-diketone. In the reaction in the presence of a base, the base reacts with the produced water to generate sodium hydroxide, ammonia, hydrogen, etc. As a result, the abstraction of α-hydrogens from the β-diketone may not proceed sufficiently, making it difficult to obtain high yields.

[0046] In the production method of the present invention, water, alcohol, etc. are removed under reduced pressure of 15 kPa or less to react the ketone with the carboxylic acid ester. Although the exact mechanism is not clear, this allows for the specific and effective removal of water and alcohol, which inhibit the reaction between the ketone and the carboxylic acid ester, thereby improving the yield of the resulting β-diketone derivative. [Brief explanation of the drawing]

[0047] [Figure 1] This is a schematic cross-sectional view showing an example of the configuration of a polarizing plate having a phase difference film. [Modes for carrying out the invention]

[0048] The present invention provides a method for producing a β-diketone derivative, in which a ketone compound having the structure represented by the general formula (1) and a carboxylic acid ester compound having the structure represented by the general formula (2) are reacted in the presence of a base under reduced pressure of 15 kPa or less to produce a β-diketone derivative having the structure represented by the general formula (3). The above features are technical features common to or corresponding to the embodiments described below.

[0049] In one embodiment of the present invention, the reaction is carried out under reduced pressure of 15 kPa in order to remove the alcohol produced as the reaction proceeds. This allows the alcohol to be evaporated at a relatively low temperature, making it easier to remove the alcohol from the reaction system and improving the yield of the resulting β-diketone derivative.

[0050] In embodiments of the present invention, it is preferable to react a ketone compound with a carboxylic acid ester compound in the presence of a dehydrating agent. This allows the dehydrating agent to sufficiently remove water and alcohol, thereby improving the yield of the resulting β-diketone derivative.

[0051] In embodiments of the present invention, it is preferable that the dehydrating agent is one or more compounds selected from the group consisting of carbonate esters, phosphite esters, alkoxysilanes, and titanate esters. This allows the dehydrating agent to sufficiently remove water and alcohol, thereby improving the yield of the resulting β-diketone derivative.

[0052] In embodiments of the present invention, it is preferable that the alkoxysilane contains a compound having the structure represented by the general formula (4) above. This allows the dehydrating agent to sufficiently remove water and alcohol, thereby improving the yield of the resulting β-diketone derivative.

[0053] In embodiments of the present invention, it is preferable that the base is one or more compounds selected from the group including metal alkoxides, sodium amides, and sodium hydride. This promotes the abstraction of α-hydrogens and nucleophilic reactions in the base, thereby improving the yield of the resulting β-diketone derivative.

[0054] In embodiments of the present invention, it is preferable that the ketone compound has the structure represented by the above general formula (1a). This allows for the acquisition of useful β-diketone derivatives in high yield.

[0055] In embodiments of the present invention, it is preferable that the carboxylic acid ester compound has the structure represented by the above general formula (2a). This allows for the acquisition of useful β-diketone derivatives in high yield.

[0056] The present invention provides a method for producing a pyrazole derivative, which involves producing a β-diketone derivative using the method described above for producing a β-diketone derivative, and then reacting the produced β-diketone derivative with hydrazine to produce a pyrazole derivative having the structure represented by the general formula (5). This improves the yield of the resulting pyrazole derivative.

[0057] The phase difference film of the present invention contains a resin, a pyrazole derivative having the structure represented by the general formula (5), and a compound having the structure represented by the general formula (6), wherein the content of the compound having the structure represented by the general formula (6) is in the range of 0.0001 to 0.1 parts by mass when the total amount of resin is 100 parts by mass. This makes it possible to obtain a phase difference film in which the retardation value changes with respect to humidity fluctuations are small. Furthermore, it is possible to reduce internal haze in the phase difference film and suppress the occurrence of blocking.

[0058] Hereinafter, one or more embodiments of the present invention will be described with reference to the drawings. However, the scope of the present invention is not limited to the disclosed embodiments. In this application, "~" is used to mean that the numerical values ​​described before and after it are included as the lower limit and upper limit.

[0059] Before describing the details of the manufacturing method, we will first describe the compound (β-diketone derivative) having the structure represented by general formula (3) that is produced by this method.

[0060] <β-diketone derivatives> In this embodiment, a β-diketone derivative having the structure represented by the following general formula (3) can be produced using a ketone and a carboxylic acid ester as raw materials.

[0061] [ka]

[0062] In general formula (3), R 1This represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or a tertiary alkyl group. 1 In ketones having substituents represented by , only one α-hydrogen is abstracted by the base, and this α-hydrogen is abstracted, allowing the desired reaction to proceed. Examples of aromatic hydrocarbon groups include phenyl, p-tolyl, and naphthyl groups. Examples of aromatic heterocyclic groups include 2-pyrrole, 2-furyl, 2-thienyl, pyrrole, imidazolyl, oxazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, 2-benzothiazolyl, pyrazolinone, pyridyl, pyridinone, and 2-pyrimidinyl groups. Examples of tertiary alkyl groups include tert-butyl and tert-octyl groups.

[0063] From the perspective of suppressing the formation of polymers, R 1 It is preferably an aromatic hydrocarbon group or a tertiary alkyl group. In particular, R 1 It is more preferably an aromatic hydrocarbon group, and even more preferably a phenyl group.

[0064] In general formula (3), Ar 1 This represents an aromatic hydrocarbon group or an aromatic heterocyclic group that may be substituted. 1 In carboxylic acid esters having substituents represented by , since there are no α-hydrogens, the reaction of abstracting an α-hydrogen does not proceed, and the desired reaction proceeds. Examples of aromatic rings of the optionally substituted aromatic hydrocarbon group include benzene, methylbenzene, and naphthalene. Examples of aromatic heterocycles of the optionally substituted aromatic heterocyclic group include pyrrole, furan, thiophene, imidazole, oxazole, thiazole, benzimidazole, benzoxazole, benzothiazole, pyrazolinone, pyridine, pyridinone, and pyrimidine.

[0065] From the perspective of high yield, Ar 1 It is preferably an aromatic hydrocarbon group, and more preferably benzene as the aromatic ring of the aromatic hydrocarbon group.

[0066] In general formula (3), R 2 This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include the methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group.

[0067] In general formula (3), n represents an integer from 0 to 2. When n is 2, two R 1 The two R values ​​may be the same or different. When n is 2, the two R values ​​are 2 They may be the same or different.

[0068] In general formula (3), R 1 and Ar 1 The aromatic hydrocarbon group and aromatic heterocyclic group represented by may further have substituents.

[0069] The substituents include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl groups (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.), cycloalkyl groups (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), alkenyl groups (vinyl group, allyl group, etc.), cycloalkenyl groups (2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, etc.), alkynyl groups (ethynyl group, propargyl group, etc.), Aromatic hydrocarbon ring groups (phenyl group, p-tolyl group, naphthyl group, etc.), aromatic heterocyclic groups (2-pyrrole group, 2-furyl group, 2-thienyl group, pyrrole group, imidazolyl group, oxazolyl group, thiazolyl group, benzimidazolyl group, benzoxazolyl group, 2-benzothiazolyl group, pyrazolinone group, pyridyl group, pyridinone group, 2-pyrimidinyl group, triazine group, pyrazole group, 1,2,3-triazole group, 1,2,4-triazole group, oxazole group, isoxazole group, 1,2,4-oxadiazole group, 1,3, 4-Oxadiazole group, thiazole group, isothiazole group, 1,2,4-thiodiazole group, 1,3,4-thiadiazole group, etc.), cyano group, nitro group, alkoxy group (methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group, etc.), aryloxy group (phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group, etc.), acyloxy group (formyloxy group, acetyloxy group) Xy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group, etc.), amino group (amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilinino group, diphenylamino group, etc.), acylamino group (formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, etc.), alkyl and arylsulfonylamino groups (methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,Examples include 5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, etc., alkylthio groups (methylthio group, ethylthio group, n-hexadecylthio group, etc.), arylthio groups (phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group, etc.), sulfamoyl groups (N-ethylsulfamoyl group, N-(3-dodecyloxypropyl)sulfamoyl group, N,N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N-(N'phenylcarbamoyl)sulfamoyl group, etc.), sulfo groups, acyl groups (acetyl group, pivaloyl group, benzoyl group, etc.), and carbamoyl groups (carbamoyl group, N-methylcarbamoyl group, N,N-dimethylcarbamoyl group, N,N-di-n-octylcarbamoyl group, N-(methylsulfonyl)carbamoyl group, etc.).

[0070] In particular, the substituent is preferably a halogen atom, an alkyl group, an acyl group, an acyloxy group, an acylamino group, an alkoxy group, or an aryloxy group.

[0071] From the viewpoint of solubility, the substituent is more preferably an alkyl group, an acyl group, an alkoxy group, or an aryloxy group.

[0072] In general formula (3), R 1 Tertiary alkyl groups and R represented by 2 The C1 to C6 alkyl group represented by may further have substituents. Examples of substituents include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.).

