TW201840651A - Optical film and method for producing optical film - Google Patents

Abstract

An objective of the present invention is to provide an optical film containing a polyamide-imide resin which can be especially suitably used as a front plate of a flexible display or the like, and can increase the surface hardness even under relatively low temperature heating conditions. The optical film of the present invention contains a polyamide-imide resin having a peak value of tan [delta] by DMA measurement within the range of 300 to 370 DEG C, and has a YI value of 3 or less.

Description

 Optical film and optical film manufacturing method  

The present invention relates to an optical film containing a polyamidoximine resin and a method of producing the optical film.

Video display devices such as liquid crystal display devices and organic EL display devices are widely used for various purposes such as mobile phones and smart watches, not only for televisions. With the expansion of this use, an image display device (flexible display) having flexibility characteristics is expected. The video display device is composed of a display element such as a liquid crystal display element or an organic EL display element, and a constituent member such as a polarizing plate, a phase difference plate, and a panel. In order to achieve a flexible display, all of the constituent members must be flexible.

The current panel uses glass. The transparency of the glass is high, and the type of glass can exhibit high hardness, but the opposite is also very rigid and easily broken, so it is difficult to utilize the panel material as a flexible display.

Therefore, as an alternative material for glass, the application of polymer materials is discussed. Since the panel made of a polymer material is easy to exhibit flexible properties, it can be expected to be used for various applications. As the resin having flexibility, various ones may be mentioned, and one of them is a polyamidoximine resin. The polyamidoximine resin can be used for various purposes from the viewpoint of transparency or heat resistance.

For example, Patent Document 1 describes a copolymerized polyamidoquinone imine resin which is copolymerized by a compound containing a polyoxyalkylene group and has a specific logarithmic viscosity and elongation at break. Patent Document 2 describes a polyamidoximine resin which is obtained by polymerizing specific monomers (a), (b1) and (b2). Patent Document 3 describes a polyamidoximine resin which is produced by using a 3-carboxylic acid component having an acid anhydride group, an isocyanate or a diamine, and has a predetermined number average molecular weight.

 [Previous Technical Literature]    [Patent Literature]  

Patent Document 1: Japanese Laid-Open Patent Publication No. H9-328550

Patent Document 2: Japanese Laid-Open Patent Publication No. 2008-285660

Patent Document 3: Japanese Laid-Open Patent Publication No. 2009-286826

Conventionally, when a film containing a polyimide film is used as a panel, in order to improve surface hardness and the like, a film is heated under high temperature conditions. However, the film may yellow due to heating under high temperature conditions. When the film contains additives (such as ultraviolet absorbers) in addition to the polyamidoximine resin, the additive may decompose and the film quality may be impaired. problem.

Accordingly, it is an object of the present invention to provide an optical film containing a polyamidoximine resin which is particularly suitable for use as a panel of a flexible display or the like, and which can improve surface hardness even at a relatively low temperature.

In order to solve the above problems, the inventors of the present invention have focused on various characteristics of polyamidoximine resins, focusing on heating temperature and surface hardness. As a result, it has been found that the present invention can be completed by using a polyamidoximine resin which satisfies specific conditions, that is, it is possible to increase the surface hardness under a relatively low temperature heating condition.

That is, the present invention encompasses the following preferred forms.

[1] An optical film comprising a polyamidoximine resin having a YI value of 3 or less, and the polyamidoximine resin having a peak of tan δ obtained by DMA measurement in a range of 300 to 370 °C.

[2] The optical film according to the above [1], which has a pencil hardness of 3B or more in accordance with an illuminance condition of 4000 lux according to ASTM D3363.

[3] The optical film according to the above [1] or [2], wherein the optical film further contains an additive having a light absorbing function.

[4] The optical film according to any one of [1] to [3] wherein the light absorbing function additive is selected from the group consisting of an ultraviolet absorber and a bluing agent.

[5] The optical film according to any one of [1] to [4] wherein the polyamidoximine resin contains a fluorine atom.

[6] The optical film according to any one of the above [1], wherein the polyamidoximine resin contains at least a constituent unit represented by the formula (1).

[In the formula (1), R ¹ to R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and a hydrogen atom contained in R ¹ to R ⁸ may be used. Each of them is independently substituted with a halogen atom, and A each independently represents -O-, -S-, -CO- or -NR ⁹ -, and R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms which can be substituted with a halogen atom, and m is 1 An integer up to 4, * indicates a bond key. ]

[7] The optical film according to any one of [1] to [6] wherein the polyamidoximine resin has at least a constituent unit derived from a dicarboxylic acid.

[8] The optical film according to any one of the above [1], wherein the polyamidoximine resin has at least a diamine derived from a fluorine atom and/or a fluorine atom A constituent unit of a carboxylic acid dianhydride.

[9] The optical film according to any one of [1] to [8], wherein the optical film has a thickness of 30 μm or more.

[10] A method for producing an optical film, comprising at least the steps of: (1) applying a resin composition containing at least a polyamidamine resin and a solvent to a support; and (2) 1) a step of drying the coating film of the resin composition at a temperature of 240 ° C or lower and then peeling off the support; or (2-2) drying the coating film of the resin composition at a temperature of 240 ° C or lower, The step of peeling off the support and the step of heating the peeled film at a temperature of 240 ° C or lower.

[11] The production method according to the above [10], wherein the resin composition further contains an additive having a light absorbing function.

[12] The production method according to [10] or [11] wherein the solvent comprises dimethylacetamide.

The optical film of the present invention can increase the surface hardness at a relatively low temperature. Therefore, the optical film of the present invention can have both sufficient surface hardness, high transparency, and low yellowness.

Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described herein, and various modifications may be made without departing from the spirit and scope of the invention.

The optical film of the present invention contains a polyamidoximine resin having a peak of tan δ obtained by DMA measurement in the range of 300 to 370 °C. Hereinafter, the temperature at which the peak of tan δ obtained by the DMA measurement of the polyamidoximine resin is also referred to as "tan δ peak temperature". Further, the tan δ peak temperature of the resin is also referred to as the temperature of the glass transition temperature of the resin. The above range is lower than the tan δ peak temperature generally possessed by conventional polyamidoximine resins. The optical film of the present invention containing the polyamidoximine resin having a peak of tan δ in the above-mentioned predetermined temperature range can achieve a sufficiently high surface hardness at a relatively low temperature. It is presumed that the free volume of the resin is reduced under heating conditions at a lower temperature. Further, the above mechanism does not impose any limitation on the present invention. Since the optical film of the present invention can achieve a sufficiently high surface hardness at a low temperature, it is possible to suppress yellowing of the film due to heating, and an additive having a light absorbing function, such as an additive having low heat resistance, as the case may be. Decomposition, which can improve the quality of the film. When the tan δ peak temperature of the polyamidoximine resin contained in the optical film of the present invention is less than 300 ° C, the elastic modulus of the resin is lowered, so that it is difficult to exhibit high surface hardness. Further, when the tan δ peak temperature exceeds 370 ° C, high-temperature heat treatment is required to exhibit high surface hardness, and the optical properties of the resin may be lowered. The tan δ peak temperature of the polyamidoximine resin contained in the optical film of the present invention is preferably 305 to 365 °C. In one embodiment, the tan δ peak temperature of the polyamidoximine resin contained in the optical film of the present invention is preferably 305 to 365 ° C, more preferably 320 to 365 ° C, still more preferably 340 to 365 ° C.

The method of adjusting the tan δ peak temperature of the polyamidoximine resin to the above range is not particularly limited, and for example, the constituent unit represented by the following formula (1) contained in the polyamidoximine resin is adjusted. A method for adjusting the imidization ratio in a polyamidoximine resin, and the like. In addition, when the amount of the constituent unit represented by the following formula (1) is increased or the imidization ratio in the polyamidoximine resin is increased, tan δ tends to decrease, so that it will have a desired value. These adjustments can be made.

The tan δ peak temperature was measured by DMA measurement. Specifically, the DMA measuring instrument (DMA Q800 manufactured by TA Instrument Co., Ltd.) can be used for evaluation according to the examples of the present specification.

The optical film of the present invention has a YI value of 3 or less. When the YI value exceeds 3, the yellowness of the optical film becomes too high, so that sufficient visibility can not be obtained. The YI value of the optical film of the present invention is preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.0 or less. If the YI value is less than or equal to the above upper limit, the visibility of the optical film can be further improved. Further, the lower limit of the YI value is not particularly limited, and usually it is preferably 0 or more. The YI value indicates the yellowness (Yellow Index: YI value) of the film, and was measured in accordance with JIS K 7373:2006 using a spectrophotometer (UV-visible near-infrared spectrophotometer V-670 manufactured by JASCO Corporation). Specifically, the three stimulation values (X, Y, and Z) obtained by measuring the transmittance of light of 300 to 800 nm are calculated by the following formula.

YI=100×(1.2769X-1.0592Z)/Y

The pencil hardness (surface hardness) of the optical film of the present invention is measured in accordance with ASTM D 3363 under an illumination of 4000 lux, preferably 3 B or more, more preferably 2 B or more, still more preferably B or more, and particularly preferably Above HB, it is preferably H or more, and most preferably 2H or more. When the pencil hardness of the optical film of the present invention is at least the above lower limit, when used as a panel (glass film) of an image display device, it is easy to suppress damage on the surface of the image display device, and it is easy to prevent shrinkage and expansion of the optical film, so that it is preferable. . The upper limit of the pencil hardness of the optical film of the present invention is not particularly limited. The pencil hardness can be measured in accordance with JIS K5600-5-5:1999. Specifically, the measurement was carried out at a load of 100 g and a scanning speed of 60 mm/min, and was evaluated under an illuminance condition of a light amount of 4000 lux. Moreover, when evaluating the pencil hardness, there are different cases depending on the illuminance conditions used. Specifically, compared with the pencil hardness measured by the evaluation under the illuminance condition of the light amount of 4000 lux, the pencil hardness measured by the evaluation under the illuminance condition of a lower light amount is less likely to be observed on the film due to the lower amount of light. As a result, the result is higher than the actual situation. Therefore, the pencil hardness in the present specification is a value obtained by evaluation under the illuminance condition of a light amount of 4000 lux.

The thickness of the optical film of the present invention is preferably 20 μm or more, more preferably 30 μm or more, and still more preferably 40 μm or more, from the viewpoint of the influence of the pencil hardness on the film thickness. The thickness of the optical film of the present invention is preferably 300 μm or less, more preferably 200 μm or less, still more preferably 100 μm or less, from the viewpoint of bending resistance. The above thickness is measured using a contact type digital scale.

The total light transmittance (Tt) of the optical film of the present invention is measured in accordance with JIS K 7105:1981, preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, and particularly preferably more than 90 percent. When the total light transmittance is equal to or higher than the above lower limit, the visibility of the optical film of the present invention when assembled into a video display device is easily improved. Further, the upper limit of the total light transmittance of the optical film of the present invention is generally 100% or less. The total light transmittance was measured in accordance with JIS K 7105: 1981 using a fully automatic direct reading haze computer HGM-2DP manufactured by, for example, a Suga test machine.

