TW202132423A - Method for producing polyamide-based resin powder including bringing a polyamide-based resin solution (a) into contact with a poor solvent solution (b1) - Google Patents

Abstract

The present invention provides a method for producing polyamide-based resin powder that can easily and efficiently manufacture polyamide-based resin powders with smaller particle diameters and smaller particle size differences. The manufacturing method of the polyamide-based resin powder of the present invention at least includes a contact step of bringing a polyamide-based resin solution (a) into contact with a poor solvent solution (b1). The polyamide-based resin solution (a) is obtained by dissolving polyamide-based resins in a good solvent for the polyamide-based resin. The poor solvent solution (b1) contains at least one poor solvent for the polyamide-based resin. An area of a supply interface region in the contact step above is set to Xm2. When an addition rate of the polyamide-based resin solution (a) or the poor solvent solution (b) is set to Y kg/min, an addition flux below 400 is calculated according to the formula (A): addition flux ((kg/min)/m2)=Y/X.

Description

Manufacturing method of polyamide resin powder

The present invention relates to a manufacturing method of polyamide resin powder.

At present, image display devices such as liquid crystal display devices or organic EL display devices are not only used in televisions, but also widely used in various applications such as mobile phones and smart watches. With the expansion of such uses, an image display device (flexible display) with flexible characteristics is being sought.

The image display device includes display elements such as a liquid crystal display element or an organic EL display element, and also includes constituent members such as a polarizing plate, a phase difference plate, and a front panel. In order to achieve a flexible display, all the constituent members must have flexibility.

So far, glass has been used as the front panel. Glass has high transparency and can exhibit high hardness according to the type of glass, but on the other hand, it has very high rigidity and is easy to break, so it is difficult to use as a front panel material for flexible displays.

Therefore, research is underway to use polymer materials as a material to replace glass. Before the polymer material is included, the panel tends to exhibit flexibility characteristics, so it is expected to be used in various applications. As the resin having flexibility, various resins may be mentioned, for example, polyamide resins and polyimide resins.

When using polyamide-based resins and polyimide-based resins to manufacture front panels and other components, powders of these resins are used for easy handling. For example, Patent Document 1 discloses a polyimide powder, which has a specific average particle size and can obtain a film with a light transmittance of 80% or more at 450 nm. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2017/179367

[The problem to be solved by the invention]

The inventor of the present invention studied the production method of polyamide-based resin powder and found that the drying of polyamide-based resin powder with small particle size and small difference in particle size during the production of polyamide-based resin powder In the step, the drying time is shortened and uneven drying is less likely to occur. In addition, in the dissolving step when the polyamide-based resin powder is used to manufacture an optical film, such as the varnish manufacturing step, the dissolution time becomes shorter and the dissolution unevenness is less likely to occur. For example, Patent Document 1 describes a method for producing polyimide powder, which is to add a polyimine poor solvent to a polyimide solution to precipitate the polyimine to form a powder. However, according to the research of the present inventors, in the case of polyamide resins, depending on the addition conditions of poor solvents, etc., it is sometimes impossible to obtain polyamide resin powders with smaller particle diameters and smaller differences in particle diameters. body.

Therefore, the object of the present invention is to provide a method for producing polyamide-based resin powders that can easily and efficiently produce polyamide-based resin powders with smaller particle diameters and smaller particle diameter differences. [Technical means to solve the problem]

In order to solve the above-mentioned problems, the inventors focused on the method of adding poor solvents and conducted intensive research. As a result, it was discovered that a method for producing polyamide-based resin powder including the step of dissolving polyamide-based resin in a good solvent (a) in contact with a poor solvent under specific conditions , The above-mentioned problems can be solved, thereby completing the present invention.

That is, the present invention includes the following suitable forms. [1] A method for producing polyamide-based resin powder, which includes at least a contact step of contacting a polyamide-based resin solution (a) with a poor solvent solution (b), the above-mentioned polyamide-based resin solution (a) It is prepared by dissolving a polyamide resin in a good solvent for the polyamide resin, and the poor solvent liquid (b) contains at least one poor solvent for the polyamide resin; in the contact step When the area of the supply interface area in the middle is set to X m ² , and the addition rate of the polyamide resin solution (a) or the poor solvent solution (b) is set to Y kg/min, the addition rate calculated according to the formula (A) The amount is 400 or less: Add flux ((kg/min)/m ² )=Y/X formula (A). [2] The production method as described in the above [1], wherein the contact step is performed by adding a poor solvent solution (b) to the polyamide resin solution (a). [3] The production method as described in [1] or [2] above, wherein in the contact step, when the poor solvent solution (b) is added to the polyamide resin solution (a), the polyamide The stirring power of the resin solution (a) is set to Z kW/m ³ , when the polyamide resin solution (a) is added to the poor solvent solution (b), the stirring power of the poor solvent solution (b) is set to Z kW/m ³ , the ratio R of the above-mentioned added flux to the stirring power calculated according to formula (B) is 300 or less: ratio R=(Y/X)/Z formula (B). [4] The manufacturing method described in any one of [1] to [3] above, wherein the contact step includes at least a first contact step and a second contact step in which the ratio R is different from each other, and in the first contact step The ratio R _{1 is} smaller than the ratio R ₂ in the second contact step. [5] The production method described in [4] above, wherein the ratio R ₁ in the first contact step is 150 or less. [6] The production method as described in any one of [1] to [5] above, wherein the viscosity of the polyamide resin solution (a) is 0.5 to 100 Pa·s. [7] The production method as described in any one of [1] to [6] above, wherein the polyamide resin is selected from the group consisting of polyamide resins and polyimide resins. [8] The production method as described in any one of [1] to [7] above, wherein in the contact step, the addition of the polyamide resin solution (a) or the poor solvent solution (b) is selected Free sprayer, drip nozzle, water sprayer and nozzle dispersion plate consisting of more than one type. [9] The production method as described in the above [8], wherein the addition is performed using a sprayer. [10] The production method as described in any one of [1] to [9] above, wherein the polyamide-based resin solution (a) further contains at least one poor solvent. [11] The production method described in [10] above, which further comprises contacting the polyamide-based resin solution (a ₀ ) with the poor solvent solution (b ₀ ) to obtain the above-mentioned polyamide-based resin solution (a) Step, the polyamide resin solution (a ₀ ) is prepared by dissolving the polyamide resin in a good solvent for the polyamide resin, and the poor solvent solution (b ₀ ) contains the polyamide resin At least one poor solvent for resin. When [12] As the above-mentioned [11] according to the manufacturing method, wherein the step of obtaining a polyamide resin solution (a) of the manipulation polyamide resin solution (a ₀₎ and the poor solvent solution (b ₀₎ in contact The area of the supply interface area is set to P m ² , and the addition rate of the polyamide resin solution (a ₀ ) or poor solvent solution (b ₀ ) is set to Q kg/min, the addition calculated according to formula (C) Flux exceeds 400: Add flux ((kg/min)/m ² )=Q/P formula (C). [Effects of Invention]

According to the present invention, it is possible to provide a method for producing polyamide-based resin powder that is easy to produce a polyamide-based resin powder with a small particle size and a small difference in particle size.