[0073] The following are specific examples of β-diketone derivatives having the structure represented by general formula (3). However, the β-diketone derivatives having the structure represented by general formula (3) are not limited in any way by the following examples. Furthermore, the β-diketone derivatives may also be tautomers thereof, and may form hydrates, solvates, or salts.

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] <Method for producing β-diketone derivatives> Next, a method for producing β-diketone derivatives having the structure represented by general formula (3) will be described.

[0082] The manufacturing method of this embodiment involves reacting a ketone compound having the structure represented by the following general formula (1), which is a reaction raw material, with a carboxylic acid ester compound having the structure represented by the following general formula (2), under a base and reduced pressure. Specifically, the manufacturing method of this embodiment includes a reaction step of producing a compound having the structure represented by the general formula (3), and a removal step of removing the produced compound having the structure represented by the general formula (3) from the reaction solution.

[0083] [ka]

[0084] R in general formula (1) 1 and R 2 This is R in general formula (3). 1 and R 2 It is synonymous with [the above].

[0085] From the viewpoint of usefulness and high yield, compounds having the structure represented by general formula (1) are preferably compounds having the structure represented by the following general formula (1a). In the following general formula (1a), R in general formula (1) 1 This is a phenyl group that may be substituted.

[0086] [ka]

[0087] R in general formula (1a) 2 This is R in general formula (1). 2 This is equivalent to: In general formula (1a), X 1 represents a substituent, m 1 X represents an integer from 0 to 5. 1 The substituents represented by the above-mentioned R 1 and Ar 1 Examples include the same substituents as those found in aromatic hydrocarbon groups and aromatic heterocyclic groups represented by . 1 The substituents may all be the same or all be different.

[0088] [ka]

[0089] Ar in general formula (2) 1 This is Ar in general formula (3). 1 This is synonymous with R. 3 and R 4Each of these independently represents an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include the methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group. n represents an integer from 0 to 2. When n is 2, two R 3 They may be the same or different.

[0090] From the viewpoint of usefulness and high yield, compounds having the structure represented by general formula (2) are preferably compounds having the structure represented by the following general formula (2a). In the following general formula (2a), Ar in general formula (2) 1 This is a phenyl group that may be substituted.

[0091] [ka]

[0092] R in general formula (2a) 3 and R 4 This is R in general formula (2). 3 and R 4 These are synonymous. In general formula (2a), X 2 represents a substituent, m 2 X represents an integer from 0 to 4. 2 The substituents represented by the above-mentioned R 1 and Ar 1 Examples include the same substituents as those found in aromatic hydrocarbon groups and aromatic heterocyclic groups represented by . 2 The substituents may all be the same or all be different.

[0093] The following are specific examples of ketone compounds having the structure represented by general formula (1). However, the ketone compounds having the structure represented by general formula (1) are not limited in any way by the following examples.

[0094] [ka]

[0095] [ka]

[0096] The following are specific examples of carboxylic acid ester compounds having the structure represented by general formula (2). However, the carboxylic acid ester compounds having the structure represented by general formula (2) are not limited in any way by the following examples.

[0097] [ka]

[0098] [ka]

[0099] <Reaction Process> In the reaction step, a ketone compound having the structure represented by general formula (1) and a carboxylic acid ester compound having the structure represented by general formula (2) are reacted in the presence of a base under reduced pressure of 15 kPa or less.

[0100] (Depressurization conditions) In this embodiment, by carrying out the reaction under reduced pressure, the alcohol evaporates at a relatively low temperature, and the evaporated alcohol is discharged from the reaction system. Specifically, the pressure during the reaction is preferably in the range of 0.1 to 10 kPa, and more preferably in the range of 0.3 to 3 kPa.

[0101] When the reaction is carried out under a pressure of 0.1 kPa or higher, especially 0.3 kPa or higher, the generated alcohol evaporates while the evaporation and distillation of the solvent used is suppressed. Furthermore, when the reaction is carried out under a pressure of 15 kPa or lower, especially 10 kPa or lower, and even 3 kPa or lower, the decrease in the evaporation efficiency of the alcohol can be suppressed.

[0102] (Dehydrating agent) In this embodiment, "dehydrating agent" refers to a substance that is highly hygroscopic or a substance that readily reacts chemically with water. By reacting in the presence of a dehydrating agent, the water produced by the self-condensation of ketones reacts with the dehydrating agent before the base, thereby suppressing the reaction between the base and water. Many dehydrating agents also readily adsorb alcohol in addition to water, contributing to the removal of alcohol as well.

[0103] The dehydrating agent is not particularly limited, but organic compounds are preferred.

[0104] Examples of organic compounds include carbonate esters (dimethyl carbonate, trimethyl carbonate, triethyl carbonate, etc.), phosphate esters (triethyl phosphate), phosphite esters (trimethyl phosphite), alkoxysilanes, titanate esters (tetrabutoxytitanium), alkoxy compounds (methyl orthoformate, ethyl orthoformate, dimethoxypropane, etc.), aliphatic monoisocyanates (methyl isocyanate, ethyl isocyanate, propyl isocyanate, etc.), aromatic monoisocyanates (p-toluenesulfonyl isocyanate), aliphatic acid anhydrides (acetic anhydride, etc.), aromatic acid anhydrides (benzoic anhydride, etc.), and the like. These can be used individually or in combination of two or more types.

[0105] From the viewpoint of dehydration capacity and stability, the dehydrating agent is preferably a carbonate ester, a phosphite ester, an alkoxysilane, or a titanate ester, and among these, alkoxysilane is more preferred.

[0106] The alkoxysilane preferably has a structure represented by the following general formula (4).

[0107] [ka]

[0108] In general formula (4), R 5 This represents an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include the methyl group, ethyl group, propyl group, and butyl group.

[0109] In general formula (4), R 6 This represents an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups.

[0110] Examples of alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, hexenyl, and cyclohexenyl groups. Examples of aryl groups include phenyl, tolyl, and xylyl groups. Examples of aralkyl groups include benzyl, phenethyl, phenylpropyl, phenylbutyl, phenylpentyl, and naphthylmethyl groups.

[0111] In general formula (4), p represents an integer from 0 to 3. 6 These may all be the same or different. 4-n R 5 They may all be the same or they may all be different.

[0112] The following are specific examples of alkoxysilanes having the structure represented by general formula (4). However, the alkoxysilanes having the structure represented by general formula (4) are not limited in any way by the following examples.

[0113] [ka]

[0114] The amount of dehydrating agent used is not particularly limited as long as it is an amount that allows the reaction to proceed. The amount of dehydrating agent used is preferably in the range of 0.05 to 3 times, and more preferably in the range of 0.1 to 1 time, relative to the number of moles of the carboxylic acid ester compound used.

[0115] (base) The base may be an inorganic base or an organic base. Examples of inorganic bases include potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, potassium hydroxide, sodium hydroxide, sodium amide, sodium hydride, and lithium diisopropylamide (LDA).

[0116] Examples of organic bases include sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, sodium butoxide, potassium butoxide, diisopropylethylamine, N,N'-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, N-methylmorpholine, imidazole, N-methylimidazole, pyridine, and lithium diisopropylamide. These can be used individually or in combination of two or more.

[0117] In particular, the base is preferably sodium amide, sodium hydride, sodium methoxide, sodium ethoxide, sodium butoxide, or potassium methoxide. Inorganic bases may be added in powder form or dispersed in a solvent. Organic bases may be added dissolved in a solvent. For example, sodium methoxide may be added as a 28% DMF (dimethylformamide) solution.

[0118] From a reactivity standpoint, the pKa of the conjugate acid of a base in water at 25°C is preferably in the range of 15 to 38. A pKa of 15 or higher indicates a higher reactivity than the pKa of the α-hydrogen in many ketone compounds. Furthermore, a pKa of 38 or lower can suppress side reactions. The pKa value of a base in water at 25°C can be measured from electrical conductivity, etc.

[0119] The amount of base used is not particularly limited as long as it is sufficient for the reaction to proceed. Preferably, the amount is in the range of 1.00 to 5.00 times the number of moles of pyrazole rings formed by the reaction, and more preferably in the range of 1.05 to 3.00 times.

[0120] (solvent) The reaction solvent used is not particularly limited as long as the reaction proceeds. Preferably, the solvent is an aprotic organic solvent (such as tetrahydrofuran, acetonitrile, N,N-dimethylacetamide, dimethyl sulfoxide, N,N-dimethylformamide, N-methylformamide, pyridine, N-methyl-2-pyrrolidine, 1,3-dimethyl-2-imidazolidinone, etc.), and more preferably an organic solvent with an organic solvent donor number in the range of 25 to 35 (such as N,N-dimethylacetamide, dimethyl sulfoxide, N,N-dimethylformamide, N-methylformamide, pyridine, N-methyl-2-pyrrolidine, 1,3-dimethyl-2-imidazolidinone, etc.).

[0121] In this embodiment, "donor number" refers to the measure of donority proposed by Gutmann, i.e., the measure of the solvent's Lewis base properties. Specifically, the donor number DN is the enthalpy (-ΔHSbCl5) of the reaction between SbCl5 in 1,2-dichloroethane and the solvent, expressed in kcalmoles. -1 This value is calculated in units and expressed as a dimensionless number.