The elastic modulus of the optical film of the present invention is preferably 5.9 GPa or less, more preferably 5.5 GPa or less, still more preferably 5.2 GPa or less, particularly preferably 5.0 GPa or less, and most preferably from the viewpoint of film softness. Below 4.5GPa. When the elastic modulus is equal to or less than the above upper limit, it is easy to suppress damage of other members due to the optical film when the flexible display is bent. Further, the lower limit of the elastic modulus of the optical film of the present invention is not particularly limited, but is usually 2.0 GPa or more. For the elastic modulus, for example, Autograph AG-IS manufactured by Shimadzu Corporation can be used to measure the SS curve with a test piece having a width of 10 mm at a distance between the clamps of 500 mm and a tensile speed of 20 mm/min, and the inclination is measured by the inclination angle thereof. .

The number of times of the reverse bending of the optical film of the present invention is measured from the viewpoint of the bending resistance of the film, and is measured at a temperature of R = 1 mm, 135 °, a weight of 0.75 kgf, and a speed of 175 cpm until the film is broken, preferably 10,000 times or more, and more preferably. It is 20,000 times or more, more preferably 30,000 times or more, particularly preferably 40,000 times or more, and most preferably 50,000 times or more. When the number of times of the reverse bending of the optical film of the present invention is at least the above lower limit, it is easy to suppress wavy wrinkles which are generated when the optical film is bent. Further, the upper limit of the number of times of repeated bending of the optical film is not particularly limited, and it is usually sufficient for practical use as long as it can be bent about 1,000,000 times or less. For the number of times of the reverse bending, for example, a MIT folding fatigue tester (type 0530) manufactured by Toyo Seiki Seisakusho Co., Ltd. can be used, and a test piece cut out from an optical film having a thickness of 50 μm and a width of 10 mm can be obtained as a measurement sample.

The weight average molecular weight (Mw) of the polyamidoximine resin contained in the optical film of the present invention is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 50,000 or more, particularly preferably 70,000 or more, and still more Preferably, it is 100,000 or more, preferably 800,000 or less, more preferably 600,000 or less, still more preferably 500,000 or less, and particularly preferably 450,000 or less. When the weight average molecular weight (Mw) of the polyamidoximine resin is at least the above lower limit, the bending resistance of the optical film of the present invention is easily improved. When the weight average molecular weight (Mw) of the polyamidoximine resin is less than or equal to the above upper limit, the solubility of the polyamidoximine resin in the solvent is improved, and the polymerization used in the production of the optical film of the present invention can be suppressed. The viscosity of the amidoximine varnish makes it easy to manufacture the optical film of the present invention. Moreover, since the extension of an optical film becomes easy, workability is favorable. The weight average molecular weight (Mw) can be determined, for example, by GPC measurement, in terms of standard polystyrene, and can be specifically determined by the method described in the examples.

The imidization ratio of the polyamidoximine resin contained in the optical film of the present invention is preferably 90% or more, more preferably 95% or more. When the imidization ratio is at least the above lower limit, it is easy to exhibit high surface hardness. The upper limit of the imidization ratio of the polyamidoximine resin is not particularly limited, and may be 100% or less. The imidization ratio is a double value of the number of moles of the constituent unit derived from the tetracarboxylic dianhydride in the polyamidoximine resin, and the imine bond in the polyamidoximine resin The ratio of the number of ears is determined by two-dimensional NMR in this specification. The details of the measurement conditions of the two-dimensional NMR are as described in the examples.

The polyamidoximine resin contained in the optical film of the present invention preferably has at least a constituent unit represented by the formula (1).

[In the formula (1), R ¹ to R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and a hydrogen atom contained in R ¹ to R ⁸ may be used. Each of them is independently substituted with a halogen atom, and A each independently represents -O-, -S-, -CO- or -NR ⁹ -, and R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms which can be substituted with a halogen atom, and m is 1 An integer of 4, * indicates a key bond].

When the polyamidoximine resin has a constituent unit represented by the formula (1), the main chain of the polyamidoximine resin may be imparted when the film is formed by the -A- in the above formula. Highly curved construction. By making the polyamidoximine resin moderately have a structure capable of imparting high flexibility, the tan δ peak temperature of the polyamide amide resin can be appropriately lowered, and as a result, heating conditions at a lower temperature can be achieved. The surface hardness of the film containing the polyamidoximine resin is increased.

The symbols in the formula (1) are explained below.

A independently represents -O-, -S-, -CO- or -NR ⁹ -, respectively, and R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. From the viewpoint of the flexibility of the optical film of the present invention, A preferably represents -O- or -S-, respectively, and more preferably -O-.

R ¹ to R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. From the viewpoints of flexibility and surface hardness of the optical film of the present invention, R ¹ to R ⁸ preferably each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a carbon number of 1 The alkyl group to 3 is more preferably a hydrogen atom. Here, the hydrogen atoms contained in R ¹ to R ⁸ may be independently substituted with a halogen atom.

m is an integer of 1 to 4, and is preferably an integer of 1 to 3, more preferably 1 or 2, still more preferably 1 from the viewpoint of availability of raw materials. When m is in the above range, the availability of the raw material is good, and the flexibility of the optical film of the present invention is easily improved.

In a preferred embodiment of the present invention, the formula (1) is a constituent unit represented by the formula (1'). In this case, the optical film of the present invention can exhibit high surface hardness while having a low modulus of elasticity and easy to have high flexibility.

The preferred embodiment of the polyamidoquinone imide resin contained in the optical film of the present invention has a constituent unit represented by formula (1) or formula (1'), and the amount of the constituent unit is based on polyamidoguanidine. The total structural unit contained in the imide resin is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, and particularly preferably 20 mol% or more. When the amount of the constituent unit represented by the formula (1) or the formula (1') is at least the above lower limit, it is easy to obtain a polyamidoximine resin having a peak of tan δ in a temperature range of 370 ° C or lower.

Further, the amount of the constituent unit represented by the formula (1) or the formula (1') is preferably 45 mol% or less, more preferably 40 mol, based on the total constituent unit contained in the polyamidoximine resin. % or less, more preferably 30% or less. When the amount of the constituent unit represented by the formula (1) or the formula (1') is at most the above upper limit, it is easy to obtain a polyamidoximine resin having a peak of tan δ in a temperature range of 300 ° C or higher.

The polyamidoximine resin contained in the optical film of the present invention can be produced, for example, as a main raw material of a dicarboxylic acid, a diamine or a tetracarboxylic acid, and preferably has at least a constituent unit derived therefrom. Here, the constituent unit represented by the formula (1) or the formula (1') is preferably a constituent unit derived from a dicarboxylic acid.

The polyamidoximine resin contained in the optical film of the present invention preferably has at least a constituent unit derived from a dicarboxylic acid from the viewpoint of pencil hardness or elastic modulus. The constituent unit derived from the dicarboxylic acid is preferably a constituent unit derived from carboxylic acid dichloride.

The dicarboxylic acid may, for example, be a compound represented by the formula (2). The polyamidoximine resin may have a constituent unit derived from a dicarboxylic acid or may have a constituent unit derived from two or more dicarboxylic acids.

In the formula (2), Z represents a divalent organic group, and B ¹ and B ² each independently represent OH or a halogen atom, preferably a chlorine atom. ]

The polyamidoximine resin contained in the optical film of the present invention has a preferred embodiment from the constituent unit of the dicarboxylic acid represented by the formula (2), and the amount of the constituent unit is based on polyamidofluorene. The total structural unit contained in the amine resin is preferably 5 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol% or more. When the amount of the constituent unit of the dicarboxylic acid represented by the formula (2) is at least the above lower limit, it is easy to exhibit a high surface hardness. Further, the amount of the constituent unit derived from the dicarboxylic acid represented by the formula (2) is preferably 45 mol% or less, more preferably 40 mol%, based on the total structural unit contained in the polyamidoximine resin. The following, more preferably 30% or less. When the amount of the constituent unit of the dicarboxylic acid represented by the formula (2) is at most the above upper limit, it is easy to obtain a polyamidoximine resin having a peak of tan δ in a temperature range of 370 ° C or lower.

Z in the formula (2) represents a divalent organic group, and preferably an organic group in which a hydrogen atom in the organic group is substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. The divalent organic group may, for example, be a group represented by the formula (2a) and the formula (2b); the hydrogen atom in the group represented by the formula (2a) and the formula (2b) is a methyl group, a fluorine group or a chlorine group. Or a trifluoromethyl-substituted group; and a divalent straight-chain hydrocarbon group having a carbon number of 6 or less.

[In the formulae (2a) and (2b), * represents a bond, and U ¹ represents a single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -Ar-, -SO ₂ -, -CO-, -O-Ar-O-, -Ar-O-Ar-, -Ar- CH ₂ -Ar-, -Ar-C(CH ₃ ) ₂ -Ar- or -Ar-SO ₂ -Ar-. Ar represents a aryl group having 6 to 20 carbon atoms which may be substituted by a fluorine atom, and a specific example thereof may be a phenyl group. ]

Specific examples of the dicarboxylic acid represented by the formula (2) include an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, and the like, and a similar chlorine compound or an acid anhydride, and two or more kinds thereof may be used in combination. Specific examples thereof include terephthalic acid; isophthalic acid; naphthalene dicarboxylic acid; 4,4'-biphenyldicarboxylic acid; 3.3'-biphenyldicarboxylic acid; and chain hydrocarbons having a carbon number of 8 or less. a dicarboxylic acid compound, and a compound in which two benzoic acids are bonded by a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - or a phenylene group, And such bismuth chloride compounds. The dicarboxylic acid represented by the above formula (2) preferably contains 4,4'-oxybis(benzoic acid) and/or a ruthenium chloride compound thereof. Specifically, it is preferable to contain 4,4'-oxybis(benzidine chloride), and it is more preferable to use 4,4'-oxybis(benzidine chloride) and p-quinone chloride.

In a preferred embodiment of the present invention in which the polyamidoximine resin has a constituent unit derived from a dicarboxylic acid, it is considered that the surface hardness, the modulus of elasticity, and the flexibility of the optical film of the present invention are easily improved. The amine quinone imine resin preferably has at least a structural unit derived from the dicarboxylic acid represented by the formula (1) in the formula (2). When the polyamidoximine resin has two or more constituent units derived from a dicarboxylic acid, Z in the formula (2) is a constituent unit of the dicarboxylic acid represented by the formula (1), and is composed of an optical film. The viewpoint of the surface hardness, the modulus of elasticity, and the flexibility is preferably 5 mol% or more, and more preferably 7 mol% or more based on the entire constituent unit derived from the dicarboxylic acid contained in the polyamidoximine resin. More preferably, it is 9 mol% or more, and particularly preferably 11 mol% or more. The upper limit of the amount of the constituent unit of the dicarboxylic acid represented by the formula (1) in the formula (2) is not particularly limited, and the constituent unit derived from the dicarboxylic acid contained in the polyamidoximine resin is contained. As long as it is 100% or less. The ratio of Z derived from the formula (2) to the structural unit of the dicarboxylic acid represented by the formula (1) can be measured, for example, by ¹ H-NMR, or can be calculated from the packing ratio of the raw material.

The polyamidoximine resin contained in the optical film of the present invention preferably has at least a constituent unit derived from a diamine from the viewpoints of transparency, low hygroscopicity, and solubility in a solvent.