Hereinafter, embodiments of the present invention will be described in detail. Furthermore, the scope of the present invention is not limited to the embodiments described here, and various changes can be made without departing from the scope of the present invention.

The manufacturing method of the polyamide resin powder of the present invention (hereinafter also referred to as "the manufacturing method of the present invention") includes at least a contact step of bringing the polyamide resin solution (a) into contact with the poor solvent solution (b) , The polyamide resin solution (a) is prepared by dissolving a polyamide resin in a good solvent for the polyamide resin, and the poor solvent solution (b) contains a solution for the polyamide resin. At least one poor solvent; set the area of the supply interface area in the above contact step as X m ² , and set the addition rate of the polyamide resin solution (a) or the poor solvent solution (b) to Y kg/min When the addition flux calculated according to formula (A) is 400 or less: addition flux ((kg/min)/m ² )=Y/X formula (A).

The production method of the present invention includes at least a contact step of bringing the polyamide resin solution (a) into contact with the poor solvent solution (b), and the flux of addition in the contact step is 400 or less.

(Polyamide resin solution (a)) The polyamide resin solution (a) is a solution obtained by dissolving a polyamide resin in a good solvent. Here, in this specification, the polyamide resin means at least one resin selected from the group consisting of polyamide resin, polyamide resin, and polyamide precursor resin. The polyamide resin is a resin containing repeating structural units containing an amido group, and the polyimide resin is a resin containing repeating structural units containing both an amido group and an imide group. In addition, the polyamide imide precursor resin is a polyamide imide resin that is imparted to the polyamide imide resin by the imidization precursor resin, and is also called a polyamide acid resin. In this specification, the aforementioned polyimide precursor resin is also referred to as "polyamide resin".

The polyamide resin solution (a) can be, for example, a reaction solution obtained by polymerizing the raw material monomers of the polyamide resin in a solvent (especially a good solvent for the polyamide resin). The solution obtained by dissolving the isolated polyamide resin in a good solvent may also be a solution obtained by adding a poor solvent to these solutions. From the viewpoint of easy and efficient implementation of the steps from the synthesis of the polyamide resin to the production of the polyamide resin powder, it is preferable to perform the polymerization reaction of the monomer in the following good solvent and use the obtained reaction solution As the polyamide-based resin solution (a), or adding a poor solvent to the obtained reaction solution, the obtained solution is used as the polyamide-based resin solution (a).

The good solvent contained in the polyamide-based resin solution (a) is a solvent that easily dissolves the polyamide-based resin, for example, the solubility of the polyamide-based resin at room temperature (20-30°C) is 1% by mass The above solvent. The good solvent contained in the polyamide resin solution may be one solvent or a mixture of two or more solvents. As a good solvent, for example, acetone, N,N-dimethylformamide (sometimes referred to as DMF), dimethyl sulfide (sometimes referred to as DMSO), γ-butyrolactone (sometimes Denoted as GBL), N,N-dimethylacetamide (sometimes denoted as DMAc), etc. Furthermore, whether the solvent used is a good solvent can be confirmed by the following method. The polyamide-based resin is added to the solvent so that it becomes 1% by mass, heating, stirring, etc. as necessary, so that the resin is dissolved in the solvent, and the solution at room temperature (20-30°C) becomes If the solution is uniform and transparent, the solvent is a good solvent. If the solution does not become uniform and transparent, the solvent is a poor solvent and not a good solvent. For example, in this embodiment, the solvent is measured in a container and stirred, the polyamide resin is added to it so that it becomes 1% by mass, and stirring is performed at room temperature (24° C.) for 3 hours. As a result, it can be judged that if there is no dissolution residue and the solution becomes uniform and transparent, it is a good solvent, and if there is a dissolution residue, it is a poor solvent rather than a good solvent.

From the viewpoint of volumetric efficiency, the solubility of the good solvent to the polyamide resin is preferably 3% by mass or more, more preferably 5% by mass or more. The upper limit of the solubility of the good solvent to the polyamide resin is not particularly limited. From the viewpoint of reducing the amount of poor solvent used, it is preferably 40% by mass or less, and more preferably 25% by mass or less. Furthermore, in this specification, the solubility of a certain solvent S to the polyamide resin is based on the case where the amount of polyamide resin soluble in G parts by mass of solvent S is H parts by mass (%)=G/(G+H)×100 is the value calculated by the formula.

When the polyamide-based resin solution (a) contains a good solvent and does not contain a poor solvent, based on the viewpoint that the viscosity is easy to adjust to easy-to-handle, relative to the total amount of the polyamide-based resin solution, the polyamide The content of the good solvent in the resin solution (a) is preferably 60% by mass or more, more preferably 75% by mass or more. In addition, from the viewpoint of reducing the amount of poor solvent used, relative to the total amount of the polyamide resin solution, the content of the good solvent in the polyamide resin solution is preferably 98% by mass or less, more preferably 95% by mass %the following.

When the polyamide-based resin solution (a) contains a good solvent and does not contain a poor solvent, from the viewpoint of volumetric efficiency, the polyamide-based resin solution (a The content of the polyamide resin in) is preferably 1% by mass or more, more preferably 3% by mass or more. In addition, from the viewpoint of easy adjustment in operation to a viscosity that is easy to handle, relative to the total amount of the polyamide-based resin solution, the content of the polyamide-based resin in the polyamide-based resin solution is preferably 20% by mass or less, More preferably, it is 10% by mass or less.

When the polyamide-based resin solution (a) further contains at least one poor solvent, based on the viewpoint that the viscosity is easy to adjust to the easy-to-handle viscosity, relative to the total amount of the polyamide-based resin solution (a), the polyamide resin solution (a) The content of the good solvent in the amide resin solution (a) is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more. In addition, from the viewpoint of reducing the amount of poor solvent used, relative to the total amount of the polyamide resin solution (a), the content of the good solvent in the polyamide resin solution (a) is preferably 95% by mass or less , More preferably 90% by mass or less.

When the polyamide-based resin solution (a) further contains at least one poor solvent, from the viewpoint of volumetric efficiency, the polyamide-based resin solution (a) is relative to the total amount of the polyamide-based resin solution The content of the polyamide resin is preferably 1% by mass or more, more preferably 2% by mass or more. In addition, from the viewpoint of easy adjustment in operation to a viscosity that is easy to handle, relative to the total amount of the polyamide-based resin solution, the content of the polyamide-based resin in the polyamide-based resin solution is preferably 20% by mass or less, More preferably, it is 10% by mass or less.

When the polyamide resin solution (a) further contains at least one poor solvent, the poor solvent may be one solvent or a mixture of two or more solvents. The poor solvent in this specification is a solvent that is not easy to dissolve the polyamide resin, for example, refers to a solvent whose solubility to the polyamide resin does not reach 1% by mass at room temperature (20-30°C). Examples of poor solvents include alcohol-based solvents such as methanol and 2-propanol (for example, alcohols with 1 to 4 carbon atoms), ethyl acetate, tetrahydrofuran, toluene, hexane, and water. Furthermore, the method for evaluating whether the solvent used is a poor solvent is as described above. In this case, the polyamide-based resin solution (a) may further contain one kind of poor solvent, or may further contain a mixed solvent of two or more kinds of poor solvents.