[0122] Many organic solvents have a similar number of donors, even if it hasn't been reported as a measured value. The donor properties of organic solvents can be inferred to some extent. Donor properties tend to increase as the alkyl group size increases. For example, DN(HOH)=18.0, DN(CH3OH)=19.0, DN(C2H5OH)=20.0, and DN(C3H7OH)=30.0, with the number of donors increasing sequentially with increasing alkyl groups. This can be thought to be because a larger alkyl group results in a greater inductive effect, and the electron density of the hydrogen in the hydroxyl group (-OH) increases, leading to stronger electron-donating properties.

[0123] In this way, by comparing a substance with a known number of donors, we can determine the degree of donor activity in that substance by considering the increase or decrease in electron density in atoms exhibiting donor properties, and measured values ​​such as literature values ​​are not necessarily required.

[0124] Using a solvent with a donor count of 25.0 or more can promote the abstraction of α-hydrogens by the base and nucleophilic reactions. This reduces the concentration of reaction intermediates and suppresses the formation of polymers. Furthermore, using a solvent with a donor count of 35.0 or less can suppress other side reactions and improve the reaction rate. It is more preferable for the solvent donor count to be in the range of 26.0 to 30.0.

[0125] The method of adding the raw materials, dehydrating agent, base, and solvent used in the reaction is not particularly limited. For example, the ketone compound and the carboxylic acid ester compound may be dispersed or dissolved in the solvent, and the dehydrating agent and base may be added to each. Then, the solutions of the ketone compound and the carboxylic acid ester compound may be mixed and reacted. If the dehydrating agent is not added, only the base may be added.

[0126] Furthermore, from the standpoint of worker safety, a method may be used in which the ketone compound and carboxylic acid ester compound are dispersed or dissolved in a solvent, and a dehydrating agent and a base are added to this solution in small amounts to carry out the reaction. If a dehydrating agent is not added, only the base is added. This method can suppress a rapid increase in reaction heat and improve the reaction rate.

[0127] The solution temperature during the reaction is not limited as long as it is within the temperature at which the reaction proceeds. From the viewpoint of productivity, the reaction temperature is preferably in the range of -20 to 100°C, more preferably in the range of -15 to 70°C, and even more preferably in the range of -10 to 20°C.

[0128] The reaction is preferably carried out under an inert atmosphere, and more preferably under a nitrogen or argon atmosphere. The flow rate of the inert gas when carrying out the reaction under an inert atmosphere is not particularly limited and may be adjusted as appropriate according to the required reaction equipment.

[0129] The completion of the reaction can be determined by the disappearance of the peaks of the ketone compound, carboxylic acid ester compound, or reaction intermediate used as a starting material, using a general analytical instrument used by those skilled in the art to confirm the progress of the reaction, such as HPLC (high-performance liquid chromatography).

[0130] <Removal process> After the reaction is complete, the β-diketone derivative having the structure represented by general formula (3) is removed from the reaction solution.

[0131] Methods for extracting β-diketone derivatives include recrystallization, crystallization, reprecipitation, and column chromatography. Among these, recrystallization, crystallization, or reprecipitation is preferred from the viewpoint of mass production.

[0132] The method for treating the reaction solution is not particularly limited, but from the viewpoint of using a base, a method of neutralizing the reaction solution by adding an acid is preferred. Examples of acids used for neutralization include hydrochloric acid, sulfuric acid, nitric acid, and acetic acid, with acetic acid being preferred. The amount of acid used for neutralization is not particularly limited, as long as the pH of the reaction solution is within the range of 1 to 9. The amount of acid is preferably in the range of 0.1 to 3.0 times, and more preferably in the range of 0.2 to 1.5 times, the number of moles of base used.

[0133] When extracting the reaction solution using a suitable organic solvent, it is preferable to wash the organic solvent with water after extraction and then concentrate the solution. Examples of organic solvents include ethyl acetate, toluene, dichloromethane, tetrahydrofuran, and diethyl ether. Alternatively, a mixed solvent may be obtained by mixing these organic solvents with tetrahydrofuran or an alcohol-based solvent. Among these, ethyl acetate, toluene, or tetrahydrofuran are preferred as the organic solvent.

[0134] The method for crystallizing the β-diketone derivative is not particularly limited. A preferred method is to add water to the neutralized reaction solution and crystallize it, or to neutralize the solution in which the β-diketone derivative is dissolved and then crystallize it.

[0135] To improve the yield, it is also preferable to add water to precipitate crystals.

[0136] The amount of water added is not particularly limited. Preferably, the amount of water added is in the range of 0.5 to 1 times the mass of the solvent used in the reaction, and more preferably in the range of 0.6 to 0.8 times.

[0137] The following method is most preferred for extracting the β-diketone derivative: Cool the reaction solution to a temperature of 0 to 10°C. Then, add an acid to the reaction solution in an amount of 1.0 to 1.2 times the number of moles of the base used in the reaction to neutralize the base and adjust the reaction solution to an acidic to neutral pH. Adjust the concentration of the adjusted reaction solution by vacuum distillation or solvent addition and allow crystallization.

[0138] During the removal process, there is a high probability that the worker will come into contact with the reaction solution or crystallization solution, but this method allows the worker to perform the operation relatively safely.

[0139] The crude product obtained by isolating the β-diketone derivative from the reaction solution may be purified to improve its purity. Purification methods include recrystallization, suspension purification, and column chromatography. Of these, from the viewpoint of productivity, recrystallization or suspension purification are preferred.

[0140] The solvents that can be used in the recrystallization method and the suspension purification method are not particularly limited, and include alcoholic solvents, etheric solvents, acetone, ethyl acetate, toluene, heptane, N,N-dimethylformamide, and the like.

[0141] For example, compound (3)-11 can be produced using compound (1)-1 as the ketone compound and compound (2)-11 as the carboxylic acid ester compound.

[0142] [ka]

[0143] <How to use β-diketone derivatives> β-diketone derivatives having the structure represented by general formula (3) can be used as various reaction intermediates, and are particularly preferred as precursors for pyrazole derivatives or as raw materials for metal complexes.

[0144] <Pyrazole derivatives> Pyrazole derivatives can be synthesized using β-diketone derivatives having the structure represented by general formula (3) as precursors.

[0145] The following are specific examples of pyrazole derivatives, but pyrazole derivatives are not limited in any way to these examples.

[0146] [ka]

[0147] <Method for producing pyrazole derivatives> By reacting the β-diketone derivative produced by the above manufacturing method with hydrazine, a pyrazole derivative having the structure represented by the following general formula (5) can be produced. This pyrazole derivative has two pyrazole rings.

[0148] [ka]

[0149] Ar in general formula (5) 1 This is Ar in general formula (3). 1 This is equivalent to the following: However, Ar in general formula (5) 1 R is a divalent linking group. 1 This is R in general formula (3). 1 It is synonymous with [the above].

[0150] The β-diketone derivative may be reacted with hydrazine as is in the reaction solution obtained by the above reaction step. The β-diketone derivative may be reacted with hydrazine after being removed as crude crystals by the above extraction step. The β-diketone derivative may be reacted with hydrazine after being purified by means of recrystallization, suspension purification, etc. The concentration of hydrazine used is preferably in the range of 40 to 80% by mass, and more preferably in the range of 50 to 60% by mass.

[0151] The solvents that can be used in the production of pyrazole derivatives are not particularly limited, but aprotic polar organic solvents or alcoholic solvents are preferred. Among alcoholic solvents, methanol, ethanol, isopropyl alcohol, or butanol are more preferred, and isopropyl alcohol is even more preferred. Among aprotic polar organic solvents, acetonitrile, N,N-dimethylacetamide, N,N-dimethylformamide, or N-methyl-2-pyrrolidine are more preferred, and among these, N,N-dimethylformamide is even more preferred.

[0152] The amount of solvent used is not particularly limited. The amount of solvent used is preferably in the range of 0.5 to 30.0 times, more preferably in the range of 1.0 to 25.0 times, and even more preferably in the range of 3.0 to 20 times, relative to the mass of the compound having the structure represented by general formula (3).

[0153] The amount of hydrazide used is not particularly limited, as long as it is sufficient for the reaction to proceed. It is preferably in the range of 1.00 to 5.00 times the number of moles of pyrazole rings formed, and more preferably in the range of 1.05 to 3.00 times.

[0154] The method of adding the β-diketone derivative, solvent, and hydrazine used in the reaction is not particularly limited. The β-diketone derivative may be added last.

[0155] Alternatively, the β-diketone derivative may be dispersed or dissolved in a solvent and then hydrazine may be added. In particular, from the viewpoint of safety, it is preferable to disperse or dissolve the β-diketone derivative in a solvent, dilute it with water to a concentration in the range of 40 to 80% by mass, and then add the hydrazine in small amounts. This method can suppress the temperature rise caused by the rapid progress of the reaction.