The diamine may, for example, be a compound represented by the formula (3).

H ₂ NX-NH ₂ (3) [In the formula (3), X represents a divalent organic group. ]

The polyamidoximine resin may have a constituent unit derived from one diamine or may have a constituent unit derived from two or more kinds of diamines.

The polyamidoximine resin contained in the optical film of the present invention has a preferred embodiment from the constituent unit of the diamine represented by the formula (3), and the amount of the constituent unit is based on polyamidoquinone imine. The total constituent unit contained in the resin is preferably 47.5 mol% or more, more preferably 49.0 mol% or more, still more preferably 49.5 mol% or more. When the amount of the constituent unit of the diamine represented by the formula (3) is at least the above lower limit, a high molecular weight polyamidoquinone imide resin is easily obtained, and a high surface hardness is easily exhibited. Further, the amount of the constituent unit derived from the diamine represented by the formula (3) is preferably 50.5 mol% or less, more preferably 50.0 mol% or less, based on the total structural unit contained in the polyamidoximine resin. More preferably, it is 49.99% or less. When the amount of the constituent unit of the diamine represented by the formula (3) is at most the above upper limit, it is easy to exhibit high transparency and low yellowness.

X in the formula (3) represents a divalent organic group, and preferably an organic group in which a hydrogen atom in the organic group can be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. The divalent organic group can be exemplified by the formula (3a), the formula (3b), the formula (3c), the formula (3d), the formula (3e), the formula (3f), the formula (3g), the formula (3h), and the formula. a group represented by (3i); a group in which a hydrogen atom in the group represented by the formula is substituted with a methyl group, a fluorine group, a chloro group or a trifluoromethyl group; and a chain hydrocarbon group having a carbon number of 6 or less.

[Formula (3a), Formula (3b), Formula (3c), Formula (3d), Formula (3e), Formula (3f), Formula (3g), Formula (3h), and Formula (3i), * represents a bond junction bond, V ¹ to V ^3, each independently represents a single bond, -O -, - S -, - CH 2 -, - CH 2 -CH 2 -, - CH (CH 3) -, - C (CH 3 ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - or -CO-. ]

In one example, V ¹ and V ³ are a single bond, -O- or -S-, and V ² is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or -SO ₂ -. The bonding position of V ¹ and V ² to each ring and the bonding position of V ² and V ³ to each ring are preferably, respectively, a meta or para position, and more preferably a para position, for each ring.

Among the bases represented by the formula (3a), the formula (3b), the formula (3c), the formula (3d), the formula (3e), the formula (3f), the formula (3g), the formula (3h), and the formula (3i) From the viewpoint of surface hardness and flexibility of the optical film of the present invention, it is preferably a group represented by the formula (3d), the formula (3e), the formula (3f), the formula (3g) or the formula (3h), more preferably It is a group represented by the formula (3e), the formula (3f) or the formula (3g). Further, from the viewpoint of the surface hardness and flexibility of the optical film of the present invention, V ¹ to V ^{3 are} preferably independently a single bond, -O- or -S-, more preferably a single bond or -O-. .

Specific examples of the diamine represented by the formula (3) include an aliphatic diamine, an aromatic diamine, and a mixture thereof. In the present embodiment, the "aromatic diamine" is a diamine in which an amine group is directly bonded to an aromatic ring, and an aliphatic group or other substituent may be contained in a part of the structure. The aromatic ring may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and an anthracene ring, but are not limited thereto. Among these, a benzene ring is preferred. In addition, the "aliphatic diamine" is a diamine in which an amine group is directly bonded to an aliphatic group, and may contain an aromatic group or another substituent in a part of the structure.

The aliphatic diamine may, for example, be a non-cyclic aliphatic diamine such as hexamethylenediamine, or 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane. And a cycloaliphatic diamine such as norbornanediamine and 4,4'-diaminodicyclohexylmethane. These may be used alone or in combination of two or more.

Examples of the aromatic diamine include p-phenylenediamine, meta-phenylenediamine, 2,4-toluenediamine, m-xylylenediamine, p-xylenediamine, and 1,5-diaminonaphthalene. And an aromatic diamine having an aromatic ring such as 2,6-diaminonaphthalene; 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4' -diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl hydrazine, 3, 4'-Diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-amino) Phenoxy)benzene, 4,4'-diaminodiphenylanthracene, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy) Phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2 2'-Dimethylbenzidine, 2,2-bis(trifluoromethyl)benzidine (also described as TFMB), 4,4'-bis(4-aminophenoxy)biphenyl, 9, 9-bis(4-aminophenyl)anthracene, 9,9-bis(4-amino-3-methylphenyl)anthracene, 9,9-bis(4-amino-3-chlorophenyl)茀, and 9,9-bis(4-amino-3-fluorophenyl)anthracene have two An aromatic diamine on the aromatic ring. These may be used alone or in combination of two or more.

An aromatic diamine, preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3, 3'-Diaminodiphenyl ether, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 1,4-bis(4-aminophenoxyl) Benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4- Aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2'-dimethylbenzidine, 2,2-dual ( Trifluoromethyl)-4,4'-benzidine, 4,4'-bis(4-aminophenoxy)biphenyl, preferably 4,4'-diaminodiphenylmethane, 4, 4'-Diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylanthracene, 1,4-bis(4-aminophenoxyl) Benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-dimethyl Anthranil, 2,2-bis(trifluoromethyl)-4,4'-benzidine, 4,4'-bis(4-aminophenoxy)biphenyl. These may be used alone or in combination of two or more.

Among the above-mentioned diamine compounds, from the viewpoints of surface hardness, flexibility, bending resistance, transparency, and yellowness of the optical film of the present invention, it is preferred to use a group selected from aromatic diamines having a biphenyl structure. More than one, more preferably selected from the group consisting of 2,2'-dimethylbenzidine, 2,2-bis(trifluoromethyl)benzidine, 4,4'-bis(4-aminophenoxy) More than one of a group consisting of biphenyl and 4,4'-diaminodiphenyl ether, and more preferably 2,2-bis(trifluoromethyl)benzidine.

In a preferred embodiment of the present invention in which the polyamidoximine resin has a constituent unit derived from a diamine, the polyamidoquinone imide resin is considered from the viewpoint of easily improving the surface hardness and transparency of the optical film of the present invention. It is preferably a constituent unit having at least a diamine represented by the formula (3e') in the formula (3).

[In the formula (3e'), R ¹⁰ to R ¹⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and a hydrogen atom contained in R ¹⁰ to R ¹⁷ , Alternatively, they may be independently substituted with a halogen atom, and * represents a bond. ]

In the formula (3e'), R ¹⁰ to R ¹⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably a hydrogen atom or a carbon number of 1 to More preferably, it is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Here, the hydrogen atoms contained in R ¹⁰ to R ¹⁷ may be independently substituted with a halogen atom. From the viewpoints of surface hardness, flexibility, and transparency of the optical film of the present invention, R ¹⁰ to R ^{17 are more} preferably independently a hydrogen atom, a methyl group, a fluorine group, a chloro group or a trifluoromethyl group. It is a hydrogen atom or a trifluoromethyl group.

In a preferred embodiment of the invention, the polyamidoximine resin preferably has at least a constituent unit derived from a diamine represented by the formula (3e" in the formula (3).

In the formula (3e), * indicates a bond key.]

In this case, the optical film of the present invention has high transparency, and since the polyamidoximine resin has a skeleton of a fluorine element, the solubility of the polyamidoximine resin in a solvent is improved, and the present invention can be produced under pressure. The viscosity of the polyamidoximine varnish used in the optical film is easy to manufacture the optical film of the present invention.

When the polyamidoximine resin has two or more constituent units derived from a diamine, the composition derived from the formula (3) wherein X is a diamine represented by the formula (3e'), preferably the formula (3e") The amount of the unit is preferably 30 mol% or more, more preferably 50%, based on the entire constituent unit derived from the diamine contained in the polyamidoximine resin, from the viewpoint of improving the transparency and ease of production of the optical film. The molar percentage is more than 70% by mole, and more preferably 70% by mole or more. The upper limit of the amount of the constituent unit of the diamine represented by the formula (3e'), preferably the formula (3e"), from the formula (3) It is not particularly limited, and the entire constituent unit derived from the diamine contained in the polyamidoximine resin may be 100 mol% or less. The ratio of the constituent unit of the diamine represented by the formula (3e') or the formula (3e"), wherein X in the formula (3) is, for example, ¹ H-NMR can be used, and the packing ratio of the raw material can also be used. Calculate.

The polyamidoximine resin contained in the optical film of the present invention preferably has at least a constituent unit derived from tetracarboxylic dianhydride from the viewpoints of transparency, hygroscopic property, and solubility in a solvent.

The tetracarboxylic dianhydride may, for example, be a compound represented by the formula (4). The polyamidoximine resin may have one constituent unit derived from tetracarboxylic dianhydride or two or more constituent units derived from tetracarboxylic dianhydride.

In the formula (4), Y represents a tetravalent organic group. ]

The polyamidoximine resin contained in the optical film of the present invention has a preferred embodiment from the constituent unit of the tetracarboxylic dianhydride represented by the formula (4), and the amount of the constituent unit is based on polyamine. The total constituent unit contained in the quinone imine resin is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more. When the amount of the constituent unit of the tetracarboxylic dianhydride represented by the formula (4) is at least the above lower limit, the ratio of the constituent unit derived from the dicarboxylic acid can be suppressed, and it is easy to obtain tan δ in a temperature range of 370 ° C or lower. Peak polyamidoximine resin. Further, the amount of the constituent unit derived from the tetracarboxylic dianhydride represented by the formula (4) is preferably 45 mol% or less, more preferably 40 mol, based on the total structural unit contained in the polyamidoximine resin. Less than or equal to the ear, more preferably 30% by mole or less. When the amount of the constituent unit derived from the tetracarboxylic dianhydride represented by the formula (4) is less than or equal to the above lower limit, the ratio of the constituent unit derived from the dicarboxylic acid can be increased, and a high surface hardness can be easily exhibited.

Y in the formula (4) represents a tetravalent organic group, and preferably an organic group in which a hydrogen atom in the organic group can be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. The tetravalent organic group can be exemplified by the formula (4a), the formula (4b), the formula (4c), the formula (4d), the formula (4e), the formula (4f), the formula (4g), the formula (4h), and the formula. a group represented by (4i) and formula (4j); a group in which a hydrogen atom in the group represented by the formula is substituted with a methyl group, a fluorine group, a chloro group or a trifluoromethyl group; and a tetravalent number of carbon 6 or less a linear hydrocarbon group.