The poor solvent contained in the polyamide resin solution (a) is preferably a poor solvent containing an alcohol having 1 to 4 carbon atoms. As a C1-C4 alcohol, methanol, ethanol, 2-propanol, butanol, etc. are mentioned, for example. The poor solvent contained in the polyamide-based resin solution (a) can be one alcohol with 1 to 4 carbon atoms, a mixture of two or more alcohols with 1 to 4 carbon atoms, or one or two alcohols. A mixture of more than one kind of alcohols with 1 to 4 carbon atoms and other poor solvents.

When the polyamide-based resin solution (a) further contains at least one poor solvent, it is easy to adjust the viscosity to be easy to handle based on the operation, and it is easy to efficiently produce a smaller particle size and smaller difference in particle size From the viewpoint of the powder of polyamide-based resin, the content of the poor solvent in the polyamide-based resin solution (a) is preferably 5% by mass or more, more preferably 10% relative to the total amount of the polyamide-based resin solution. % By mass or more, more preferably 15% by mass or more. In addition, from the viewpoint of preventing the precipitation of polyamide-based resin in the polyamide-based resin solution (a) and improving production efficiency, relative to the total amount of the polyamide-based resin solution, the polyamide-based resin solution (a) The content of the poor solvent is preferably 40% by mass or less, more preferably 30% by mass or less.

When the polyamide-based resin solution (a) further contains at least one poor solvent, the production method of the present invention may further include contacting the polyamide-based resin solution (a ₀ ) with the poor solvent solution (b ₀ ) and The step of obtaining the polyamide resin solution (a), wherein the polyamide resin solution (a ₀ ) is obtained by dissolving a polyamide resin in a good solvent for the polyamide resin, and the disadvantages are The solvent liquid (b ₀ ) contains at least one poor solvent for the polyamide resin. Obtained in the step polyamide resin solution (a) of the manipulation polyamide resin solution (a ₀₎ and the poor solvent solution (b ₀₎ is supplied when the area of the interface area of the contact to P m ^2, poly When the addition rate of the amide resin solution (a ₀ ) or the poor solvent solution (b ₀ ) is set to Q kg/min, the addition flux calculated according to formula (C) is not particularly limited, based on the viewpoint that it is easy to improve production efficiency , Preferably more than 400. Adding flux ((kg/min)/m ² )=Q/P formula (C)

Based on the point of view that in the subsequent contact step with the poor solvent liquid (b), etc., it is easy to efficiently produce polyamide-based resin powders with smaller particle diameters and smaller differences in particle diameters. The total amount of polyamide resin contained in the resin solution (a), and the amount of precipitated polyamide resin contained in the polyamide resin solution (a) is preferably 10% by mass or less, more preferably It is 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0% by mass. In addition, the amount of precipitated polyamide resin contained in the polyamide resin solution (a) is obtained by performing solid-liquid separation by filtering the polyamide resin solution (a), etc., and measuring The quality of the solid object. In addition, the amount of the precipitated polyamide-based resin contained in the polyamide-based resin solution (a) may be the amount measured at the temperature at which the step of contacting with the poor solvent solution (b) is performed. The amount of the precipitated polyamide-based resin contained in the polyamide-based resin solution (a) being 0% by mass means that the polyamide-based resin is not deposited in the polyamide-based resin solution (a).

Based on the following contact steps of contacting the polyamide resin solution (a) with the poor solvent solution (b), it is easy to produce polyamide resin powder with a smaller particle size and smaller difference in particle size It is especially important to adjust the addition flux before and after this time based on the time when the powder of the polyamide-based resin starts to precipitate. Therefore, it is preferable that the polyamide-based resin does not precipitate in the polyamide-based resin solution (a) before contact with the poor solvent solution (b). In addition, from the same viewpoint, when the polyamide resin solution (a) does not contain a poor solvent or contains a poor solvent, it is preferably relative to the mixture obtained after the contact step (the mixture before the solid-liquid separation step) The amount of poor solvent contained in ), the amount of poor solvent contained in the polyamide resin solution (a) is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 45% by mass the following.

The viscosity of the polyamide-based resin solution (a) depends on the content of the polyamide-based resin in the polyamide-based resin solution (a), the molecular weight of the polyamide-based resin, etc., based on the viewpoint that the production efficiency can be easily improved, preferably It is 0.5 Pa·s or more, more preferably 0.6 Pa·s or more, and even more preferably 0.7 Pa·s or more, because it is easy to handle, and it is easy to produce a polyamide series with smaller particle size and smaller difference in particle size. From the viewpoint of the resin powder, it is preferably 100 Pa·s or less, more preferably 50 Pa·s or less, and still more preferably 10 Pa·s or less. The viscosity can be measured using a viscometer, for example, it can be measured under the measurement conditions described in the examples.

(Poor solvent liquid (b)) In the contact step included in the production method of the present invention, the polyamide resin solution (a) is brought into contact with the poor solvent solution (b). Poor solvent solution (b) is a solvent containing at least one poor solvent, which can be one poor solvent, a mixed solvent of two or more poor solvents, or a mixed solvent containing more than one poor solvent and a good solvent The solvent should just show poor solvent properties to the polyamide resin as a mixed solvent of the poor solvent liquid (b). Examples of poor solvents include alcohol-based solvents such as methanol and 2-propanol (for example, alcohols with 1 to 4 carbon atoms), ethyl acetate, tetrahydrofuran, toluene, hexane, and water. Furthermore, the method for evaluating whether the solvent used is a poor solvent is as described above.

The poor solvent liquid (b) in contact with the polyamide resin solution (a) is preferably a solvent containing water, more preferably a solvent containing 70% by mass or more of water. When the poor solvent solution (b) contains water, the ratio is based on the total amount of the poor solvent solution (b) based on the viewpoint that it is easy to remove the good solvent or alcohol that may be contained in the precipitated polyamide resin It is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, particularly preferably 70% by mass or more, especially more preferably 75% by mass or more In particular, it is more preferably 80% by mass or more, particularly preferably 85% by mass or more, and even more preferably 90% by mass or more. In addition, relative to the total mass of the poor solvent (b), the content of the alcohol contained in the poor solvent (b) is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less, More preferably, it is 3% by mass or less.

(Contact step) The production method of the present invention includes at least a contact step of bringing the polyamide resin solution (a) into contact with the poor solvent solution (b), and the flux of addition in the contact step is 400 or less. In the production method of the present invention, the contact step of bringing the polyamide resin solution (a) into contact with the poor solvent solution (b) may be a one-step contact step or a two-step or more contact step. Here, that the contact step has two or more stages means that there are two or more stages in which the stirring speed, the addition speed, the type of poor solvent used, and the like are different from each other.

When the contact step of bringing the polyamide resin solution (a) and the poor solvent solution (b) into contact is two or more stages, as long as it includes at least the polyamide resin solution (a ) The step of contacting with the poor solvent solution (b) is sufficient.