[0156] The temperature of the solution during the reaction is not particularly limited as long as it is within the temperature at which the reaction proceeds. The reaction temperature is preferably in the range of 20 to 100°C, more preferably in the range of 40 to 90°C, and even more preferably in the range of 50 to 80°C.

[0157] The reaction is preferably carried out under an inert atmosphere, and more preferably under a nitrogen or argon atmosphere.

[0158] The method for treating the reaction solution is not particularly limited, but from the viewpoint of productivity and purity, it is preferable to crystallize it under basic conditions and filter it. When neutralizing the reaction solution by adding an acid, examples of acids that can be used for neutralization include hydrochloric acid, sulfuric acid, nitric acid, and acetic acid, with acetic acid being the most preferred. The amount of acid used for neutralization is not particularly limited, as long as the pH of the reaction solution is within the range of 1 to 9. The amount of acid is preferably in the range of 0.1 to 3.0 times the number of moles of base used, and more preferably in the range of 0.2 to 1.5 times.

[0159] When extracting the reaction solution using a suitable organic solvent, it is preferable to wash the organic solvent with water after extraction and then concentrate the solution. Examples of organic solvents include ethyl acetate, toluene, dichloromethane, tetrahydrofuran, and diethyl ether. Alternatively, a mixed solvent may be obtained by mixing these organic solvents with tetrahydrofuran or an alcohol-based solvent. Among these, ethyl acetate or tetrahydrofuran are preferred as the organic solvent.

[0160] When pyrazole derivatives are synthesized using β-diketone derivatives, structural isomers with different -NH- positions on the pyrazole ring may be produced. In this embodiment, structural isomers may be formed, and the product may be a mixture of structural isomers.

[0161] 1) Example of production of pyrazole derivative PY-2 For example, the pyrazole derivative PY-2 can be synthesized by the following scheme.

[0162] [ka]

[0163] Compound (3)-11 (100 g) synthesized by the above manufacturing method is dissolved in N,N-dimethylformamide (130 mL), and the resulting solution is heated to approximately 50°C. Hydrazine monohydrate (36.5 g) is added dropwise to the heated solution, and after the addition is complete, the solution is stirred at approximately 60°C for 1 hour to allow the reaction to proceed. After the reaction is complete, the resulting reaction solution is added to a mixture of isopropyl alcohol (50 mL) and water (100 mL) at a temperature of 30-40°C. After the addition is complete, the precipitated crystals are filtered off. The filtered crystals are washed with a mixture of water and ethanol, and the washed crystals are dried under reduced pressure. In this manufacturing example, 92.5 g of pyrazole derivative PY-2 was obtained. The yield was 94.5%, and the purity was 99.0%.

[0164] <How to use pyrazole derivatives> Pyrazole derivatives using β-diketone derivatives as precursors can be used in pharmaceuticals, electronic materials, resin additives, and the like.

[0165] Preferred uses of pyrazole derivatives include electronic materials or resin additives. For use as electronic materials, the compound may be used by vapor deposition or coating, or by adding it to a resin.

[0166] <Phase difference film> The pyrazole derivative is preferably contained in the retardation film as an additive. Thereby, it is possible to suppress fluctuations in the retardation value of the retardation film due to fluctuations in humidity. As a result, in a display device or the like including the retardation film, it is possible to suppress a decrease in contrast, the occurrence of color unevenness, and the like. Further, the pyrazole derivative also functions as a retardation increasing agent that increases the retardation of the retardation film. The pyrazole derivative may be used alone or in combination of two or more kinds.

[0167] The content of the pyrazole derivative is not particularly limited, but is preferably in the range of 0.5 to 10% by mass, more preferably in the range of 0.5 to 5% by mass, based on the total mass of the retardation film. By being within the above range, fluctuations in the retardation value due to fluctuations in humidity can be sufficiently suppressed.

[0168] The retardation film contains a compound having a structure represented by the following general formula (6). The content of the compound having a structure represented by the general formula (6) is in the range of 0.0001 to 0.1 parts by mass when the total amount of the resin in the retardation film is 100 parts by mass. By the content being 0.0001 part by mass or more, it is possible to suppress the occurrence of blocking even when the retardation film is wound into a roll and stored and then pulled out from the roll. By the content being 0.1 part by mass or less, it is possible to suppress bleeding out of the compound having a structure represented by the general formula (6) and to reduce the internal haze.

[0169]

Chemical formula

[0170] In the formula, R 7 represents an alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 10 carbon atoms. X 3 , X 4 and X 5 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a group represented by -Si-R 8 (O-X 6 )2. R 8represents an alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 10 carbon atoms. X 6 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -Si-R 8 (O-X 6 )2.

[0171] R 7 and R 8 Specific examples of the alkyl group, alkenyl group, aryl group and aralkyl group having 1 to 10 carbon atoms represented by are the same as those of the alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 10 carbon atoms represented by the aforementioned R 6 . Specific examples of the alkyl group having 1 to 4 carbon atoms represented by X 3 ~X 6 include a methyl group, an ethyl group, a propyl group and a butyl group.

[0172] Specific examples of the compound having the structure represented by the general formula (6) are shown below, but the compound is not limited by the following specific examples.

[0173]

Chemical formula

[0174]

Chemical formula

[0175]

Chemical formula

[0176] Compounds having the structure represented by general formula (6) can also be produced by hydrolysis and condensation reactions in alkoxysilanes having the structure represented by general formula (4). Therefore, first, a β-diketone derivative having the structure represented by general formula (3) is produced using an alkoxysilane having the structure represented by general formula (4) as a dehydrating agent by the aforementioned production method. Next, a pyrazole derivative having the structure represented by general formula (5) is produced using the obtained β-diketone derivative, and the obtained pyrazole derivative is incorporated into a phase difference film. This allows for the incorporation of an appropriate amount of compound having the structure represented by general formula (6) into the phase difference film.

[0177] For example, compound (5)-2 is produced by the hydrolysis and condensation reaction of two molecules of compound (4)-1. Also, compound (5)-3 is produced by the hydrolysis and condensation reaction of three molecules of compound (4)-1. Even when the same compound (4)-1 is used as the alkoxysilane, the molecular weight (structure) and amount of the compound having the structure represented by general formula (5) produced will differ depending on the manufacturing conditions in the method for producing the β-diketone derivative and the method for producing the pyrazole derivative.

[0178] In a phase difference film, the compound having the structure represented by general formula (6) may be used alone or in combination of two or more compounds.

[0179] The resin used as the main component in the phase difference film is not particularly limited. Examples of resins include cellulose ester, acrylic resin, carbonate resin, and cycloolefin resin. Among these, cellulose ester is preferred as the resin because it can more effectively suppress fluctuations in the phase difference due to changes in humidity. The resin may be used alone or in combination of two or more types.

[0180] Examples of cellulose esters include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose propionate, and cellulose butyrate. These may be used individually or in combination of two or more.

[0181] The resin content is not particularly limited, but it is preferably in the range of 60 to 95% by mass relative to the total mass of the phase difference film.

[0182] In this embodiment, when the total amount of resin is 100 parts by mass, the content of the compound having the structure represented by general formula (6) is in the range of 0.0001 to 0.1 parts by mass. When the phase difference film contains multiple types of resin, "total amount of resin" refers to the total amount of multiple types of resin.

[0183] The phase difference film may further contain other additives. Examples of other additives include organic esters, phosphate esters, glycolic acid esters, UV absorbers, antioxidants, matting agents (fine particles), and phase difference control agents. Examples of organic esters include sugar esters, polycondensation esters, and polyhydric alcohol esters. Known additives may be used.

[0184] The phase difference film preferably has an equilibrium moisture content of 4% or less, and more preferably 3% or less, at 25°C and 60% relative humidity. An equilibrium moisture content of 4% or less makes it easier to adapt to humidity changes, and the optical properties and dimensions are less likely to change. The equilibrium moisture content can be measured by the following method: Leave the sample film in a room conditioned to 23°C and 20% RH for 4 hours or more, and then leave it in a room conditioned to 23°C and 80% RH for 24 hours. After that, the sample film is dried and vaporized at a temperature of 150°C using a trace moisture meter, and then quantified by the Karl Fischer method. As a trace moisture meter, for example, the "CA-20 model" (manufactured by Mitsubishi Chemical Corporation) can be used.

[0185] (Method of manufacturing phase difference film) The method for manufacturing a phase difference film is not particularly limited, and known manufacturing methods can be used. Examples of methods for manufacturing a phase difference film include the inflation method, T-die method, calendering method, cutting method, casting method, emulsion method, and hot pressing method. Among these, solution casting or molten casting is preferred from the viewpoint of suppressing discoloration, foreign matter defects, optical defects, etc. In particular, solution casting makes it easier to obtain a uniform and smooth film surface.

[0186] The method for adding the compound having the structure represented by general formula (6) is not particularly limited. A pyrazole derivative may be produced by the manufacturing method described above, and the compound having the structure represented by general formula (6) may be added by incorporating the obtained pyrazole derivative into the phase difference film. Alternatively, the pyrazole derivative and the compound having the structure represented by general formula (6) may be added to the phase difference film separately.