[Formula (4a), Formula (4b), Formula (4c), Formula (4d), Formula (4e), Formula (4f), Formula (4g), Formula (4h), Formula (4i), and Formula (4j) Where * represents a bonding bond, W ¹ represents a single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -Ar-, -SO ₂ -, -CO-, -O-Ar-O--, -Ar-O-Ar-, -Ar-CH ₂ -Ar-, -Ar-C (CH ₃ ) ₂ -Ar- or -Ar-SO ₂ -Ar-. Ar represents an extended aryl group having 6 to 20 carbon atoms which may be substituted by a hydrogen atom or a fluorine atom, and specific examples thereof include a stretching phenyl group. ]

Formula (4a), formula (4b), formula (4c), formula (4d), formula (4e), formula (4f), formula (4g), formula (4h), formula (4i), and formula (4j) Among the bases to be represented, from the viewpoint of surface hardness and flexibility of the optical film of the present invention, a group represented by the formula (4g), the formula (4i) or the formula (4j) is preferred, and the formula (4g) is more preferred. The basis of the representation. Further, W ^{1 is} preferably a single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )- from the viewpoint of surface hardness and flexibility of the optical film of the present invention. , -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -, more preferably a single bond, -O-, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ - Or -C(CF ₃ ) ₂ -, more preferably a single bond, -O-, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -, most preferably -O- or -C( CF ₃ ) ₂ -.

The tetracarboxylic dianhydride represented by the formula (4) may, for example, be an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride. One type of tetracarboxylic dianhydride may be used, and two or more types may be used in combination.

Specific examples of the aromatic tetracarboxylic dianhydride include, for example, non-condensed polycyclic aromatic tetracarboxylic dianhydride, monocyclic aromatic tetracarboxylic dianhydride, and condensed polycyclic aromatic tetracarboxylic dianhydride. Specific examples of the non-condensed polycyclic aromatic tetracarboxylic dianhydride include 4,4'-oxydiphthalic acid dianhydride (also referred to as OPDA) and 3,3',4,4'-diphenyl. Ketone tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2 ',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylfluorene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenoxyphenyl)propane dianhydride, 4,4'- (hexafluoroisopropylidene) diacetic anhydride (also described as 6FDA), 1,2-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyl) Phenyl)ethane dianhydride, 1,2-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, double ( 3,4-Dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 4,4'-(p-phenylenedioxy)diphthalic acid dianhydride, and 4,4' - (m-phenylenedioxy) dicarboxylic acid dianhydride. Further, examples of the monocyclic aromatic tetracarboxylic dianhydride include 1,2,4,5-benzenetetracarboxylic dianhydride and condensed polycyclic aromatic tetracarboxylic dianhydride, and examples thereof include 1, 2, The 4,5-benzenetetracarboxylic dianhydride and the condensed polycyclic aromatic tetracarboxylic dianhydride may, for example, be 2,3,6,7-naphthalenetetracarboxylic dianhydride. These may be used alone or in combination of two or more.

Among these, 4,4'-oxydiphthalic acid dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 2,2', 3,3 are preferred. '-Diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylfluorene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyl) Phenyl) propane dianhydride, 2,2-bis(3,4-dicarboxyphenoxyphenyl)propane dianhydride, 4,4'-(hexafluoroisopropylidene) diruthenic acid dianhydride, 1, 2-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,2-bis(3,4-dicarboxyl) Phenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-di Carboxyphenyl)methane dianhydride, 4,4'-(p-phenylenedioxy)diphthalic acid dianhydride and 4,4'-(m-phenylenedioxy)diphthalic acid dianhydride, more preferably, 4, 4'-oxydiphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride and 4,4'-(hexafluoroisopropylidene)dicarboxylic acid dianhydride.

The aliphatic tetracarboxylic dianhydride may, for example, be a cyclic or acyclic aliphatic tetracarboxylic dianhydride. The cyclic aliphatic tetracarboxylic dianhydride may, for example, be a tetracarboxylic dianhydride having an alicyclic hydrocarbon structure, and specific examples thereof include 1,2,4,5-cyclohexanetetracarboxylic dianhydride. a cycloalkane tetracarboxylic dianhydride such as 1,2,3,4-cyclobutane tetracarboxylic dianhydride or 1,2,34-cyclopentane tetracarboxylic dianhydride; bicyclo[2.2.2] octane -7-ene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl 3,3'-4,4'-tetracarboxylic dianhydride and the positional isomers thereof. These may be used alone or in combination of two or more. Specific examples of the acyclic aliphatic tetracarboxylic dianhydride include, for example, 1,2,3,4-butanetetracarboxylic dianhydride, and 1,2,3,4-pentanetetracarboxylic dianhydride. Etc., these may be used alone or in combination of two or more. Further, a cyclic aliphatic tetracarboxylic dianhydride and an acyclic aliphatic tetracarboxylic dianhydride may be used in combination.

Among the above tetracarboxylic dianhydrides, 4,4'-oxydicarboxylic acid is preferred from the viewpoint of easily improving the surface hardness, flexibility, bending resistance, transparency, and yellowness of the optical film. Anhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3' -biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylfluorene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4, 4'-(hexafluoroisopropylidene)dicarboxylic acid dianhydride, and mixtures thereof, more preferably 4,4'-oxydiphthalic acid dianhydride, 3,3', 4,4'- Biphenyltetracarboxylic dianhydride and 4,4'-(hexafluoroisopropylidene)dicarboxylic acid dianhydride, and mixtures thereof, more preferably 4,4'-(hexafluoroisopropylene Base) dicapric acid dianhydride.

In a preferred embodiment of the present invention, the polyamidoximine resin having a constituent unit derived from a tetracarboxylic dianhydride, preferably having at least Y derived from the formula (4) A constituent unit of the tetracarboxylic dianhydride represented by the formula (4g').

[In the formula (4g'), R ¹⁸ to R ²⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and a hydrogen atom contained in R ¹⁸ to R ²⁵ , Alternatively, they may be independently substituted with a halogen atom, and * represents a bond. In this case, the optical film of the present invention has high transparency, and since the polyamidoximine resin has a highly curved skeleton, the solubility of the polyamidoximine resin in the solvent is improved, and the production cost can be lowered. The viscosity of the polyamidoximine varnish used in the optical film of the invention is easy to manufacture the optical film of the present invention.

In the formula (4g'), R ¹⁸ to R ²⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably a hydrogen atom or a carbon number of 1 to The alkyl group of 6 or more preferably represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the hydrogen atom contained in R ¹⁸ to R ²⁵ may be independently substituted with a halogen atom, respectively. From the viewpoint of the surface hardness and flexibility of the optical film of the present invention, R ¹⁸ to R ^{25 are more} preferably independently a hydrogen atom, a methyl group, a fluorine group, a chloro group or a trifluoromethyl group, particularly preferably a hydrogen atom. Or trifluoromethyl.

In the above preferred embodiment, the polyamidoximine resin preferably has at least a constituent unit derived from the tetracarboxylic dianhydride represented by the formula (4g") in the formula (4).

[In the formula (4g"), * represents a bonding bond.] In this case, the optical film of the present invention has high transparency, and since the polyamidoximine resin has a skeleton of a fluorine-containing element, the polyamide The solubility of the imine resin in a solvent is improved, and the viscosity of the polyamidoximine varnish used in the production of the optical film of the present invention can be lowered, so that the production of the optical film of the present invention can be facilitated.

When the polyamidoximine resin has a constituent unit derived from two or more kinds of tetracarboxylic dianhydride, Y derived from the formula (4) is represented by the formula (4g'), preferably the formula (4g"). The amount of the constituent unit of the tetracarboxylic dianhydride is preferably from the viewpoint of improving the transparency of the optical film and the ease of production, based on the entire constituent unit derived from the tetracarboxylic dianhydride contained in the polyamidoximine resin. 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more. Y derived from the formula (4) is represented by the formula (4g'), preferably the formula (4g") The upper limit of the amount of the constituent unit of the tetracarboxylic dianhydride is not particularly limited, and may be 100 mol% or less based on the entire constituent unit derived from the tetracarboxylic dianhydride contained in the polyamidoximine resin. . The ratio of the constituent unit derived from the formula (4) to the tetracarboxylic dianhydride represented by the formula (4g') or the formula (4g") can be measured, for example, by ¹ H-NMR, or may be derived from a raw material. The filling ratio is calculated.

The polyamidoximine resin contained in the optical film of the present invention may further contain a constituent unit derived from a tricarboxylic acid. The tricarboxylic acid may, for example, be an aromatic tricarboxylic acid, an aliphatic tricarboxylic acid or a ruthenium chloride compound or an acid anhydride of the above analogs. One type of tricarboxylic acid may be used, or two or more types may be used in combination. Specific examples include, for example, an acid anhydride of 1,2,4-benzenetricarboxylic acid; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; phthalic anhydride and benzoic acid as a single bond, -O -, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - or a phenyl-bonded compound.

In a preferred embodiment of the present invention, the optical film of the present invention contains a polyamidoximine resin having a tan δ peak obtained by DMA measurement in the range of 300 to 370 ° C, which is a dicarboxylic acid (such as ruthenium chloride). a dicarboxylic acid analog), a diamine, and a tetracarboxylic acid (a tetracarboxylic acid analog such as ruthenium chloride or tetracarboxylic dianhydride), and optionally a tricarboxylic acid compound such as a ruthenium chloride compound or a tricarboxylic acid anhydride. A condensation type polymer of a polycondensation product of the analog). In this form, the polyamidoximine resin has a constituent unit represented by the formula (5) and a constituent unit represented by the formula (6).

In the formulae (5) and (6), X, Y and Z have the same meanings as described above. ]

X, Y and Z in the formulas (5) and (6) are the same as X in the formula (3), Y in the formula (4) and Z in the formula (2), respectively, for the formula (2) The above description of X, Y and Z in the formula (4) is also applicable to the X, Y and Z in the formulas (5) and (6). The constituent unit represented by the formula (5) is generally a constituent unit derived from a diamine and a tetracarboxylic acid, and the constituent unit represented by the formula (6) is generally a constituent unit derived from a diamine and a dicarboxylic acid.

In a preferred embodiment of the present invention, the polyamidoquinone imide resin having a tan δ peak obtained by DMA measurement in the range of 300 to 370 ° C of the optical film of the present invention may further have the formula (7). The constituent unit shown and/or the constituent unit represented by the formula (8).

In the formula (7), X ¹ represents a divalent organic group, Y ¹ represents a tetravalent organic group, and in the formula (8), X ² represents a divalent organic group, and Y ² represents a trivalent organic group. ]

In the formula (7), Y ¹ each independently represents a tetravalent organic group, and preferably an organic group in which the hydrogen atom in the organic group can be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. Y ¹ can be exemplified by the formula (4a), the formula (4b), the formula (4c), the formula (4d), the formula (4e), the formula (4f), the formula (4g), the formula (4h), and the formula (4i). And a group represented by the formula (4j) and a linear hydrocarbon group having a tetravalent carbon number of 6 or less. The polyamidoximine resin may have a structural unit represented by the formula (7), and may have a structural unit represented by two or more formulas (7) in which Y ¹ and/or X ^{1 are} different from each other.

In the formula (8), Y ² each independently represents a trivalent organic group, and preferably an organic group in which the hydrogen atom in the organic group can be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. Y ² can be exemplified by the formula (4a), the formula (4b), the formula (4c), the formula (4d), the formula (4e), the formula (4f), the formula (4g), the formula (4h), and the formula (4i). Any one of the bond bonds of the group represented by the formula (4j) is substituted with a hydrogen atom and a trivalent carbon number of 6 or less. The polyamidoximine resin may have a structural unit represented by the formula (8), and may have a structural unit represented by two or more formulas (8) in which Y ² and/or X ^{2 are} different from each other.