The method of contacting the polyamide resin solution (a) with the poor solvent solution (b) is not particularly limited, as long as the contact is carried out. For example, in the polyamide resin solution (a) The method of adding the poor solvent solution (b) or the method of adding the polyamide resin solution (a) to the poor solvent solution (b). From the viewpoint that it is easy to obtain a powder with a smaller particle size and a smaller difference in particle size, it is preferable to make the polyamide-based resin solution by adding a poor solvent solution (b) to the polyamide-based resin solution (a) (a) Contact with poor solvent liquid (b). In addition, from the viewpoint of easy adjustment of the addition speed, it is more preferable to add by dripping. Through the aforementioned contact, the polyamide resin is precipitated, and a mixture containing the precipitated polyamide resin is obtained. Furthermore, it is only necessary to precipitate at least a part of the polyamide-based resin of the polyamide-based resin dissolved in the polyamide-based resin solution in the mixture containing the precipitated polyamide-based resin.

Regarding the addition flux in the above contact step, the area of the supply interface region in the above contact step is set to X m ² , and the addition rate of the polyamide resin solution (a) or poor solvent solution (b) is set to When Y kg/min, calculate according to formula (A): Add flux ((kg/min)/m ² )=Y/X formula (A) In the contact step included in the manufacturing method of the present invention, the above-mentioned addition The flux is below 400.

^{The area (X m 2} ) of the supply interface area in the contact step is obtained by supplying the polyamide resin solution (a) to the poor solvent solution (b) or supplying the poor solvent solution (a) to the polyamide resin solution (a). b), and the area of the interface area where contact is first generated in each of these contact steps. The addition (supply) of the polyamide resin solution (a) or the poor solvent solution (b) is preferably carried out using one or more selected from the group consisting of sprayers, drip nozzles, water jets, and nozzle dispersion plates. . For example, when the above-mentioned contacting step is performed by supplying the poor solvent solution (b) to the polyamide resin solution (a), the poor solvent solution (b) can be supplied from one or more nozzles, for example, It can be supplied by nozzles with multiple branches, can be supplied by one or more water jets and sprayers, or can be supplied by the method of installing a dispersion plate at the tip of the nozzle. For example, the solid cone nozzle JJXP manufactured by Ikeuchi Co., Ltd., the multi-head nozzle 7JJXP, the wide-angle solid cone nozzle BBXP, the mountain fan nozzle VP, the eccentric equal fan nozzle INOVVE, and the fan nozzle NZRVF manufactured by MISUMI Co., Ltd. can be used as sprayers. , Supply poor solvent (b). For example, the shower head S1040F1 or rotary shower head S1040F5 manufactured by SANEI Co., Ltd. can be used as a water sprayer to supply the poor solvent (b). In the case of performing the contact step by supplying the polyamide-based resin solution (a) to the poor solvent solution (b), the polyamide-based resin solution (a) is supplied from the nozzle or the like.

For example, in the case of supplying using one nozzle with one ejection port, the cross-sectional area of the inner diameter of the ejection port shall be the area of the supply interface area. When using one nozzle with two or more ejection ports for supply, the total internal diameter cross-sectional area of all ejection ports provided in the nozzle is set as the area of the supply interface area. When using two or more nozzles with one or two or more nozzles for supply, calculate the supply interface area of each nozzle in the same way as when using one nozzle, and set the total of these as supply The area of the interface area. In the case of using sprinklers, the total cross-sectional area of the inner diameters of all spouting outlets of one or more sprinklers is also set as the area of the supply interface area. In the case of using a sprayer, the sprayer has the function of spraying from the spray outlet to a wider area, so the spraying area of the supply liquid is set as the area of the supply interface area. In other words, when one or more liquid drop nozzles and/or water jets are used for supply, the sum of the cross-sectional areas of the inner diameters of all the nozzles provided in the liquid drop nozzles and/or water jets is set as The area of the supply interface area, when a sprayer is used for supply, the spray area of the spray liquid sprayed from the sprayer to the supply interface is set as the area of the supply interface area. In the case of using a nozzle dispersion plate, the spray area sprayed from the nozzle dispersion plate is set as the area of the supply interface area. Here, for example, when two or more nozzles are used for supply, when part or all of the supply interface area of each nozzle overlaps, the total area of each supply interface area is divided by the area of the overlapped area. The area of is set as the area of the supply interface area. In the case of using more than two sprinklers, sprayers, etc., when there is an overlapping area, the area of the supply interface area is also calculated in the same way.

When using a spray nozzle, based on the viewpoint that it is easy to obtain a powder with a smaller particle size and a smaller difference in particle size, the ratio of the supply interface area to the cross-sectional area of the tank (supply interface area/cross-sectional area of the tank) is preferred. The lower limit is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.25 or more. This makes it easy to suppress rapid precipitation or coarsening of particles. The upper limit of the ratio is not particularly limited, but from the viewpoint of ease of handling, it is preferably 0.9 or less, more preferably 0.7 or less, still more preferably 0.5 or less, and still more preferably 0.45 or less.

Regarding the addition rate Y (kg/min), for example, in the case of performing the contact step by adding the poor solvent solution (b) to the polyamide resin solution (a), the contact step can be It is calculated by dividing the amount of the added poor solvent solution (b) by the time required for the addition of the poor solvent solution (b). When the contact step is performed by adding the polyamide resin solution (a) to the poor solvent solution (b), the polyamide resin solution (a) added in the contact step can be used The amount is calculated by dividing the time required for the addition of the polyamide resin solution (a). When the contact step includes two or more steps with different addition speeds, the flux should be 400 or less in at least one step, and it is preferably weighted based on the amount of poor solvent added in each step The weighted average addition rate Y is calculated by averaging, and the addition flux calculated using the above-mentioned weighted average addition rate Y is 400 or less.

When the addition flux (Y/X) calculated according to the above formula exceeds 400, the concentration of the poor solvent is likely to be locally higher. In addition, the concentration of the poor solvent tends to change rapidly. If the concentration of the poor solvent is locally too high, the polyamide resin powder will be precipitated locally, and the polyamide resin powder will precipitate together with impurities, or the solidified polyamide resin contains a solvent, so it is difficult to obtain fine particles. Powder. Due to the rapid increase in the concentration of poor solvents, it is also difficult to obtain fine powders. Furthermore, as a result, the difference in particle size is also likely to occur. If the addition flux (Y/X) calculated according to the above formula is 400 or less, a powder with a smaller particle size and a smaller difference in particle size can be obtained. From the viewpoint of easy availability of such powders, the addition flux is preferably 400 or less, more preferably 300 or less, still more preferably 100 or less, and still more preferably 80 or less. The lower limit of the addition flux (Y/X) is not particularly limited. From the viewpoint of easy improvement of production efficiency, it is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1.0 or more.

The addition can be carried out continuously or intermittently. In the case of intermittent addition, the addition flux can be calculated using the addition speed of the addition step.