[0187] In the molten casting method, first, molten pellets containing resin are prepared. Next, the molten pellets and additives such as pyrazole derivatives are melt-kneaded together and then extruded through a die into a web. The extruded web is cooled and solidified to form a film. After stretching the film, it is wound up.

[0188] In the solution casting method, first, a resin and additives such as pyrazole derivatives are dissolved in a solvent to prepare a dope (preparation step). Next, the prepared dope is cast onto a belt-shaped or drum-shaped metal support (casting step). The cast dope is dried as a web (solvent evaporation step), and the dried web is peeled from the metal support to form a film (peeling step). After stretching the film (stretching step), it is wound up (winding step). The details of the solution casting method will be explained below.

[0189] In the preparation process, a resin and additives such as pyrazole derivatives are added to an organic solvent mainly composed of a good solvent for the resin, and dissolved with stirring to prepare a dope. Alternatively, a resin solution and an additive solution in which additives such as pyrazole derivatives are dissolved are mixed to prepare a dope. The organic solvent used for preparing the dope is not particularly limited as long as it can dissolve the resin and additives such as pyrazole derivatives simultaneously.

[0190] In the casting process, first, the prepared dope is passed through a feed pump and fed to a pressure die. Next, the dope is cast from the pressure die slit at the casting position on an endless metal support that is infinitely transferred. The dope film formed on the metal support is also referred to as a web.

[0191] The surface temperature of the metal support is preferably within the range of -50°C or higher and not higher than the temperature at which the solvent boils and foams. By raising the surface temperature to a certain extent, the drying rate of the web can be increased, and by not raising it too high, it is possible to suppress the web from foaming or the flatness of the web from deteriorating. Also, the web may be gelled by cooling the metal support and peeled off from the metal support with a large amount of residual solvent. Specifically, the surface temperature of the metal support is more preferably within the range of 0 to 100°C, and even more preferably within the range of 5 to 30°C.

[0192] The method for controlling the temperature of the metal support is not particularly limited. Examples of the method for controlling the temperature include a method of blowing warm air or cold air, a method of bringing warm water into contact with the back side of the metal support, etc. Among them, the method using warm water is preferable because heat transfer is efficiently performed and the time until the temperature of the metal support becomes constant is short. [[ID = 13]] [[ID = 14]]

[0193] [[ID = 15]] In the solvent evaporation step, the web is heated on a metal support to evaporate the solvent. The method of evaporating the solvent is not particularly limited. Examples of the method of evaporating the solvent include a method of blowing air from the web side, a method of transferring heat by a liquid from the back surface of the metal support, a method of transferring heat from the front and back by radiant heat, etc. Among them, from the viewpoint of good drying efficiency, a method of transferring heat by a liquid from the back surface of the metal support is preferable.

[0194] In the peeling step, the web with the solvent evaporated on the metal support is peeled at the peeling position. The residual solvent amount of the web at the time of peeling is preferably adjusted within the range of 50 to 120% by mass depending on the strength of the drying conditions, the length of the metal support, etc. The peeling tension is preferably 190 N / m or less from the viewpoint of being difficult to wrinkle during peeling.

[0195] A drying step may be provided between the peeling step and the stretching step. The drying step may be divided into a preliminary drying step and a main drying step. The web may be dried while being conveyed by a number of rollers arranged vertically, or may be dried while being conveyed with both ends of the web fixed by clips. The means for drying the web is not particularly limited. Examples of the means for drying include hot air, infrared rays, heating rollers, microwaves, etc.

[0196] The drying temperature is preferably within the range of 100°C or higher and the glass transition temperature of the web - 5°C or lower, and the drying time is preferably within the range of 10 to 60 minutes. The drying temperature is preferably within the range of 100 to 200°C, and more preferably within the range of 110 to 160°C.

[0197] In the stretching step, it is preferable to stretch the web in the MD direction and the TD direction. Note that the stretching may be only in either the MD direction or the TD direction. Among them, it is preferable to stretch in the TD direction by a tenter stretching device. The stretching may be uniaxial stretching or biaxial stretching. In biaxial stretching, it may be stretched in one direction and the tension in the other direction may be relaxed and contracted.

[0198] When the glass transition temperature of the web is denoted as Tg, the temperature during stretching is preferably within the range of (Tg+15) to (Tg+50)°C. Being within this range makes it easier to adjust the retardation value. Furthermore, it allows for a reduction in stretching stress, thus lowering haze. Additionally, it suppresses the occurrence of breakage, resulting in superior film flatness and coloration.

[0199] Here, "glass transition temperature Tg" refers to the intermediate glass transition temperature (Tmg) determined in accordance with JIS K7121 (1987) by measuring it at a heating rate of 20°C / min using a commercially available differential scanning calorimeter. The glass transition temperature Tg can be measured, for example, using a differential scanning calorimeter "DSC220" (manufactured by Seiko Instruments Inc.) in accordance with JIS K7121 (1987).

[0200] The stretching ratio is preferably at least 1.1 times in the TD direction. More preferably, the stretching ratio is within the range of 1.1 to 1.5 times, and even more preferably within the range of 1.1 to 1.3 times. Within this range, the movement of molecules in the web is large, and the desired retardation value can be obtained. In addition, the behavior of the web's dimensional change can be controlled within the desired range.

[0201] Stretching is preferably performed in the MD direction when the residual solvent content of the web is 40% by mass or more, and preferably in the TD direction when it is less than 40% by mass. Since the web after the aforementioned peeling process has a large amount of residual solvent, it can be stretched in the MD direction with a tension similar to that of the peeling tension. As the web dries and the amount of residual solvent decreases, the stretching rate in the MD direction decreases. The stretching ratio in the MD direction can be calculated from the rotation speed on the metal support and the operating speed of the tenter.

[0202] Methods for stretching in the TD direction include the entire drying process described in Japanese Patent Publication No. 62-46625, or a method of drying while holding both ends of the web in the width direction with clips or pins in the TD direction (width direction) (tenter method). Among these, the tenter method is preferred.

[0203] In the winding process, the web is wound as a film after the amount of residual solvent in the web is 2% by mass or less. From the viewpoint of dimensional stability, it is more preferable to wind the web after the amount of residual solvent is 0.4% by mass or less. The winding method is not particularly limited. Examples of winding methods include the constant torque method, constant tension method, tapered tension method, and programmed tension control method with constant internal stress.

[0204] (Retardation value) Phase difference films inevitably exhibit retardation upon stretching. The in-plane retardation value Ro and the retardation value Rt in the thickness direction are obtained from the refractive index n in the following measurement. x , n y and n z It can be calculated from this. The measurement is performed using an automated birefringent AxoScan Mueller Matrix Polarimeter (manufactured by Axometrics Co., Ltd.) to measure the three-dimensional refractive index at a wavelength of 590 nm in an environment of 23°C and 55% RH.

[0205] The phase difference film preferably has an in-plane retardation value Ro defined by the following formula (i) in the range of 40 to 70 nm. Furthermore, the thickness-direction retardation value Rt defined by the following formula (ii) is preferably in the range of 100 to 300 nm. This improves visibility in VA-mode liquid crystal displays. The retardation value of the phase difference film can be adjusted by stretching it while adjusting the stretching ratio in the TD direction (lateral direction).

[0206] Equation (i): Ro = (n x -n y ) × d (nm) Equation (ii): Rt = {(n x +n y ) / 2-n z} × d(nm) [In equations (i) and (ii), n x This represents the refractive index in the direction x where the refractive index is maximum in the in-plane direction of the film. yThis represents the refractive index in the direction y perpendicular to direction x in the in-plane direction of the film. z represents the refractive index in the film thickness direction z. d represents the film thickness (nm).

[0207] <Polarizing plate> The phase difference film is preferably provided on the polarizer. Specifically, the phase difference film is preferably bonded to at least one side of the polarizer using water-based adhesive or an active energy ray-curable adhesive.

[0208] Figure 1 shows an example of the configuration of a polarizing plate having a phase difference film. The polarizing plate 51 has, in order from the viewing side, a protective film 52, a polarizer 53, and a phase difference film 54. Note that the configuration of the polarizing plate is not limited to this and may have other films as well. Known films can be used for the protective film 52 and the polarizer 53. [Examples]

[0209] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, the units "parts" or "%" are used, and unless otherwise specified, they represent "parts by mass" or "mass%". Furthermore, in the following examples, the operations were carried out at room temperature (25°C) unless otherwise specified.

[0210] 1. Production of β-diketone derivatives <Example-1> In Example 1, acetophenone (compound (1)-1) was used as the ketone compound, and dimethyl isophthalate (compound (2)-11) was used as the carboxylic acid ester compound. 1,3-bis(3-phenyl-3-oxopropanoyl)benzene (compound (3)-11) was synthesized as the β-diketone derivative at 1.5 kPa. Sodium methoxide and potassium methoxide were used as bases, and triethoxypropylsilane (compound (4)-1) was used as the dehydrating agent. Dehydrated DMF (dimethylformamide) was used as the solvent, and the amount of water in the solvent was kept to a minimum.