In the formulae (7) and (8), X ¹ and X ² each independently represent a divalent organic group, and preferably an organic group in which the hydrogen atom in the organic group can be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. X ¹ and X ² can be exemplified by the formula (3a), the formula (3b), the formula (3c), the formula (3d), the formula (3e), the formula (3f), the formula (3g), the formula (3h), and the formula. a group represented by (3i); a group in which a hydrogen atom in the group represented by the formula is substituted with a methyl group, a fluorine group, a chloro group or a trifluoromethyl group; and a chain hydrocarbon group having a carbon number of 6 or less.

In a preferred embodiment of the present invention, the polyamidoximine resin contained in the optical film of the present invention is a constituent unit represented by the formulas (5) and (6), and optionally (7). And / or a constituent unit represented by the formula (8). In this form, the amount of the constituent unit represented by the formula (5) and the constituent unit represented by the formula (6) contained in the polyamidoximine resin is from the viewpoint of easily improving the flexibility and surface hardness of the optical film. The total of the constituent units represented by the formulas (5) and (6) and, as the case of the formula (7) and/or the formula (8), is preferably 80% or more, more preferably 90% or more, and further More preferably 95% or more. Further, the upper limit of the amount of the constituent unit represented by the formula (5) and the formula (6) contained in the polyamidoximine resin is based on the formula (5) and the formula (6), or the formula (7). The sum of the constituent units represented by the formula (8) and/or the formula (8) is usually 100% or less. Further, the above ratio can be measured, for example, by ¹ H-NMR, or can be calculated from the packing ratio of the raw materials.

The polyamidoximine resin contained in the optical film of the present invention preferably contains a halogen atom, more preferably contains a fluorine atom. Specific examples of the fluorine-containing substituent include a fluorine group and a trifluoromethyl group. By containing a halogen atom in the polyamidoximine resin, it is easy to reduce the yellowness (YI value) of the optical film of the present invention, and it is easy to achieve both high flexibility and bending resistance. The halogen atom is preferably a fluorine atom from the viewpoints of reduction in yellowness, reduction in water absorption, and bending resistance of the optical film of the present invention. From the above viewpoints, the polyamidoximine resin is preferably a constituent unit having at least a diamine derived from a fluorine atom and/or a tetracarboxylic dianhydride containing a fluorine atom.

The content of the halogen atom in the polyamidoximine resin is agglomerated by the optical film of the present invention from the viewpoint of a decrease in yellowness (increased transparency), a decrease in water absorption, and deformation inhibition of an optical film. The mass of the amidoxime resin is preferably from 1 to 40% by mass, more preferably from 3 to 35% by mass, still more preferably from 5 to 32% by mass.

Hereinafter, a method for producing a polyamidoximine resin contained in the optical film of the present invention will be described. The polyamidoximine resin can be produced, for example, by subjecting the above-mentioned dicarboxylic acid, diamine, and tetracarboxylic acid as main raw materials to the above-mentioned tricarboxylic acid, which is optionally added together, by condensation polymerization. .

The reaction temperature of the above polycondensation reaction is not particularly limited and is, for example, 50 to 350 °C. The reaction time is also not particularly limited and is, for example, about 30 minutes to 10 hours. The reaction can be carried out in an inert environment or under reduced pressure, as needed. Further, the reaction can be carried out in a solvent, and the solvent can be, for example, a solvent to be used in the preparation of a polyamidoximine varnish.

In the above polycondensation reaction, an imidization catalyst can also be used. The imidization catalyst may, for example, be an aliphatic amine such as tripropylamine, dibutylpropylamine or ethyldibutylamine; N-ethylpiperidine, N-propoperidine, N-butyrrolidine, N-butyro Alicyclic amines such as pyridine and N-propyl hexahydroazide (monocyclic); azabicyclo[2.2.1]heptane, azabicyclo[3.2.1]octane, azabicyclo[2.2.2 An alicyclic amine (polycyclic) such as octane and azabicyclo[3.2.2]nonane; and pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3- Ethylpyridine, 4-ethylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 3,4-cyclopentenopyridine, 5,6,7,8-tetrahydroisoquinoline, and An aromatic amine such as isoquinoline.

In view of improving the visibility and quality of the optical film of the present invention, the optical film of the present invention preferably further contains an additive having a light absorbing function in addition to the above polyamidoximine resin. The additive having a light absorbing function may, for example, be an ultraviolet absorber or a bluing agent. The additive having a light absorbing function is preferably selected from the group consisting of an ultraviolet absorber and a bluing agent because it is easy to improve the visibility and quality of the optical film of the present invention. The optical film of the present invention may contain an additive having a light absorbing function, and may further contain two or more additives having a light absorbing function. Here, when a film having a light absorbing function such as an ultraviolet absorber or a bluing agent is added to a film containing a polyamidoximine resin in the related art, since the heat resistance of the additives is low, heating is performed at a high temperature. In the step of the film containing the polyamidoximine resin, decomposition or the like may occur, which may cause deterioration of the film quality. Therefore, for example, it is necessary to add such an additive to a layer different from the layer containing the polyamidoximine resin, and then apply it to a polyimide film or the like. By the optical film of the present invention containing a polyamidoximine resin having a peak of tan δ in a predetermined temperature range, a sufficiently high surface hardness can be achieved at a relatively low temperature, so that even with a polyamine The layer of the amine resin adds an additive having a light absorbing function to the same layer, and also suppresses decomposition of the additives and the like, and can suppress a decrease in film quality.

The ultraviolet absorber can be appropriately selected and used as a general user of the ultraviolet absorber in the field of a resin material. The ultraviolet absorber may also contain a compound that absorbs light having a wavelength of 400 nm or less. The ultraviolet absorber is, for example, at least one compound selected from the group consisting of a diphenylketone compound, a salicylate compound, a benzotriazole compound, and a triazine compound. When the optical film of the present invention contains an ultraviolet absorber, the deterioration of the polyimide film can be suppressed, so that the visibility of the optical film can be improved. In the present specification, the term "systemic compound" means a derivative of a compound to which the "system compound" is added. For example, the "diphenyl ketone compound" means a diphenyl ketone as a main skeleton and a compound having a substituent bonded to a diphenyl ketone.

When the optical film contains the ultraviolet absorber, the amount of the ultraviolet absorber added may be selected depending on the type of the ultraviolet absorber, and based on the total mass of the optical film, the content is preferably 1% by mass or more, more preferably 2% by mass or more. More preferably, it is 3% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less. The amount of addition is preferably different depending on the ultraviolet absorber to be used, but the amount of addition is adjusted so that the light transmittance at 400 nm is about 20 to 60%, and the light resistance of the optical film of the present invention is easily improved, and transparency is easily obtained. A high optical film is preferred.

The bluing agent can be suitably selected and used as a bluing agent in the field of resin materials. The bluing agent is an additive (dye, pigment) that absorbs light in a wavelength range such as orange to yellow in the visible light range to adjust the hue, and examples thereof include inorganic dyes or pigments such as ultramarine blue, Prussian blue, and cobalt blue; For example, an organic dye or pigment such as an indigo blue agent or a condensed polycyclic ring blue agent. The bluing agent is not particularly limited, and from the viewpoint of heat resistance, light resistance, and solubility, a condensed polycyclic blue agent is preferred, and a bluing agent is more preferred. From the viewpoint of heat resistance, the bluing agent preferably has a thermal decomposition temperature of 200 ° C or higher, preferably 240 ° C or higher. The condensed polycyclic ring-forming agent may, for example, be an anthraquinone-based blue agent, an indigo-based blue agent, or an indigo-based blue agent.

When the optical film contains a bluing agent, the amount of the bluing agent added may be selected depending on the type of the bluing agent, and based on the total mass of the optical film, the basis is preferably 0.01% by mass or more, more preferably 0.02% by mass or more. More preferably, it is 0.03 mass% or more, preferably 1.0 mass% or less, more preferably 0.5 mass% or less, still more preferably 0.2 mass% or less.

The optical film of the present invention may further contain an inorganic material such as inorganic particles in addition to the polyamidoximine resin. The inorganic material may, for example, be an inorganic particle such as a titanium oxide particle, an alumina particle, a zirconium oxide particle or a cerium oxide particle, or an anthracene compound such as a tetra-alkoxy alkane such as ethyl orthosilicate. From the viewpoint of the stability of the polyamidoximine varnish, the inorganic material is preferably inorganic particles, particularly preferably cerium oxide particles. The inorganic particles may be bonded to each other by a molecule having a decane bond (i.e., -SiOSi-).

The average primary particle diameter of the inorganic particles is preferably from 10 to 100 nm, more preferably from 20 to 80 nm, from the viewpoints of transparency of the optical film, mechanical properties, and aggregation inhibition of the inorganic particles. In the present invention, the average primary particle diameter can be determined by measuring the average value of the particle diameter in the fixed direction at 10 points by a transmission electron microscope.

The optical film of the present invention may also contain an inorganic material. The content of the inorganic material in the optical film is preferably from 0 to 90% by mass, more preferably from 0.01 to 60% by mass, still more preferably from 5 to 40% by mass, based on the total mass of the optical film. When the content of the inorganic material is within the above range, it is easy to achieve both transparency and mechanical properties of the optical film.

The optical film of the present invention may also contain other additives. Other additives may, for example, be antioxidants, mold release agents, stabilizers, flame retardants, pH adjusters, cerium oxide dispersants, lubricants, tackifiers, and leveling agents. The content of the other additive is preferably 0% by mass or more and 20% by mass or less, and more preferably 0.01% by mass or more and 10% by mass or less based on the mass of the optical film of the present invention.

(layer composition)

The layer constitution of the optical film of the present invention is not particularly limited, and may be a single layer or a plurality of layers of two or more layers. When the optical film of the present invention further contains an additive such as an additive having a light absorbing function, it is preferable to contain the additive and the polyimide amide resin in one layer from the viewpoint of film formation and economical efficiency of the image display device. . In this case, the optical film of the present invention is more preferably a laminate comprising the additive and the polyimide layer, or a laminate having at least the layer containing the additive and the polyamide amide resin. From the viewpoint of impact resistance, the optical film of the present invention preferably has a multilayer structure having at least two or more layers containing a polyamidoximine resin. When the optical film of the present invention further contains an additive such as an additive having a light absorbing function, it may be a laminate having at least a layer containing the additive and the polyamide amide imide resin, or may have at least a layer containing the additive. A laminate with a layer containing a polyamidoximine resin.

The optical film of the present invention may be a polyamidoquinone laminate which further laminates one or more functional layers in the above layer. The functional layer may, for example, be a layer having various functions such as a hard coat layer, an ultraviolet absorbing layer, an adhesive layer, a refractive index adjusting layer, and a primer layer. The optical film of the present invention may have a singular or plural functional layer. In addition, a functional layer can also have a plurality of functions. For example, an optical film composed of a plurality of layers can be formed on the film containing the polyamidoximine resin to form the above functional layer.

The optical film of the present invention can be produced, for example, by a production method comprising at least the following steps: (1) a step of applying a resin composition containing at least a polyamidamine resin and a solvent to a support; (2-1) a step of drying the coating film of the resin composition at a temperature of 240 ° C or lower and then peeling off the support; or (2-2) drying the coating film of the resin composition at a temperature of 240 ° C or lower Thereafter, the step of peeling off the support and the step of heating the peeled film at a temperature of 240 ° C or lower.