The above-mentioned addition flux can be adjusted by adjusting the addition rate (Y kg/min) and the area of the supply interface area (X m ² ) in the contact step of the polyamide resin solution (a) and the poor solvent solution (b). , And adjust to the above required range. As described above, the addition rate is calculated by dividing the amount of the poor solvent solution (b) added in the contact step by the time required for the addition, and can be adjusted by adjusting the addition amount and the addition time. The area of the supply interface area (X m ² ) can be adjusted by the following methods: the method of adjusting the inner diameter cross-sectional area and the number of nozzles used; in the case of using spray nozzles, in addition to these, the spray nozzles are also adjusted The height from the supply interface or the method of ejection pressure, etc.

When the contact step includes two or more steps with different fluxes, the flux (Y/X) should be 400 or less in at least one step. The amount is calculated based on the weighted average of the amount of poor solvent added in each step to calculate the average addition flux. The above average addition flux is 400 or less. For the average added flux in this case, the above-mentioned preferred descriptions and preferred numerical ranges related to the added flux also apply.

In the contact step, generally, when the poor solvent solution (b) is added to the polyamide resin solution (a), the contact step is performed while stirring the polyamide resin solution (a), and the polyamide resin solution (a) is stirred while performing the contact step. When the amide resin solution (a) is added to the poor solvent solution (b), the contact step is performed while stirring the poor solvent solution (b). Here, when the poor solvent solution (b) is added to the polyamide-based resin solution (a), the stirring power of the polyamide-based resin solution (a) is set to Z kW/m ³ , and then When the polyamide resin solution (a) is added to the poor solvent solution (b), the stirring power of the poor solvent solution (b) is set to Z kW/m ³ , and the above addition rate calculated according to the formula (B) The ratio R of the amount to the stirring power is preferably 300 or less, more preferably 150 or less, still more preferably 100 or less, and even more preferably 50 or less: Ratio R=(Y/X)/Z Formula (B) In addition, The ratio R is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. If the ratio R is less than the above upper limit, the difference in particle size becomes small, and if it is more than the lower limit, it is easy to improve production efficiency.

The stirring power (Z[kW/m ³ ]) is calculated according to the formula (D): Z=Np×ρ×(n/60) ³ ×d ⁵ /V/1000 formula (D) (in formula (D), Np represents Power number, ρ represents the density of the liquid [kg/m ³ ], n represents the stirring speed [rpm], d represents the blade diameter of the stirring blade [m], V represents the volume of the liquid [m ³ ]) The power number Np can be based on the previous The relationship between the power number Np and the Reynolds number Re described in the literature formula or the manufacturer's catalog is calculated, and the Reynolds number Re is calculated according to the formula (E). Re=ρ×n/60×d ² /μ Formula (E) (In formula (E), μ represents liquid viscosity [Pa·s], ρ represents liquid density [kg/m ³ ], n represents stirring speed [rpm ], d represents the blade diameter of the stirring blade [m]) For example, in this embodiment, three swept blades are used, according to the catalog of Kobelco Environmental Shulijing Co., Ltd. "Glasslined Reactor" (No.114E, Printed in Japan Mar .2018) Np-Re line diagram described on page 8 ((3) Oval Section Three-blades retreat impeller with beaver-tail baffle, refer to https://www.kobelco-eco.co.jp/product/process/punf_pdf /p_glasslinedreactor.pdf), find the power number Np.

As a method of adjusting the stirring power to adjust the ratio R, a method of adjusting the stirring speed or a method of changing the volume of the liquid can be exemplified.

The aforementioned contact step preferably includes at least a first contact step and a second contact step in which the ratio R is different from each other. Furthermore, in this case, it is preferable that the ratio R _{1 in the} first contact step is smaller than the ratio R ₂ in the second contact step. Furthermore, in this case, from the viewpoint of making the difference in particle size smaller, the ratio R ₁ in the first contact step is preferably 150 or less, more preferably 100 or less, still more preferably 50 or less, and more preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. In addition, from the viewpoint of easy improvement of production efficiency, the ratio R ₂ in the second contact step is preferably 300 or less, more preferably 150 or less, still more preferably 100 or less, and preferably 2 or more, more preferably 3 or more , And more preferably 5 or more.

(Solid-liquid separation step) After the above-mentioned contact step, a mixture containing at least the precipitated polyamide resin, a good solvent and a poor solvent is obtained. By subjecting the mixture to solid-liquid separation, a polyamide-based resin powder is obtained. Furthermore, if the mixture obtained through the contacting step is subjected to solid-liquid separation, a polyamide-based resin combination containing the precipitated polyamide resin contained in the mixture and a part of the solvent contained in the mixture can be obtained Things. The polyamide-based resin composition is also called a wet cake composition, and is used to obtain an intermediate of polyamide-based resin powder.

The solid-liquid separation method is not particularly limited. For example, a method generally referred to as filtration can be mentioned. Specifically, it can be exemplified: a method of separation by gravity through filters with different permeability of precipitates and solvents; The method of separation by centrifugal force; the method of separation by pressure difference. Examples of filters that can be used include centrifugal filters, Druck filters, suction filters, and pressure reduction filters.

(Drying step) The production method of the present invention may further include a drying step of drying the polyamide-based resin composition to obtain polyamide-based resin powder. The drying conditions are not particularly limited, as long as the solvent in the polyamide resin composition can be removed. For example, it can be heated at a temperature of about 50 to 250°C for about 1 to 48 hours under reduced pressure or atmospheric pressure. And other conditions. From the viewpoint of easy improvement of production efficiency, drying may be performed by heating at a temperature of preferably 100°C or higher, more preferably 150°C or higher, preferably 0.5-10 hours, more preferably 1-5 hours.

<Polyamide resin powder> The polyamide resin powder produced by the production method of the present invention is preferably used for ^{color difference measurement based on the L *} a ^* b ^* color system (according to JIS Z 8781-4: In 2013), L ^* ≧90, -10≦a ^* ≦10, and -10≦b ^* ≦10 are satisfied. From the viewpoint of easily improving the transparency and visibility of the finally obtained polymer material, the L ^* in the above-mentioned color difference measurement is preferably 90 or more, more preferably 93 or more, and still more preferably 95 or more. The upper limit of L ^* is not particularly limited, as long as it is 100 or less. In the above color difference measurement, a ^* represents an index of redness. Based on the viewpoint that it is easy to improve the visibility of the finally obtained polymer material, it is preferably -10 or more and 10 or less, more preferably -7 or more and 7 or less, and still more preferably -5 above 5 below. In the above-mentioned color difference measurement, b ^* represents an index of blueness. Based on the viewpoint that it is easy to improve the visibility of the polymer material finally obtained, it is preferably -10 or more and 10 or less, more preferably -5 or more and 10 or less, and more preferably It is above -3 and below 7. The above-mentioned color difference can be measured using a color difference meter. According to the production method of the present invention, it is possible to prevent impurities contained in the polyamide resin solution from being included in the precipitate when the polyamide resin powder is deposited. Therefore, according to the manufacturing method of the present invention, it is easy to manufacture the polyamide resin powder having the above-mentioned color difference value.