[0211] [Chemistry]

[0212] Dimethyl isophthalate (22 g, 113 mmol), sodium methoxide (3.0 g, 55.6 mmol), and potassium methoxide (15.8 g, 226 mmol) were added to a 500 mL flask in the reactor, and an argon atmosphere was maintained. Subsequently, dehydrated DMF (65 mL) and triethoxypropylsilane (5.2 mL, 22.6 mmol) were added to the flask. The reactor was cooled to 0 °C and stirred at a rotational speed of 200 rpm using a mechanical stirrer.

[0213] Acetophenone (33 mL, 283 mmol) was added dropwise to the flask over 10 minutes. Subsequently, the reactor was removed from the cooling bath and the reaction temperature was raised to room temperature. A diaphragm pump was connected to the reactor, and the system was evacuated to 1.5 kPa and stirred for 24 hours. After completion of the reaction, the vacuum in the system was released, and the reactor was cooled to 0 °C. Aqueous acetic acid was added to the flask for neutralization, and toluene (60 mL) was added to the flask and stirred for 15 minutes. Subsequently, the reactor was heated to raise the reaction temperature to 70 °C and stirred for 30 minutes. After allowing the reactor to cool to room temperature, the aqueous layer in the flask was removed.

[0214] Subsequently, acetone (25 mL) was added to the flask, the reactor was heated to raise the reaction temperature to 60 °C, and stirred for 2 hours. After allowing the reactor to cool to room temperature, the solid was recovered by suction filtration and returned to the flask. Toluene (40 mL) and acetone (15 mL) were added to the flask. The reactor was heated and stirred at a reaction temperature of 50 °C for 30 minutes. After allowing the reactor to cool to room temperature, the solid was recovered by suction filtration and returned to the flask.

[0215] Acetone (25 mL) and water (60 mL) were added to a flask. The reactor was heated and stirred at a reaction temperature of 50°C for 30 minutes. After the reactor was allowed to cool to room temperature, the solid was recovered by suction filtration and returned to the flask. Acetone (25 mL) and water (60 mL) were added to a flask. The reactor was heated and stirred at a reaction temperature of 50°C for 30 minutes. After the reactor was allowed to cool to room temperature, the solid was recovered by suction filtration and returned to the flask.

[0216] Water (175 mL) was added to the flask. The reactor was heated and stirred at a reaction temperature of 50°C for 30 minutes. After the reactor was allowed to cool to room temperature, the solid was recovered by suction filtration and returned to the flask. Acetone (20 mL) and water (100 mL) were added to the flask. The reactor was heated and stirred at a reaction temperature of 50°C for 30 minutes. The solid was recovered by suction filtration, and the recovered solid was dried in a sample dryer at 80°C and 0.10 kPa for 8 hours. This yielded 1,3-bis(3-phenyl-3-oxopropanoyl)benzene as a pale yellow solid (34.3 g). The yield was 82%.

[0217] Furthermore, nuclear magnetic resonance analysis of the obtained pale yellow solid, i.e. 1 The results of the 1H NMR (400MHz, CDCl3) were as follows: δ: 8.58 (1H,t,J=1.6Hz), 8.44 (2H,dd,J=1.8Hz,7.8Hz), 8.23-8.21 (4H,m), 7.78 (1H,t,J=7.8Hz), 7.71-7.66 (2H,m), 7.62-7.58 (4H,m), 7.48 (1H,s).

[0218] <Comparative Examples 1-2 and Example 2> In Comparative Examples 1 and 2 and Example 2, acetophenone (compound (1)-1) was used as the ketone compound, and dimethyl isophthalate (compound (2)-11) was used as the carboxylic acid ester compound. 1,3-bis(3-phenyl-3-oxopropanoyl)benzene (compound (3)-11) was synthesized as the β-diketone derivative. Sodium methoxide and potassium methoxide were used as bases. Unlike Example 2, the reactions in Comparative Examples 1 and 2 were carried out at atmospheric pressure.

[0219] Dimethyl isophthalate (2.2 g, 11.3 mmol) and sodium methoxide (1.49 g, 27.5 mmol) were added to a 100 mL flask in the reactor, and the mixture was kept under an argon atmosphere. Next, the solvents shown in Table I below were added to the flask, the mixture was cooled to 0°C, and stirred. Acetophenone (2.62 mL, 22.6 mmol) was added dropwise to the flask over 10 minutes, and the reactor was removed from the cooling bath. The pressure inside the reactor was adjusted to the degree shown in Table I below, the reaction temperature was raised, and the mixture was stirred for 24 hours. After the reaction was complete, the reactor was cooled to 0°C. Acetic acid (2.0 mL, 35 mmol) and water (50 mL) were added to the flask, and the product was extracted with methylene chloride (200 mL). An internal standard was added to the organic layer containing the product, and the yield was determined by the internal standard method.

[0220] The solvent, temperature, and yield results for Comparative Examples 1-2 and Examples 1-2 are shown in Table I below. In Table I, DMF represents dimethylformamide and THF represents tetrahydrofuran. The "DMF" in Table I differs from dehydrated DMF in that it contained trace amounts of water. "NMR yield" refers to the yield obtained from nuclear magnetic resonance analysis, i.e. 1 The yield was calculated using the internal standard method based on the results of 1H NMR (400 MHz, CDCl3).

[0221] [Table 1]

[0222] <Examples 3-9> In Examples 3 to 9, acetophenone (compound (1)-1) was used as the ketone compound, and dimethyl isophthalate (compound (2)-11) was used as the carboxylic acid ester compound. 1,3-bis(3-phenyl-3-oxopropanoyl)benzene (compound (3)-11) was synthesized as the β-diketone derivative. Sodium methoxide and potassium methoxide were used as the bases. In Examples 3 to 9, the type or amount of dehydrating agent used was changed.

[0223] Dimethyl isophthalate (2.2 g, 11.3 mmol) and sodium methoxide (1.49 g, 27.5 mmol) were added to a 100 mL flask in the reactor, and the reaction was carried out under an argon atmosphere. Next, anhydrous DMF (6.5 mL) and a dehydrating agent (2.26 mmol) were added to the flask, the mixture was cooled to 0°C, and stirred. Acetophenone (2.62 mL, 22.6 mmol) was added dropwise to the flask over 10 minutes, the reactor was removed from the cooling bath, and the reaction temperature was raised to room temperature. A diaphragm pump was connected to the reactor, and the system was subjected to a reduced pressure of 1.5 kPa and stirred for 24 hours. After the reaction was complete, the reduced pressure in the system was released, and the reactor was cooled to 0°C. Acetic acid (2.0 mL, 35 mmol) and water (50 mL) were added to the flask, and the product was extracted with methylene chloride (200 mL). An internal standard substance was added to the organic layer containing the product, and the yield was determined by the internal standard method.

[0224] Details of the dehydrating agents and yield results for Examples 3 to 9 are shown in Table II below.

[0225] [Table 2]

[0226] As illustrated in Examples 3 to 9, good NMR yields can be obtained by using a dehydrating agent. In particular, extremely good NMR yields can be obtained by using an alkoxysilane having the structure represented by general formula (4) as the dehydrating agent.

[0227] <Examples 10-12> In Examples 10 to 12, acetophenone (compound (1)-1) was used as the ketone compound, and dimethyl isophthalate (compound (2)-11) was used as the carboxylic acid ester compound. 1,3-bis(3-phenyl-3-oxopropanoyl)benzene (compound (3)-11) was synthesized as the β-diketone derivative. Triethoxypropylsilane was used as the dehydrating agent. In Examples 10 to 12, the type or amount of base used was changed.

[0228] Dimethyl isophthalate (2.2 g, 11.3 mmol) and a base (27.5 mmol) were added to a 100 mL flask in the reactor, and the mixture was kept under an argon atmosphere. Next, anhydrous DMF (6.5 mL) and triethoxypropylsilane (0.52 mL, 2.26 mmol) were added to the flask, the mixture was cooled to 0°C, and stirred. Acetophenone (2.62 mL, 22.6 mmol) was added dropwise to the flask over 10 minutes, the reactor was removed from the cooling bath, and the reaction temperature was raised to room temperature. A diaphragm pump was connected to the reactor, and the system was subjected to a reduced pressure of 1.5 kPa and stirred for 24 hours. After the reaction was complete, the reduced pressure in the system was released, and the reactor was cooled to 0°C. Acetic acid (2.0 mL, 35 mmol) and water (50 mL) were added to the flask, and the product was extracted with methylene chloride (200 mL). The resulting organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The concentrated residue was washed with methanol to obtain 1,3-bis(3-phenyl-3-oxopropanoyl)benzene as a pale yellow solid. In Examples 10 to 12, the isolation yield was determined by washing with methanol, rather than by NMR yield.

[0229] Details of the bases and yield results in Examples 10 to 12 are shown in Table III below.