The present invention also provides a method of producing the above optical film.

a resin composition (in the present specification, also referred to as "polyamidiamine imide varnish") containing at least a polyamidoximine resin and a solvent used in the step (1), and mixing the above dicarboxylic acid A diamine, a tetracarboxylic acid, and, if necessary, other components (a tertiary amine which acts as an imidization catalyst, a dehydrating agent, etc.) are reacted to produce a polyamidoximine resin mixture. The tertiary amine may, for example, be an aromatic amine or an aliphatic amine as described above. The dehydrating agent may, for example, be acetic anhydride, propionic anhydride, isobutyric anhydride, trimethylacetic anhydride, butyric anhydride or isovaleric anhydride. A resin composition containing at least a polyamidoximine resin and a solvent is prepared by adding a solvent and, if necessary, the above additives, to the polyamidoximine resin mixture. A weak solvent may be added to the polyamidolimine mixture, and the polyamidoximine resin may be precipitated by a reprecipitation method, and the precipitate may be removed by drying to dissolve the precipitated polyamidolimine resin precipitate. A mixture of polyamidoximines is obtained as a solvent. Further, in place of the polyamidoximine resin mixture, a solution of the commercially available polyamidoximine resin or a commercially available solid amidoxime resin may be dissolved in a solvent to form a solution.

The solvent used for the production of the polyamidoximine varnish is not particularly limited as long as it can dissolve the polyamidoximine resin. The related solvent may, for example, be a guanamine solvent such as N,N-dimethylacetamide or N,N-dimethylformamide; or a lactone solvent such as γ-butyrolactone or γ-valerolactone. a sulfur-containing solvent such as dimethylhydrazine, dimethyl hydrazine or cyclobutyl hydrazine; a carbonate-based solvent such as ethylene carbonate or propylene carbonate; and a combination thereof (mixed solvent). Among these solvents, a guanamine solvent or a lactone solvent is preferred, and a solvent containing dimethylacetamide is more preferred. Further, the polyamidoximine varnish may contain water, an alcohol solvent, a ketone solvent, an acyclic ester solvent, an ether solvent or the like.

Next, the polyamidoquinone imide is coated on a support such as a resin substrate, a SUS tape, or a glass substrate by a known roll-to-roll or batch method. A varnish can form a coating film of polyamidoximine varnish. Examples of the support include a PET film, a PEN film, a polyimide film, and a polyimide film. Among them, from the viewpoint of excellent heat resistance, a PET film, a PEN film, a polyimide film, and other polyamidoximine films are preferable. From the viewpoint of adhesion to the optical film of the present invention and cost, a PET film is more preferable.

Next, in the step (2-1) or the step (2-2), the coating film of the polyamidoximine varnish is dried at a temperature of 240 ° C or lower, dried, and then peeled off from the support. The drying of the coating film is preferably carried out at a temperature of from 50 to 240 °C. The coating film may be dried in an inert environment or under reduced pressure as needed. The optical film of the present invention can be obtained by peeling off the coating film from the support after drying. Further, the production method of the present invention may further comprise the step of, for example, removing the surface hardness (for example, pencil hardness) of the optical film of the present invention, as described in the step (2-2). The optical film is heated at a temperature of 240 ° C or lower.

A surface treatment step of applying a surface treatment may also be performed on the surface of at least one side of the optical film manufactured above. The surface treatment may, for example, be a UV ozone treatment, a plasma treatment, or a corona discharge treatment.

When the heating is carried out in the step carried out after the step (2-1) or the step (2-2), the temperature is preferably 280 ° C or lower, more preferably 240 ° C or lower.

In a preferred embodiment of the present invention, the optical film of the present invention contains an additive such as an additive having a light absorbing function, when the optical film of the present invention contains a polyamidoximine resin and the additive in the same layer, the layer The polyamidoximine varnish obtained by further adding the additive to the resin composition containing at least the above-mentioned polyamidoximine resin and a solvent can be produced in the same manner as described above. In a preferred embodiment of the present invention, which comprises an additive such as an additive having a light absorbing function and a polyamidoximine resin in a layer, it is preferred to use a thermal decomposition temperature of 200 ° C or higher, more preferably 240 ° C or higher. additive.

The optical film of the present invention may further have a functional layer. The functional layer may, for example, be a layer having various functions such as a hard coat layer, an ultraviolet absorbing layer, an adhesive layer, a refractive index adjusting layer, and a primer layer. The optical film of the present invention may have a singular or plural functional layer. In addition, a functional layer can also have a plurality of functions.

The hard coat layer is preferably disposed on the visually recognizable side surface of the optical film. The hard coat layer may have a single layer structure or a multilayer structure. The hard coat layer contains a hard coat resin, and the hard coat resin may, for example, be an acrylic resin, an epoxy resin, a urethane resin, a chlorotoluene resin, a vinyl resin or a polyoxyn resin. An ultraviolet curable type, an electron beam hardening type, or a thermosetting type resin such as a mixed resin. In particular, the hard coat layer preferably contains an acrylic resin from the viewpoint of mechanical properties such as surface hardness and industrial viewpoint. Further, in a preferred embodiment of the present invention, since the optical film of the present invention has a high surface hardness, it has sufficient surface hardness when used in an image display device or the like even without a hard coat layer. Therefore, when the optical film of the present invention is further provided with a hard coat layer, the surface hardness of the optical film can be further improved.

The ultraviolet absorbing layer is a layer having an ultraviolet absorbing function, and may be, for example, a main material selected from the group consisting of an ultraviolet curing type transparent resin, an electron beam curing type transparent resin, and a thermosetting type transparent resin, and a main material dispersed in the main material. It is composed of a UV absorber. The functional layer can easily suppress the change in the yellowness due to light irradiation by providing the ultraviolet absorbing layer.

The adhesive layer is a layer having an adhesive function and has a function of allowing the optical film of the present invention to follow other members. The material for forming the adhesive layer can also be generally known. For example, a thermosetting resin composition or a photocurable resin composition can be used.

The adhesive layer may be composed of a resin composition containing a component having a polymerizable functional group. In this case, by adhering the optical film to another member and then polymerizing the resin composition constituting the adhesive layer, a strong adhesion can be achieved. The adhesive strength of the optical film of the present invention and the adhesive layer may be 0.1 N/cm or more, or 0.5 N/cm or more.

The adhesive layer may also contain a thermosetting resin composition or a photocurable resin composition as a material. In this case, the resin composition can be polymerized and hardened by supplying energy after the event.

The adhesive layer may also be a layer composed of an adhesive which is attached to the object by pressure bonding, called Pressure Sensive Adhesive (PSA). The pressure-sensitive adhesive may be an adhesive having a "adhesive property at normal temperature and a slight pressure to adhere to the material to be adhered" (JIS K6800), or "a specific component contained in a protective film (microcapsule) A microcapsule type adhesive which is a binder (JIS K6800) which can maintain stability by a suitable means (pressure, heat, etc.).

The hue adjustment layer is a layer having a hue adjustment function, and is a layer which can adjust the optical film of the present invention to the intended hue. The hue adjustment layer is, for example, a layer containing a resin and a coloring agent. Examples of the coloring agent include inorganic pigments such as titanium oxide, zinc oxide, iron oxide red, titanium oxide-based fired pigment, ultramarine, cobalt aluminate, and carbon black; azo compounds, quinophthalone compounds, and hydrazines; An organic pigment such as an anthraquinone compound, an anthraquinone compound, an isoindolinone compound, a indigo compound, a quinoline yellow compound, a reduced (Threne) compound, or a diketopyrrolopyrrole compound; barium sulfate; A body pigment such as calcium carbonate; and a dye such as a basic dye, an acid dye, and a mordant dye.

The refractive index adjusting layer is a layer having a function of adjusting the refractive index, and has a refractive index different from that of the layer containing the polyamidoximine resin in the optical film of the present invention, and can impart a predetermined refractive index to the optical film of the present invention. Layer. The refractive index adjusting layer may be, for example, a resin layer containing a suitably selected resin and, if appropriate, a pigment, or a metal thin film.

The pigment whose refractive index is adjusted may, for example, be cerium oxide, aluminum oxide, cerium oxide, tin oxide, titanium oxide, zirconium oxide or cerium oxide. The average primary particle diameter of the pigment may be 0.1 μm or less. By making the average primary particle diameter of the pigment to be 0.1 μm or less, it is possible to prevent the scattering of light passing through the refractive index adjusting layer, and to prevent a decrease in transparency.

Examples of the metal used for the refractive index adjusting layer include metals such as titanium oxide, cerium oxide, zirconium oxide, zinc oxide, tin oxide, antimony oxide, indium oxide, titanium oxynitride, titanium nitride, cerium oxynitride, and cerium nitride. Oxide or metal nitride.

The optical film of the present invention has a panel (i.e., a glass film) for use as a panel of an image display device, particularly a flexible display. The optical film of the present invention can be disposed as a panel on the visual recognition side surface of an image display device, particularly a flexible display. The panel has the function of protecting the image display elements in the flexible display.

The image display device may be, for example, a wearable device such as a television, a smart phone, a mobile phone, a car navigation, a tablet computer, a portable game machine, a paper, an indicator, a bulletin board, a watch, and a smart watch. The flexible display may, for example, be an image display device as described above having flexible characteristics.

 [Examples]  

Hereinafter, the present invention will be described in more detail by way of examples. In the examples, "%" and "parts" mean the meaning of mass % and mass parts unless otherwise stated. First, the evaluation method will be described.

<Measurement of Weight Average Molecular Weight (Mw)>

The weight average molecular weight (Mw) of the polyamidoximine resin is determined by gel permeation chromatography (GPC) and is obtained in terms of standard polystyrene. The specific measurement conditions are as follows.

(1) Pretreatment method

The polyamidoximine resin was added to a DMF eluent (10 mM lithium bromide solution) so as to have a concentration of 2 mg/mL, and heated at 80 ° C for 30 minutes with stirring. After cooling, it was filtered through a 0.45 μm membrane filter. The solution was used as a measurement solution.

(2) Measurement conditions

Pipe column: TSKgel SuperAWM-H×2+SuperAW2500×1 (6.0mm I.D.×150mm×3) (all are made by Tosoh Co., Ltd.)

Lysate: DMF (addition of 10 mM lithium bromide)

Flow rate: 1.0mL/min

Detector: RI detector

Column temperature: 40 ° C

Injection volume: 100μL

Molecular weight standard: standard polystyrene

<Measurement of tan δ and tan δ peak temperature>

The DMA Q800 manufactured by TA Instrument Co., Ltd. was used for measurement under the following samples and conditions to obtain a tan δ curve of the ratio of the loss modulus to the value of the storage modulus. From the apex of the peak of the tan δ curve, the tan δ peak temperature of the polyamidoximine resin was calculated.