From the viewpoints of easy drying of the powder when manufacturing the powder and the solubility of the powder when manufacturing polymer materials using the powder, the polyamide resin powder manufactured by the manufacturing method of the present invention _{The median diameter (d 50} ) in the volume-based particle size distribution obtained by the measurement is preferably 10 to 1,000 μm, more preferably 50 to 800 μm, still more preferably 100 to 600 μm, and still more preferably 200 to 500 μm. The particle size distribution can be measured using a particle size analyzer, for example, by the method described in the examples.

The polyamide resin powder produced by the production method of the present invention is measured to obtain a volume-based particle size distribution. Based on the d ₁₀ , d ₅₀ and d _{90 in} the particle size distribution, the parameters calculated by the formula (F) δ is preferably 5.0 or less, more preferably 4.5 or less, still more preferably 4.0 or less, still more preferably 3.0 or less, particularly preferably 1.5 or less, particularly preferably 1.0 or less: δ=(d ₉₀ -d ₁₀ )/ d ₅₀ formula (F) Here, d _x represents the particle size at the time when the frequency (cumulative volume from the small diameter side) in the obtained particle size distribution becomes x%, the smaller the parameter δ, the greater the difference in particle size small. When the parameter δ is less than the above upper limit, it is easy to reduce the uneven drying of the powder during the production of the powder and the uneven solubility of the powder during the production of polymer materials using the powder.

＜Polyamide resin＞ In the manufacturing method of the present invention, the polyamide resin may be at least one resin selected from the group consisting of polyamide resin, polyamide resin, and polyamide resin. The polyamide resin may be one type of polyamide resin, or a mixture of two or more types of polyamide resin. From the viewpoint of film forming properties, the polyamide resin is preferably a polyamide resin. The polyamide resin is preferably an aromatic polyamide resin. The so-called polyamide resin is aromatic, which means that the structural unit constituting the polyamide resin is preferably 50 mol% or more, more preferably 70 mol% or more, and more preferably 100 mol%. The structural unit of the aromatic structure.

[式(1)中，Y表示四價有機基，X表示二價有機基，*表示鍵結鍵。式(2)中，Z及X彼此獨立地表示二價有機基，*表示鍵結鍵。]In a preferred embodiment of the present invention, the polyamide resin is preferably a polyamide resin having a structural unit represented by formula (2), or a structural unit represented by formula (1) and formula (2) ) Polyimide resin of the structural unit represented. The formula (1) and formula (2) are described below. The description of formula (2) is related to both polyamide resin and polyimide resin. The description of formula (1) is related to Polyimide resin is related. [化1]

[In formula (1), Y represents a tetravalent organic group, X represents a divalent organic group, and * represents a bonding bond. In formula (2), Z and X independently represent a divalent organic group, and * represents a bonding bond. ]

The structural unit represented by formula (1) is a structural unit formed by the reaction of a tetracarboxylic acid compound and a diamine compound, and the structural unit represented by formula (2) is a structural unit formed by the reaction of a dicarboxylic acid compound and a diamine compound. In a preferred embodiment of the present invention in which the polyamide resin is an aromatic polyamide resin, it is preferable to constitute one of the structural unit represented by formula (1) and the structural unit represented by formula (2) At least one of the tetracarboxylic acid compound, the diamine compound, and the dicarboxylic acid compound is an aromatic compound (aromatic tetracarboxylic acid compound, aromatic diamine compound, and/or aromatic dicarboxylic acid compound).

[式(20)～式(29)中，W¹ 表示單鍵、-O-、-CH₂ -、-CH₂ -CH₂ -、-CH(CH₃ )-、-C(CH₃ )₂ -、-C(CF₃ )₂ -、-Ar-、-SO₂ -、-CO-、-O-Ar-O-、-Ar-O-Ar-、-Ar-CH₂ -Ar-、-Ar-C(CH₃ )₂ -Ar-或-Ar-SO₂ -Ar-，此處，Ar彼此獨立地表示氫原子可經氟原子取代之碳數6～20之伸芳基(例如伸苯基)，*表示鍵結鍵]， 作為Z之雜環結構，可例舉具有噻吩環骨架之基。基於容易抑制聚醯胺系樹脂粉體及所獲得之光學構件之黃度(降低YI值)之觀點，較佳為式(20)～式(29)所表示之基及具有噻吩環骨架之基，更佳為式(26)、式(28)及式(29)所表示之基。In formula (2), Z represents a divalent organic group, preferably an alkyl group having 1 to 6 carbons, an alkoxy group having 1 to 6 carbons, or an aryl group having 6 to 12 carbons (such The hydrogen atom in the group may be substituted by a halogen atom, (preferably substituted by a fluorine atom), a divalent organic group with 4 to 40 carbons, more preferably an alkyl group with 1 to 6 carbons, and a carbon number of 1 to Alkoxy group of 6 or aryl group of 6 to 12 carbons (the hydrogen atoms in these groups can be substituted by halogen atoms, preferably fluorine atoms) substituted with cyclic structure and a divalent organic group of 4 to 40 carbons Furthermore, as examples of alkyl groups having 1 to 6 carbons, alkoxy groups having 1 to 6 carbons, or aryl groups having 6 to 12 carbons, the following are the same as R ^3a and R ^{3b in formula (3)} Related exemplifications also apply. Examples of cyclic structures include alicyclic, aromatic, and heterocyclic structures. Examples of organic group Z include formula (20), formula (21), formula (22), and formula ( 23), formula (24), formula (25), formula (26), formula (27), formula (28) and formula (29) among the bonding bonds of the base represented by two non-adjacent bonds are substituted A group formed from a hydrogen atom; and a bivalent chain hydrocarbon group with a carbon number of 6 or less: [化2]

[In formulas (20) to (29), 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-, where Ar represents independently of each other an aryl group having 6 to 20 carbon atoms (such as benzene Group), * represents a bonding bond], as the heterocyclic structure of Z, a group having a thiophene ring skeleton can be exemplified. From the viewpoint of easily suppressing the yellowness (lowering YI value) of the polyamide resin powder and the obtained optical member, the group represented by the formula (20) to the formula (29) and the group having a thiophene ring skeleton are preferred , More preferably the base represented by formula (26), formula (28) and formula (29).

[式(20')～式(29')中，W¹ 及*如式(20)～式(29)中所定義] 再者，式(20)～式(29)及式(20')～式(29')中之環上之氫原子可經碳數1～6之烷基、碳數1～6之烷氧基或碳數6～12之芳基取代(該等基中之氫原子可經鹵素原子(較佳為氟原子)取代)。As the organic group Z, it is more preferably formula (20'), formula (21'), formula (22'), formula (23'), formula (24'), formula (25'), formula (26'), The divalent organic group represented by formula (27'), formula (28') and formula (29'): [化3]

[In formulas (20') to (29'), W ¹ and * are as defined in formulas (20) to (29)] Furthermore, formulas (20) to (29) and (20') ~The hydrogen atom on the ring in formula (29') can be substituted by an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons or an aryl group with 6 to 12 carbons (the hydrogen in these groups The atom may be substituted by a halogen atom (preferably a fluorine atom)).