[0230] [Table 3]

[0231] <Comparative Examples 3-4 and Examples 13-15> Acetophenone (compound (1)-1) was used as the ketone compound, and dimethyl isophthalate (compound (2)-11) was used as the carboxylic acid ester compound. 1,3-bis(3-phenyl-3-oxopropanoyl)benzene (compound (3)-11) was synthesized as the β-diketone derivative. In Comparative Examples 3 to 4, the ketone compound and carboxylic acid ester compound were reacted under reduced pressure of over 15.00 kPa (atmospheric pressure and 16.00 kPa), while in Examples 13 to 15, they were reacted under reduced pressure of less than 15.00 kPa (0.15 to 10.00 kPa).

[0232] Dimethyl isophthalate (2.2 g, 11.3 mmol) and sodium methoxide (1.49 g, 27.5 mmol) were added to a 100 mL flask in the reactor, and the mixture was kept under an argon atmosphere. Next, anhydrous DMF (6.5 mL) and triethoxypropylsilane (0.52 mL, 2.26 mmol) were added to the flask, the mixture was cooled to 0°C, and stirred. Acetophenone (2.62 mL, 22.6 mmol) was added dropwise to the flask over 10 minutes, and the reactor was removed from the cooling bath. The pressure inside the reactor was adjusted to the degree shown in Table IV below, the reaction temperature was raised, and the mixture was stirred for 24 hours. After the reaction was complete, the reactor was cooled to 0°C. Acetic acid (2.0 mL, 35 mmol) and water (50 mL) were added to the flask, and the product was extracted with methylene chloride (200 mL). An internal standard was added to the organic layer containing the product, and the yield was determined by the internal standard method.

[0233] The results for the degree of reduced pressure, temperature, and yield in Comparative Examples 3-4 and Examples 13-15 are shown in Table IV below.

[0234] [Table 4]

[0235] <Example-16> In Example 16, a β-diketone derivative was synthesized by changing the carboxylic acid ester compound. Acetophenone (compound (1)-1) was used as the ketone compound, and methyl benzoate (compound (2)-1) was used as the carboxylic acid ester compound. 3-hydroxy-1,3-diphenyl-2-propen-1-one (compound (3)-1) was synthesized as the β-diketone derivative.

[0236] [ka]

[0237] Sodium methoxide (0.77 g, 14.2 mmol) was added to a 100 mL flask and the mixture was kept under an argon atmosphere. Next, anhydrous DMF (6.5 mL), methyl benzoate (1.53 g, 11.3 mmol), and triethoxypropylsilane (0.52 mL, 2.26 mmol) were added to the flask, the mixture was cooled to 0°C, and the mixture was stirred. Acetophenone (1.66 mL, 14.2 mmol) was added dropwise to the flask over 5 minutes, the reactor was removed from the cooling bath, and the reaction temperature was raised to room temperature. A diaphragm pump was connected to the reactor, and the system was subjected to a reduced pressure of 1.5 kPa and stirred for 24 hours. After the reaction was complete, the reduced pressure in the system was released, and the reactor was cooled to 0°C. Acetic acid (1.0 mL, 17.5 mmol) and water (50 mL) were added to the flask, and the product was extracted with methylene chloride (200 mL). The resulting organic layer was concentrated, and the crude product was recrystallized with methanol to obtain 3-hydroxy-1,3-diphenyl-2-propen-1-one as a pale yellow solid (2.0 g). The yield was 80%.

[0238] The types of compounds and yield results for Example-16 are shown in Table V below.

[0239] [Table 5]

[0240] 2. Production of pyrazole derivatives For Examples 2-9, 13-15, and Comparative Examples 1-4, the product was extracted with methylene chloride (200 mL), and the resulting organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The concentrated residue was washed with methanol to obtain 1,3-bis(3-phenyl-3-oxopropanoyl)benzene as a pale yellow solid. For Examples 10-12, the isolated pale yellow solid was used directly in the production of PY-2 without performing the extraction, drying, and concentration operations described above.

[0241] In the method for producing the pyrazole derivative PY-2 described above, the raw material was changed to the pale yellow solid (100g) obtained in Examples 2 to 15 and Comparative Examples 1 to 4, respectively, and the pyrazole derivative PY-2 was synthesized.

[0242] The yield and purity for each manufacturing example are shown in Table VI below.

[0243] [Table 6]

[0244] It can be seen that pyrazole derivatives can also be produced in high yield and high purity by using the method for producing β-diketone derivatives according to this embodiment.

[0245] 3. Preparation of phase difference film <Compounds used in the examples> <Cellulose acylate> Table VII below shows the cellulose acylates C1 to C2 used in the examples.

[0246] [Table 7]

[0247] <Pyrazole derivatives> Selected from the above-mentioned group of exemplary pyrazole derivatives, indicated by the example compound number.

[0248] <Organic esters> S1: Sugar ester: BzSc (benzyl sucrose: average degree of esterification = 5.5) <Comparative Compounds> H1: Comparative example of pyrazole derivatives: The following triazole compound, molecular weight 846 <Fine particles> M1: Silylated silica microparticles "Aerosil® R812" (manufactured by Nippon Aerosil Co., Ltd.) M2: Dimethylsilylated silica "Aerosil® R972" (manufactured by Nippon Aerosil Co., Ltd.) M3: Silicone resin-based microparticles "Tospearl® 103" (manufactured by Momentive Performance Materials)

[0249] [ka]

[0250] <Preparation of Cellulose Acrylate Film 101> <Fine particle dispersion 1> Fine particles M1 11 parts by mass Ethanol 89 parts by mass The above ingredients were mixed and stirred in a dissolver for 50 minutes, and then dispersed in Mantongorin.

[0251] <Fine particle additive liquid 1> The fine particle dispersion 1 was slowly added to a dissolution tank containing methylene chloride while stirring thoroughly. Next, the resulting mixture was dispersed using an attritor so that the secondary particles had a predetermined particle size. The resulting dispersion was filtered using "Finemet® NF" (manufactured by Nippon Seisen Co., Ltd.) to prepare fine particle additive solution 1.

[0252] Methylene chloride 99 parts by mass Fine particle dispersion liquid 1 5 parts by mass

[0253] <Dope 1> Dope 1 with the following composition was prepared. First, methylene chloride and ethanol were added as solvents to a pressurized dissolution tank. Next, cellulose acylate C1, pyrazole derivative PY-2, organic ester, and fine particle additive solution 1 were added to the pressurized dissolution tank containing the solvents while stirring. The mixture in the tank was heated and stirred until completely dissolved. The resulting solution was filtered using "Asaka Filter Paper No. 244" (manufactured by Asaka Filter Paper Co., Ltd.) to prepare dope 1.

[0254] (Composition of Dope 1) Methylene chloride 365 parts by mass Ethanol 50 parts by mass Cellulose acylate C1 100 parts by mass Pyrazole derivative PY-2: 3 parts by mass Organic ester S1 5 parts by mass Fine particle additive liquid 1 1 part by mass

[0255] <Film Formation> Dope 1 was cast from a pressurized die slit onto the casting position on a stainless steel belt support for casting. The solvent was evaporated on the stainless steel belt support until the residual solvent content in the cast film reached 75% by mass. The film from which the solvent had been evaporated was then peeled off the stainless steel belt support with a peel tension of 130 N / m. The peeled film was stretched by 30% in the width direction using a tenter while applying heat at 150°C. The residual solvent content at the start of stretching was 15% by mass.

[0256] Next, in the drying zone, the peeled film was dried while being transported by numerous rollers. The drying temperature was 130°C and the transport tension was 100 N / m. As a result, a cellulose acylate film 101 with a thickness of 40 μm after drying was obtained.

[0257] <Preparation of phase difference films 102-117> In phase contrast film 101, the cellulose acylate, pyrazole derivative, fine particles, and additives were varied as shown in Table VIII. Phase contrast films 102 to 117 were prepared using the same procedure otherwise.

[0258] In this context, "additive" refers to a compound having the structure represented by general formula (6). In phase contrast film 101, a β-diketone derivative was produced without using a compound having the structure represented by general formula (4). Next, a pyrazole derivative was produced using the obtained β-diketone derivative. Phase contrast film 101 was prepared using the obtained pyrazole derivative. Analysis of the components contained in phase contrast film 101 revealed that the amount (content) of the compound having the structure represented by general formula (6) was 0 parts by mass.

[0259] On the other hand, in the phase difference film 102, a β-diketone derivative was produced using compound (4)-1. Next, a pyrazole derivative was produced using the obtained β-diketone derivative. Phase difference film 102 was prepared using the obtained pyrazole derivative. When the components contained in phase difference film 102 were analyzed, the amount (content) of compound (5)-3 added was 0.02000 parts by mass when the total amount of resin was 100 parts by mass.

[0260] The composition of each phase difference film is shown in Table VIII below. The type and content of each material were changed as described in Table VIII below. The type and content of the compound having the structure represented by general formula (6) were adjusted by changing the production conditions of the β-diketone derivative, which is a precursor of the corresponding pyrazole derivative, as described above. Specifically, in the production of the β-diketone derivative, the compound having the structure represented by general formula (4) above was used as a dehydrating agent, and other production conditions were adjusted as appropriate. The content of fine particles and additives were given as values ​​when the total amount of resin was 100 parts by mass.