Sample: length 5-15mm, width 5mm

Test mode: DMA Multiple-frequency-strain

Test mode detailed conditions:

(1) Clamp: Tension: Film (Film)

(2) Amplitude: 5μm

(3) Frequency (Frequency): 10Hz (no change in the whole temperature range)

(4) Preload Force: 0.01N

(5) Force Track (Force Track): 125N

Temperature conditions: (1) Heating range: normal temperature to 400 ° C, (2) heating rate: 5 ° C / min

Main data collected: (1) Storage modulus (E'), (2) Loss modulus (E"), (3) tan δ (E"/E')

<Measurement of imidization rate>

The imidization ratios of the polyimine resin and the polyamidoximine resin used in the examples and the comparative examples were measured by NMR, and some of the structures (A) to (E) represented by the formula (XXX) were used. The signal of the proton in the calculation. The method for calculating the imidization ratio from the measurement conditions and the obtained results is as follows.

(pre-processing method)

The sample was dissolved in dimethyl hydrazine hydride (DMSO-d6) to prepare a 2% by mass solution, which was used as a measurement sample.

(measurement conditions)

Measuring device: 600MHz NMR device manufactured by Bruker AVANCE600

Sample temperature: 303K

Determination method: ¹ H-NMR, HSQC

(Method for calculating the imidization ratio of polyimine resin)

In the ¹ H-NMR spectrum obtained by using a solution containing a polyimine resin as a measurement sample, the integrated value of the signal from the proton (A) in the formula (XXX) is taken as Int _A and will be derived from the proton (B). The integrated value of the signal is taken as Int _B . From these values, the imidization ratio (%) was determined by the formula (NMR-1).

Amination rate (%) = 100 × (1-Int _B / Int _A ) (NMR-1)

(Method for calculating the imidization ratio of polyamidoximine resin)

In the HSQC spectrum obtained by using a solution containing a polyimide resin as a measurement sample, the integrated value of the signal from the proton (C) in the formula (XXX) is taken as Int _c and will be derived from the proton (D) and the proton (E). The average value of the integral value of the signal is taken as Int _DE . From these values, the β value was obtained by the formula (NMR-2).

β=Int _DE /Int _c (NMR-2)

Next, the β value of the plural polyimine resin was determined by the formula (NMR-2) and the imidization ratio (%) was determined by the formula (NMR-1), and the correlation was obtained from the result (NMR). -3).

Amination rate (%) = -115.9 × β + 100 (NMR-3)

Then, in the HSQC spectrum obtained by using a solution containing a polyamidoximine resin as a measurement sample, the β value was obtained by the same formula (NMR-2) as described above. This β value was substituted into the above correlation formula (NMR-3), whereby the imidization ratio (%) of the polyamidoximine resin was obtained.

<Measurement of total light transmittance (Tt)>

The total light transmittance (Tt) of the sample was measured by a self-directed direct reading haze computer HGM-2DP manufactured by Suga Tester Co., Ltd. according to JIS K7105:1981.

<Measurement of yellowness (YI value)>

The yellowness of the sample (Yellow Index: YI value) was measured in accordance with JIS K 7373:2006 using an ultraviolet visible near-infrared spectrophotometer V-670 manufactured by JASCO Corporation. After background measurement was performed without a sample, the sample was placed in a sample holder, and the transmittance of light of 300 to 800 nm was measured to obtain 3 stimulation values (X, Y, and Z). The YI value is calculated according to the following formula.

YI=100×(1.2769X-1.0592Z)/Y

<Measurement of surface hardness>

The surface hardness of the sample was measured according to JIS K5600-5-4:1999, and the pencil hardness of the surface of the sample was measured. The measurement was carried out under the conditions of a load of 100 g and a scanning speed of 60 mm/min, and the presence or absence of damage was evaluated under the illuminance condition of a light amount of 4000 lux to determine the pencil hardness.

<Measurement of elastic modulus>

The elastic modulus of the sample was measured using Autograph AG-IS manufactured by Shimadzu Corporation. A sample cut into a width of 10 mm was used as a test piece, and the S-S curve was measured under the conditions of a distance between the jigs of 500 mm and a tensile speed of 20 mm/min, and the elastic modulus was calculated from the inclination angle thereof.

<Measurement of bending resistance>

For the bending resistance of the sample, the MIT folding fatigue tester (type 0530) manufactured by Toyo Seiki Seisakusho Co., Ltd. was used, and the number of times of repeated bending was measured. A sample cut into a thickness of 50 μm and a width of 10 mm was used as a test piece, and the number of times of repeated bending until the film was broken was measured under the conditions of R = 1 mm, 135 °, weighting of 0.75 kgf, and speed of 175 cpm.

[Manufacturing Example 1: Preparation of Polyamidoximine Resin (1)]

In a 1 L separable flask equipped with stirring blades under nitrogen atmosphere, 2,2'-bis(trifluoromethyl)benzidine (TFMB) 52 g (162.38 mmol) and N,N-dimethylacetamide were added. (DMAc) 734.10g, TFMB was dissolved in DMAc with stirring at room temperature. Next, 28.90 g (65.05 mmol) of 4,4'-(hexafluoroisopropylidene)dicarboxylic acid dianhydride (6FDA) was added to the flask, and the mixture was stirred at room temperature for 3 hours. Thereafter, 28.80 g (97.57 mmol) of 4,4'-oxybis(benzylidene chloride) (OBBC) was added to the flask, and the mixture was stirred at room temperature for 1 hour.

Next, 7.49 g (94.65 mmol) of pyridine and 26.56 g (260.20 mmol) of acetic anhydride were added to the flask, and the mixture was stirred at room temperature for 30 minutes, and then heated to 70 ° C in an oil bath, and stirred for further 3 hours to obtain a reaction mixture.

The obtained reaction liquid was cooled to room temperature, and a large amount of methanol was introduced into a filament form, and the deposited precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C to obtain a polyamidoximine resin (1). According to the above measurement method, the weight average molecular weight (Mw), the tan δ peak temperature, and the imidization ratio of the polyamidoximine resin (1) were measured, and the Mw was 200,000, the tan δ peak temperature was 345 ° C, and the imidization ratio was determined. It is 96%.

[Example 1: Film formation of polyamidoximine film (1)]

The polyamidoximine resin (1) obtained in Production Example 1 was added to DMAc to have a concentration of 15% by mass to prepare a polyamidoximine varnish (1). The obtained polyamidoximine varnish (1) was applied to a smooth surface of a polyester substrate (trade name "A4100", manufactured by Toyobo Co., Ltd.) so that the thickness of the self-supporting film was 55 μm using a spreader. After drying at 50 ° C for 30 minutes and then drying at 140 ° C for 15 minutes, the obtained coating film was peeled off from the polyester substrate to obtain a self-supporting film.

The self-supporting film was fixed to a metal frame and dried at 230 ° C for 30 minutes under the atmosphere to obtain a polyimide film having a thickness of 50 μm (1).

[Example 2: Film formation of polyamidoximine film (2)]

In the polyamidoximine resin (1) obtained in Production Example 1, DMAc was added to a concentration of 15% by mass, and then 100 parts by mass of the polyamidoximine resin (1) was mixed with 4 parts by mass of the ultraviolet absorber. (Sushi Chemical Co., Ltd., product name "Sumisorb 340"), made of polyamidamine varnish (2). A polyamidoxime film having a thickness of 50 μm was produced in the same manner as in Example 1 except that the polyamidoximine varnish (2) was used instead of the polyamidoximine varnish (1). 2).

[Example 3: Film formation of polyamidoximine film (3)]

The polyamidoquinone imide resin (1) obtained in Production Example 1 was added with DMAc so as to have a concentration of 15% by mass, and then 100% by mass of the polyamidoximine resin (1) was mixed with 0.05% by mass of the blue agent. (The product name "Violet B" made by CHEMIPLAS) is made into a polyamidoximine varnish (3). A polyamidoximine film having a thickness of 50 μm was produced in the same manner as in Example 1 except that the polyamidoximine varnish (3) was used instead of the polyamidoximine varnish (1). 3).

[Manufacturing Example 2: Preparation of Polyamidoximine Resin (2)]

Under a nitrogen atmosphere, a 1 L separable flask equipped with a stirring blade was charged with TFMB 52 g (162.38 mmol) and DMAc 705.94 g, and TFMB was dissolved in DMAc while stirring at room temperature. Next, 6FDA 25.28 g (56.92 mmol) was added to the flask, and the mixture was stirred at room temperature for 3 hours. Then, 21.60 g (73.18 mmol) of OBBC was added to the flask, and then 6.60 g (32.52 mmol) of p-xylylene chloride (TPC) was added to the flask, and the mixture was stirred at room temperature for 1 hour. Next, 8.11 g (102.53 mmol) of pyridine and 23.24 g (227.67 mmol) of acetic anhydride were added to the flask, and the mixture was stirred at room temperature for 30 minutes, and then heated to 70 ° C in an oil bath, and stirred for further 3 hours to obtain a reaction mixture.

The obtained reaction liquid was cooled to room temperature, and a large amount of methanol was introduced into a filament form, and the deposited precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C to obtain a polyamidoximine resin (2). According to the above measurement method, the weight average molecular weight (Mw), the tan δ peak temperature, and the imidization rate of the polyamidoximine resin (2) were measured, and the Mw was 180,000, and the tan δ peak temperature was 340 ° C. The hydrazine imidation rate is 99%.

[Example 4: Film formation of polyamidoximine film (4)]

The polyamidoximine resin (2) obtained in Production Example 2 was added to DMAc to have a concentration of 15% by mass to prepare a polyamidoximine varnish (4). A polyamidoximine film having a thickness of 50 μm was obtained in the same manner as in Example 1 except that the polyamidoximine varnish (4) was used instead of the polyamidoximine varnish (1). 4).

[Example 5: Film formation of polyamidoximine film (5)]

In the polyamidoximine resin (2) obtained in Production Example 2, DMAc was added to a concentration of 15% by mass, and then 100 parts by mass of the polyamidoximine resin (2) was mixed with 4 parts by mass of the ultraviolet absorber. (Sushi Chemical Co., Ltd., product name "Sumisorb 340"), produced as a polyamide imimine varnish (5). A polyamidoximine film having a thickness of 50 μm was obtained in the same manner as in Example 1 except that the polyamidoximine varnish (5) was used instead of the polyamidoximine varnish (1). 5).

[Example 6: Film formation of polyamidoximine film (6)]

The polyamidoximine resin (2) obtained in Production Example 2 was added with DMAc to have a concentration of 15% by mass, and then 100% by mass of the polyamidoximine resin (2) was mixed with 0.05% by mass of the blue agent. (The product name "Violet B" made by CHEMIPLAS) is made into a polyamide imimine varnish (6). A polyamidoximine film having a thickness of 50 μm was obtained in the same manner as in Example 1 except that the polyamidoximine varnish (6) was used instead of the polyamidoximine varnish (1). 6).

[Manufacturing Example 3: Preparation of Polyamidoximine Resin (3)]

Under a nitrogen atmosphere, a 1 L separable flask equipped with a stirring blade was placed, and TFMB 52 g (162.38 mmol) and DMAc 698.10 g were added, and TFMB was dissolved in DMAc while stirring at room temperature. Next, 6FDA 25.28 g (56.92 mmol) was added to the flask, and the mixture was stirred at room temperature for 3 hours. Thereafter, 20.43 g (73.18 mmol) of BPDOC was added to the flask, and then 6.60 g (32.52 mmol) of p-xylylene chloride (TPC) was added to the flask, and the mixture was stirred at room temperature for 1 hour. Next, 8.11 g (102.53 mmol) of pyridine and 23.24 g (227.67 mmol) of acetic anhydride were added to the flask, and the mixture was stirred at room temperature for 30 minutes, and then heated to 70 ° C in an oil bath, and stirred for further 3 hours to obtain a reaction mixture.