[式(d1)中，R²⁴ 係對下述式(3)中之R^3a 定義之基或氫原子，R²⁵ 表示R²⁴ 或-C(=O)-*，*表示鍵結鍵] 作為結構單元(d1)，具體而言，可例舉：R²⁴ 及R²⁵ 均為氫原子之結構單元(源自二羧酸化合物之結構單元)；R²⁴ 均為氫原子且R²⁵ 表示-C(=O)-*之結構單元(源自三羧酸化合物之結構單元)等。When the polyamide-based resin has a structural unit in which Z in the formula (2) is represented by any one of the above-mentioned formulas (20') to (29'), especially when the polyamide-based resin has the formula (2) In the case where Z in) is a structural unit represented by the following formula (3'), it is preferable that the polyamide-based resin has this structure from the viewpoint that it is easy to improve the film-forming properties of the varnish and the uniformity of the optical film The unit further has a carboxylic acid-derived structural unit represented by the following formula (d1): [化4]

[In formula (d1), R ²⁴ is the group or hydrogen atom defined for ^{R 3a} in the following formula (3) ^{, R 25} represents R ²⁴ or -C(=O)-*, * represents a bonding bond] As The structural unit (d1), specifically, can be exemplified: ^{structural units in which R 24} and R ²⁵ are both hydrogen atoms (structural units derived from dicarboxylic acid compounds); R ²⁴ are both hydrogen atoms and R ²⁵ represents -C (=O)-*The structural unit (the structural unit derived from the tricarboxylic acid compound) and so on.

[式(3)中，R^3a 及R^3b 彼此獨立地表示碳數1～6之烷基、碳數1～6之烷氧基或碳數6～12之芳基，R^3a 及R^3b 中所包含之氫原子彼此獨立地可經鹵素原子取代， W彼此獨立地表示單鍵、-O-、-CH₂ -、-CH₂ -CH₂ -、-CH(CH₃ )-、-C(CH₃ )₂ -、-C(CF₃ )₂ -、-SO₂ -、-S-、-CO-或-N(R⁹ )-， R⁹ 表示氫原子、可經鹵素原子取代之碳數1～12之一價烴基， s為0～4之整數，t為0～4之整數，u為0～4之整數，*表示鍵結鍵]， 更佳為由式(3')表示的結構單元： [化6]

[式(3')中，R^3a 、R^3b 、s、t、u、W及*如式(3)中所定義] 再者，於本說明書中，聚醯胺系樹脂具有式(2)中之Z由式(3)表示之結構單元，及聚醯胺系樹脂具有式(3)所表示之結構作為式(2)中之Z具有相同之含義，意指聚醯胺系樹脂中所包含之複數個式(2)所表示之結構單元中之至少一部分結構單元中的Z由式(3)表示。該記載亦適用於其他相同之記載。Regarding the polyamide-based resin, as Z in the formula (2), a plurality of types of Z may be included, and the plurality of types of Z may be the same or different from each other. From the viewpoint that it is easy to improve the bending resistance and impact resistance of the optical film obtained by using the polyamide resin powder of the present invention, and it is easy to improve the optical properties, it is preferable to have at least Z in formula (2) It is expressed by formula (3): [化5]

[In formula (3), R ^3a and R ^3b independently represent an alkyl group having 1 to 6 carbons, an alkoxy group having 1 to 6 carbons, or an aryl group having 6 to 12 carbons. In R ^3a and R ^3b The included hydrogen atoms can be substituted by halogen atoms independently of each other, and W independently of each other represents a single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -C( CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ -, -S-, -CO- or -N(R ⁹ )-, R ⁹ represents a hydrogen atom, the number of carbons that can be substituted by a halogen atom 1-12 monovalent hydrocarbon group, s is an integer of 0-4, t is an integer of 0-4, u is an integer of 0-4, * represents a bonding bond], more preferably represented by formula (3') Structural unit: [化6]

[In the formula (3'), R ^3a , R ^3b , s, t, u, W, and * are as defined in the formula (3)] Furthermore, in this specification, the polyamide resin has the formula (2) The Z in the formula (3) represents the structural unit, and the polyamide resin has the structure represented by the formula (3) as Z in the formula (2) has the same meaning, which means the polyamide resin Z in at least a part of the structural units represented by the plurality of structural units represented by the formula (2) is represented by the formula (3). This record also applies to other similar records.

In formula (3) and formula (3'), W independently represents a single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ -, -S-, -CO- or -N(R ⁹ )-, from the viewpoint of the bending resistance of the optical film, preferably It represents -O- or -S-, and more preferably represents -O-. R ^3a and R ^3b independently represent an alkyl group having 1 to 6 carbons, an alkoxy group having 1 to 6 carbons, or an aryl group having 6 to 12 carbons. Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tertiary, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2-ethylpropyl, n-hexyl, etc. Examples of alkoxy groups having 1 to 6 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, and Tributoxy, n-pentyloxy, n-hexyloxy, cyclohexyloxy, etc. As the aryl group having 6 to 12 carbon atoms, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group may be mentioned. From the viewpoint of the surface hardness and flexibility of the optical film, R ^3a and R ^3b independently of each other preferably represent an alkyl group having 1 to 6 carbon atoms, and more preferably represent an alkyl group having 1 to 3 carbon atoms. Here, ^{the hydrogen atoms contained in R 3a} and R ^3b may be substituted with halogen atoms independently of each other. R ⁹ represents a hydrogen atom, a monovalent hydrocarbon group of 1 to 12 carbons which may be substituted with a halogen atom. Examples of monovalent hydrocarbon groups with 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary, and n-pentyl. , 2-methylbutyl, 3-methylbutyl, 2-ethylpropyl, n-hexyl, n-heptyl, n-octyl, tertiary octyl, n-nonyl, n-decyl, etc., which can be Substituted by halogen atoms. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned. The polyamide-based resin may include a plurality of A, and the plurality of A may be the same or different from each other.

In formula (3) and formula (3′), t and u are independently an integer of 0-4, preferably an integer of 0-2, more preferably 0 or 1, and still more preferably 0.