[0261] [Table 8]

[0262] ≪Rating≫ <Retardation value> The retardation values ​​of the phase difference film were measured at a wavelength of 590 nm under conditions of 23°C and 55% relative humidity. The in-plane retardation value (Ro), defined by equation (i) below, and the thickness-direction retardation value (Rt), defined by equation (ii) below, were measured using "Axoscan" (manufactured by Axometrics).

[0263] Specifically, for each phase difference film prepared as described above, three-dimensional refractive index measurements were performed at 10 locations at a wavelength of 590 nm under conditions of 23°C and 55% RH. x , n y , n zAfter calculating the average value, the in-plane retardation value Ro and the thickness-direction retardation value Rt were calculated according to the following formula.

[0264] Equation (i): Ro = (n x -n y ) × d (nm) Equation (ii): Rt = {(n x +n y ) / 2-n z} × d(nm) [In equations (i) and (ii), n x This represents the refractive index in the direction x where the refractive index is maximum in the in-plane direction of the film. y This represents the refractive index in the direction y perpendicular to the aforementioned direction x, in the in-plane direction of the film. z represents the refractive index in the film thickness direction z. d represents the film thickness (nm).

[0265] When the retardation values ​​were measured for each of the phase difference films prepared as described above, the in-plane retardation value Ro was within the range of 50±5nm, and the thickness-direction retardation value Rt was within the range of 120±10nm.

[0266] <Phase difference variation> For each phase difference film prepared as described above, the change in phase difference in response to humidity fluctuations was evaluated according to the method described below.

[0267] For each phase difference film prepared as described above, the in-plane retardation Ro and the thickness-direction retardation Rt were measured in an environment of 23°C and 55% RH using the procedure described above. The obtained measured values ​​were referred to as measured value (I).

[0268] Next, each phase difference film was immersed in water for 24 hours, then lightly wiped dry, and the retardation Rt in the thickness direction was measured again after 30 seconds. The obtained measurement value was designated as measurement value (II).

[0269] The absolute value ΔRt(nm) of the difference between measurement (I) and measurement (II) was calculated. A smaller value of ΔRt(nm) indicates higher stability of the phase difference with respect to humidity fluctuations.

[0270] <Internal haze> Each phase difference film prepared as described above was cut into 6cm pieces, and glycerin was applied to both sides of the cut film. Two 1mm thick glass plates, "Micro Slide Glass, Part Number S9111" (manufactured by Matsunami Glass Industry Co., Ltd.), were used to sandwich the glycerin-coated film from both sides, ensuring complete optical contact between the two glass plates and the film. The haze of the obtained samples was measured according to JIS K7136. From this measurement, the haze value obtained by subtracting the haze measured separately with only glycerin sandwiched between two glass plates was calculated as the internal haze value of the film. The haze was measured using a haze meter "NDH2000" (manufactured by Nippon Denshoku Industries Co., Ltd.).

[0271] Internal haze evaluates the turbidity inside the film due to bleed-out of additives during and after the film manufacturing process; a lower value indicates better performance.

[0272] <Blocking> Each of the phase difference films prepared as described above was wound up and left at room temperature for 3 months. After that, each phase difference film was unwound, and the blocking (sticking) state of the overlapping films was visually observed, and the blocking was evaluated based on the following criteria.

[0273] (Evaluation Criteria) A: There is no blocking. B: There is almost no blocking. C: There is a slight blocking issue, but it is not a problem. D: There is significant blocking, which is at a problematic level.

[0274] The evaluation results for each phase difference film are shown in Table IX.

[0275] [Table 9]

[0276] (Comparative example) Films 101 and 106 do not contain or contain only trace amounts of compounds having the structure represented by general formula (6), so there are no practical problems, but they are relatively prone to blocking. Because film 110 contains more than 0.1 parts by mass of a compound having the structure represented by general formula (6), it is prone to high internal haze due to bleed-out, which poses a practical problem. Because film 116 does not contain pyrazole derivatives, the stability of the phase difference with respect to humidity fluctuations tends to decrease, and internal haze tends to increase due to bleed-out, which presents practical problems. Since film 117 does not contain a compound having the structure represented by general formula (6), it is prone to high internal haze caused by fine particles M3, which poses a practical problem.

[0277] (Examples) From Table IX, the following can be seen: Compared to the comparative example, the phase difference film of the present invention has lower internal haze and is less prone to blocking. Furthermore, the phase difference film of the present invention exhibits less variation in retardation value with respect to humidity fluctuations and has excellent durability against humidity changes. [Explanation of Symbols]

[0278] 51 Polarizing plate 52 protective films 53 Polarizer 54 Phase difference film

Claims

1. A ketone compound having the structure represented by the following general formula (1), A carboxylic acid ester compound having the structure represented by the following general formula (2) is used. The reaction is carried out in the presence of a base under reduced pressure of 15 kPa or less. A method for producing a β-diketone derivative having a structure represented by the following general formula (3). 【Chemistry 1】 In the formula, R １ R represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or a tertiary alkyl group. ２ This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 【Chemistry 2】 In the formula, Ar １ R represents an aromatic hydrocarbon group or an aromatic heterocyclic group that may be substituted. ３ and R ４ Each of these independently represents an alkyl group having 1 to 6 carbon atoms. n represents an integer from 0 to 2. When n is 2, R ３ They may be the same or different. 【Transformation 3】 In the formula, R １ represents an aromatic hydrocarbon group, an aromatic heterocyclic group or a tertiary alkyl group. Ar １ represents an optionally substituted aromatic hydrocarbon group or an aromatic heterocyclic group. R ２ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. n represents an integer from 0 to 2. When n is 2, R １ may be the same or different. When n is 2, R ２ may be the same or different.

2. A method for producing a β-diketone derivative according to claim 1, comprising reacting the ketone compound with the carboxylic acid ester compound in the presence of a dehydrating agent.

3. The method for producing a β-diketone derivative according to claim 2, wherein the dehydrating agent is one or more compounds selected from the group consisting of carbonate esters, phosphite esters, alkoxysilanes, and titanate esters.

4. The method for producing a β-diketone derivative according to claim 3, wherein the alkoxysilane includes a compound having a structure represented by the following general formula (4). 【Chemistry 4】 In the formula, R ５ R represents an alkyl group having 1 to 4 carbon atoms. ６ * represents an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms. *p represents an integer from 0 to 3.

5. The method for producing a β-diketone derivative according to claim 1, wherein the base is one or more compounds selected from the group including metal alkoxides, sodium amides, and sodium hydride.

6. A method for producing a β-diketone derivative according to claim 1, wherein the ketone compound has a structure represented by the following general formula (1a). 【Transformation 5】 In the formula, R ２ X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. １ m represents a substituent. １ This represents an integer from 0 to 5.

7. A method for producing a β-diketone derivative according to claim 1, wherein the carboxylic acid ester compound has a structure represented by the following general formula (2a). 【Transformation 6】 In the formula, R ３ and R ４ Each of these independently represents an alkyl group having 1 to 6 carbon atoms. ２ m represents a substituent. ２ This represents an integer from 0 to 4.

8. A method for producing a β-diketone derivative according to claim 6 or claim 7, comprising reacting the ketone compound with the carboxylic acid ester compound in the presence of a dehydrating agent.

9. The method for producing a β-diketone derivative according to claim 8, wherein the dehydrating agent is one or more compounds selected from the group consisting of carbonate esters, phosphite esters, alkoxysilanes, and titanate esters.

10. The method for producing a β-diketone derivative according to claim 9, wherein the alkoxysilane includes a compound having a structure represented by the following general formula (4). 【Transformation 7】 In the formula, R ５ R represents an alkyl group having 1 to 4 carbon atoms. ６ * represents an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms. *p represents an integer from 0 to 3.

11. The method for producing a β-diketone derivative according to claim 6 or claim 7, wherein the base is one or more compounds selected from the group including metal alkoxides, sodium amides, and sodium hydride.

12. A β-diketone derivative is produced using the method for producing a β-diketone derivative described in any one of claims 1 to 7. A method for producing a pyrazole derivative, comprising reacting a manufactured β-diketone derivative with hydrazine to produce a pyrazole derivative having the structure represented by the following general formula (5). 【Transformation 8】 In the formula, R １ Ar represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or a tertiary alkyl group. １ This represents a divalent aromatic hydrocarbon group or an aromatic heterocyclic group.

13. The product contains a resin, a pyrazole derivative having a structure represented by the following general formula (5), and a compound having a structure represented by the following general formula (6). A phase difference film in which, when the total amount of the aforementioned resin is 100 parts by mass, the content of a compound having the structure represented by the following general formula (6) is in the range of 0.0001 to 0.1 parts by mass. 【Chemistry 9】 In the formula, R １ Ar represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or a tertiary alkyl group. １ This represents a divalent aromatic hydrocarbon group or an aromatic heterocyclic group. 【Chemistry 10】 In the formula, R ７ X represents an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms. ３ , X ４ and X ５ This is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -Si-R ８ (O-X ６ ) ２ Represents the group represented by R. ８ X represents an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms. ６ This is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -Si-R ８ (O-X ６ ) ２ It represents.

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