The obtained reaction liquid was cooled to room temperature, and a large amount of methanol was introduced into a filament form, and the deposited precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C to obtain a polyamidoximine resin (3). According to the above measurement method, the weight average molecular weight (Mw), the tan δ peak temperature, and the imidization ratio of the polyamidoximine resin (3) were measured, and the Mw was 200,000, the tan δ peak temperature was 380 ° C, and the imidization ratio was determined. It is 99%.

[Comparative Example 1: Film formation of polyamidoximine film (7)]

The polyamidoximine resin (3) obtained in Production Example 3 was added to DMAc to have a concentration of 15% by mass to prepare a polyamidoximine varnish (7). The polyamidoximine varnish (1) was replaced with a polyamidoximine varnish (7), and the self-supporting film fixed to the metal frame was dried at 230 ° C for 30 minutes under the atmosphere, and the self-supporting film was allowed to be dried. A polyamidoximine film (7) having a thickness of 50 μm was obtained in the same manner as in Example 1 except that it was dried at 300 ° C for 30 minutes under the atmosphere.

[Comparative Example 2: Film formation of polyamidoximine film (8)]

Polyacetamide having a thickness of 50 μm was produced in the same manner as in Example 1 except that the polyamidoximine varnish (7) obtained in Comparative Example 1 was used instead of the polyamidoximine varnish (1). Amidinoin film (8).

[Manufacturing Example 4: Preparation of Polyamidoximine Resin (4)]

Under a nitrogen atmosphere, a 1 L separable flask equipped with a stirring blade was charged with TFMB 52 g (162.38 mmol) and DMAc 655.58 g, and TFMB was dissolved in DMAc while stirring at room temperature. Next, 6FDA 23.84 g (53.67 mmol) was added to the flask, and the mixture was stirred at room temperature for 3 hours. Thereafter, 22.12 g (108.96 mmol) of p-xylylene chloride (TPC) was added to the flask, and the mixture was stirred at room temperature for 1 hour. Next, 8.36 g (105.69 mmol) of pyridine and 21.91 g (214.66 mmol) of acetic anhydride were added to the flask, and the mixture was stirred at room temperature for 30 minutes, and then heated to 70 ° C using an oil bath, and stirred for further 3 hours to obtain a reaction mixture.

The obtained reaction liquid was cooled to room temperature, and a large amount of methanol was introduced into a filament form, and the deposited precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C to obtain a polyamidoximine resin (4). According to the above measurement method, the weight average molecular weight (Mw), the tan δ peak temperature, and the imidization ratio of the polyamidoximine resin (4) were measured, and the Mw was 200,000, the tan δ peak temperature was 379 ° C, and the imidization ratio was determined. It is 96%.

[Comparative Example 3: Film formation of polyamidoximine film (9)]

The polyamidoximine resin (4) obtained in Production Example 4 was added to DMAc to have a concentration of 15% by mass to prepare a polyamidoximine varnish (8). The polyamidoximine varnish (1) was replaced with a polyamidoximine varnish (8), and the self-supporting film fixed to the metal frame was dried at 300 ° C for 30 minutes under the atmosphere, and the self-supporting film was allowed to be dried. A polyamidoximine film (9) having a thickness of 50 μm was obtained in the same manner as in Example 1 except that it was dried at 300 ° C for 30 minutes under the atmosphere.

[Comparative Example 4: Film formation of polyamidoximine film (10)]

Polyacetamide having a thickness of 50 μm was produced in the same manner as in Example 1 except that the polyamidoximine varnish (8) obtained in Comparative Example 3 was used instead of the polyamidoximine varnish (1). Amidinoin film (10).

[Comparative Example 5: Film formation of polyamidoximine film (11)]

The same manner as in Example 1 was carried out except that the self-supporting film fixed to the metal frame was dried at 230 ° C for 30 minutes under the atmosphere, and the self-supporting film was dried at 300 ° C for 30 minutes under the atmosphere. A polyimide film having a thickness of 50 μm (11).

[Comparative Example 6: Film formation of polyamidoximine film (12)]

The same manner as in Example 2 was carried out except that the self-supporting film fixed to the metal frame was dried at 230 ° C for 30 minutes under the atmosphere, and the self-supporting film was dried at 300 ° C for 30 minutes under the atmosphere. A polyimide film having a thickness of 50 μm (12).

[Comparative Example 7: Film formation of polyamidoximine film (13)]

The same manner as in Example 4 was carried out except that the self-supporting film fixed to the metal frame was dried at 230 ° C for 30 minutes under the atmosphere, and the self-supporting film was dried at 300 ° C for 30 minutes under the atmosphere. A polyimide film having a thickness of 50 μm (13).

[Comparative Example 8: Film formation of polyamidoximine film (14)]

The same procedure as in Example 5 was carried out except that the self-supporting film fixed to the metal frame was dried at 230 ° C for 30 minutes under the atmosphere, and the self-supporting film was dried at 300 ° C for 30 minutes under the atmosphere. A polyimide film having a thickness of 50 μm (14).

[Manufacturing Example 5: Preparation of Polyimine Resin (5)]

Under a nitrogen atmosphere, a 1 L separable flask equipped with a stirring blade was charged with TFMB 52 g (162.38 mmol) and DMAc 831.46 g, and TFMB was dissolved in DMAc while stirring at room temperature. Next, 6FDA 72.24 g (16.262 mmol) was added to the flask, and the mixture was stirred at room temperature for 5 hours. Next, 9.65 g (121.97 mmol) of pyridine and 66.41 g (650.49 mmol) of acetic anhydride were added to the flask, and the mixture was stirred at room temperature for 30 minutes, and then heated to 70 ° C using an oil bath, and stirred for further 3 hours to obtain a reaction mixture.

The obtained reaction liquid was cooled to room temperature, and a large amount of methanol was introduced into a filament form, and the deposited precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C to obtain a polyimine resin (5). According to the above measurement method, the weight average molecular weight (Mw), the tan δ peak temperature, and the imidization ratio of the polyimine resin (5) were measured, and the Mw was 220,000, the tan δ peak temperature was 350 ° C, and the imidization ratio was 99. %.

[Comparative Example 9: Film formation of polyimine film (15)]

To the obtained polyimine resin (5), DMAc was added to have a concentration of 15% by mass to prepare a polyimide varnish (9). A polyimide film (15) having a thickness of 50 μm was produced in the same manner as in Example 1 except that a polyimine varnish (9) was used instead of the polyamidoximine varnish (1).

[Manufacturing Example 6: Preparation of Polyamidoximine Resin (6)]

Under a nitrogen atmosphere, a 1 L separable flask equipped with a stirring blade was charged with 14.67 g (45.8 mmol) of TFMB and 233.3 g of DMAc, and TFMB was dissolved in DMAc while stirring at room temperature. Next, 4.283 g (13.8 mmol) of 4,4'-oxydiphthalic acid dianhydride (OPDA) was added to the flask, and the mixture was stirred at room temperature for 16.5 hours. Thereafter, 1.359 g (4.61 mmol) of OBBC and 5.609 g (27.6 mmol) of TPC were placed in the flask, and the mixture was stirred at room temperature for 1 hour. Next, 4.937 g (48.35 mmol) of acetic anhydride and 1.501 g (16.12 mmol) of 4-methylpyridine were added to the flask, and the mixture was stirred at room temperature for 30 minutes, and then heated to 70 ° C in an oil bath and stirred for 3 hours. The reaction solution.

After cooling the obtained reaction liquid to room temperature, 360 g of methanol and 170 g of ion-exchanged water were added to obtain a precipitate of polyamidoximine. This was immersed in methanol for 12 hours, collected by filtration, and washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C to obtain a polyimine resin (6). According to the above measurement method, the weight average molecular weight (Mw), the tan δ peak temperature, and the imidization ratio of the polyimine resin (6) were measured, and Mw was 259,000, and the tan δ peak temperature was 362 °C.

[Example 7: Film formation of polyamidoximine film (16)]

The polyamidoximine resin (6) obtained in Production Example 6 was added to GBL to have a concentration of 12% by mass to prepare a polyamidoximine varnish (16). The polyamidoximine varnish (1) was replaced with a polyamidoximine varnish (16), and the self-supporting film fixed to the metal frame was dried at 200 ° C for 30 minutes, except that the same procedure as in Example 1 was carried out. A polyamidoximine film (16) having a thickness of 50 μm was obtained in the same manner.

The polyacrylamide imine films (1) to (14) and (16) and the polyimine film (15) obtained in the above examples and comparative examples were measured for total light transmittance according to the above measurement method. (Tt), yellowness (YI value), pencil hardness, modulus of elasticity, and bending resistance (number of times of repeated bending). The results obtained are shown in Table 1. Further, the numbers of the polyamidimide resin or the polyimide resin contained in the films are also shown in Table 1.

Claims (12)

 An optical film comprising a polyamidoximine resin having a YI value of 3 or less, and the polyamidoximine resin having a peak of tan δ obtained by DMA measurement in a range of 300 to 370 °C.    The optical film according to claim 1, wherein the optical film has a pencil hardness of 3 B or more according to an illuminance of 4000 lux, as measured according to ASTM D 3363.    The optical film according to claim 1 or 2, further comprising an additive having a light absorbing function.    The optical film according to any one of claims 1 to 3, wherein the light absorbing additive is selected from the group consisting of an ultraviolet absorber and a bluing agent.    The optical film according to any one of claims 1 to 4, wherein the polyamidoximine resin contains a fluorine atom.   The optical film according to any one of claims 1 to 5, wherein the polyamidoximine resin contains at least a constituent unit represented by the formula (1), In the formula (1), R ¹ to R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and a hydrogen atom contained in R ¹ to R ⁸ may be respectively Substituted independently with a halogen atom, A independently represents -O-, -S-, -CO- or -NR ⁹ -, and R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms which can be substituted with a halogen atom, and m is 1 to An integer of 4, * indicates a keying key.  The optical film according to any one of claims 1 to 6, wherein the polyamidoximine resin has at least a constituent unit derived from a dicarboxylic acid.    The optical film according to any one of claims 1 to 7, wherein the polyamidoximine resin has at least a diamine derived from a fluorine atom and/or a tetracarboxylic dianhydride containing a fluorine atom. The constituent unit.    The optical film according to any one of claims 1 to 8, which has a thickness of 20 μm or more.    A method for producing an optical film, the method comprising at least the steps of: (1) applying a resin composition containing at least a polyamidoximine resin and a solvent to a support; and (2-1) The coating film of the resin composition is dried at a temperature of 240 ° C or lower and then peeled off from the support; or (2-2) the coating film of the resin composition is dried at a temperature of 240 ° C or lower, and then peeled off from the support. And the step of heating the peeled film at a temperature of 240 ° C or lower.    The manufacturing method according to claim 10, wherein the resin composition further contains an additive having a light absorbing function.    The manufacturing method according to claim 10, wherein the solvent comprises dimethylacetamide.