In formula (3) and formula (3'), s is an integer in the range of 0-4. If s is in this range, the bending resistance and elastic modulus of the film containing the polyamide resin are likely to change Well. From the viewpoint that it is easy to further improve the impact resistance, elastic modulus and bending resistance of the film containing the polyamide resin, s in formula (3) and formula (3') is preferably in the range of 0 to 3 An integer is more preferably an integer in the range of 0-2, still more preferably 0 or 1, and still more preferably 0. Preferably, the structural unit comprising the structure represented by the formula (3) or the formula (3') in which Z in the formula (2) is 0 is, for example, a structural unit derived from terephthalic acid or isophthalic acid, the The structural unit is a structural unit including a structure in which s is 0 and u is 0 in formula (3) or formula (3′). From the viewpoint of easily improving the impact resistance, elastic modulus, and bending resistance of the optical film, the polyamide-based resin preferably contains structural units derived from terephthalic acid. The polyamide-based resin may include one or two or more types of Z structural units represented by formula (3) or formula (3'). Based on the viewpoint that it is easy to reduce the yellowness of the polyamide-based resin powder and the obtained optical member, and based on the viewpoint that it is easy to improve the impact resistance, elastic modulus, and bending resistance of the optical film, regarding the polyamide-based resin, Z in formula (2) preferably includes two or more structures in formula (3) or formula (3') with different values of s, and more preferably includes formula (3) or formula (3') 2 or 3 structures with different values of s in ). In this case, based on the viewpoint that it is easy to improve the impact resistance, elastic modulus, and bending resistance of the optical film, and based on the viewpoint that it is easy to reduce the yellowness of the polyamide resin powder and the obtained optical film, it is more Preferably, the polyamide resin contains a structure in which Z in the structural unit represented by formula (2) is represented by formula (3) where s is 0, and in addition to the structural unit containing the structure, it further contains a formula containing s as 1 (3) The structural unit of the structure shown. Furthermore, it is also preferable to have a structural unit represented by the above-mentioned formula (d1) in addition to the structural unit represented by the formula (2) having Z represented by the formula (3) where s is 0.

於該情形時，容易提昇光學膜之耐衝擊性、彈性模數及耐彎曲性，並且容易降低聚醯胺系樹脂粉體及光學膜之黃度。In a preferred embodiment of the present invention, regarding the polyamide-based resin, as the structure (divalent group) represented by formula (3) or formula (3'), it has a structure of s=0 and u=0. In a more preferable embodiment of the present invention, regarding the polyamide resin, as the structure represented by the formula (3) or the formula (3'), it has a structure of s=0 and u=0, and a formula (3') The structure represented by'): [化7]

In this case, it is easy to improve the impact resistance, elastic modulus and bending resistance of the optical film, and it is easy to reduce the yellowness of the polyamide resin powder and the optical film.

When the polyamide resin has the structural unit represented by the formula (3) or formula (3') in the formula (2), the structural unit represented by the formula (1) of the polyamide resin When the total of the structural units represented by formula (2) is set to 100 mol%, the ratio is preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably 40 mol% or more, It is still more preferably 50 mol% or more, particularly preferably 60 mol% or more, and more preferably 90 mol% or less, more preferably 85 mol% or less, and still more preferably 80 mol% or less. If the ratio of the structural unit represented by the formula (3) or the formula (3') in Z in the formula (2) is more than the above lower limit, it is easy to improve the impact resistance, elastic modulus, and bending resistance of the optical film. If the ratio of the structural units represented by the formula (3) or the formula (3') of Z in the formula (2) is less than the above upper limit, it is easy to suppress the hydrogen bond derived from the amide bond of the formula (3). The viscosity of resin-containing varnish increases, which easily improves the processability of the film.

In addition, when the polyamide resin has a structure in which Z in the formula (2) is represented by the formula (3) or formula (3') where s=1 to 4, the formula ( 1) When the total of the structural unit represented by the formula (2) and the structural unit represented by the formula (2) is set to 100 mol%, the formula (3) with s of 1 to 4 or the formula with Z represented by the formula (3') (2) The ratio of the structural unit represented is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 7 mol% or more, still more preferably 9 mol% or more, and more It is preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, and still more preferably 30 mol% or less. If the ratio of the structural unit represented by the formula (2) having the formula (3) represented by the formula (3') or the formula (3') with s of 1 to 4 is more than the above lower limit, the impact resistance and elasticity of the optical film are easily improved Modulus and bending resistance. If the ratio of the structural unit represented by the formula (2) having the formula (3) or Z represented by the formula (3') with s of 1 to 4 is less than the above upper limit, it is easily suppressed because it is derived from the formula (3) or The hydrogen bonds between the amide bonds of the structure represented by the formula (3') cause the viscosity of the resin-containing varnish to increase, and it is easy to improve the processability of the film. Furthermore, the ratio of structural units represented by formula (3) or formula (3') in Z in formula (1), formula (2), and formula (2) can ^{be measured, for example, using 1} H-NMR, or can also be Calculate based on the addition ratio of raw materials.

In a preferred embodiment of the present invention, Z in the polyamide resin is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 45 mol% or more, and even more Preferably, 50 mol% or more is represented by formula (3) or formula (3') where s is 0-4. If the above lower limit of Z is expressed by formula (3) or formula (3') in which s is 0-4, the impact resistance, elastic modulus, and bending resistance of the optical film are easily improved. In addition, it is sufficient that 100 mol% or less of Z in the polyamide-based resin is represented by formula (3) or formula (3') where s is 0-4. Furthermore, the ratio of the structural unit represented by formula (2) with s of 0-4 or Z represented by formula (3') in the resin can ^{be measured using 1} H-NMR, or It can also be calculated based on the addition ratio of the raw materials.

In a preferred embodiment of the present invention, Z in the polyamide resin is preferably 5 mol% or more, more preferably 8 mol% or more, further preferably 10 mol% or more, and even more Preferably, 12 mol% or more is represented by formula (3) or formula (3') in which s is 1 to 4. When the above lower limit of Z of the polyamide resin is expressed by formula (3) or formula (3') where s is 1 to 4, it is easy to improve the impact resistance, elastic modulus and bending resistance of the optical film . In addition, Z is preferably 90 mol% or less, more preferably 70 mol% or less, still more preferably 50 mol% or less, and still more preferably 30 mol% or less. 3) Or expressed by formula (3'). Below the upper limit of Z, when represented by formula (3) or formula (3') in which s is 1 to 4, it is easy to suppress that it is derived from formula (3) or formula (3') in which s is 1 to 4 The hydrogen bonds between the amide bonds of the indicated structure cause the viscosity of the resin-containing varnish to increase, which is easy to improve the processability of the film. Furthermore, the ratio of the structural unit represented by formula (2) with s of 1 to 4 or Z represented by formula (3') in the resin can ^{be measured using 1} H-NMR, or It can also be calculated based on the addition ratio of the raw materials.

In formula (1) and formula (2), X independently represents a divalent organic group, preferably represents a divalent organic group having 4 to 40 carbons, and more preferably represents a carbon number of 4 to 4 having a cyclic structure. 40 divalent organic base. The cyclic structure may, for example, be an alicyclic ring, an aromatic ring, or a heterocyclic structure. Regarding the above-mentioned organic group, the hydrogen atom in the organic group may be substituted with a hydrocarbyl group or a fluorine-substituted hydrocarbyl group. In this case, the carbon number of the hydrocarbyl group and the fluorine-substituted hydrocarbyl group is preferably 1-8. In one embodiment of the present invention, the polyamide resin of the present invention may include a plurality of types of X, and the plurality of types of X may be the same or different from each other. Examples of X include: formula (10), formula (11), formula (12), formula (13), formula (14), formula (15), formula (16), formula (17), and formula (18) ); a group in which the hydrogen atom in the group represented by the formula (10) to formula (18) is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; and a chain formula with a carbon number of 6 or less Hydrocarbyl.

[化8]

[In formulas (10) to (18), * represents a bonding bond, and V ¹ , V ² and V ³ independently represent a single bond, -O-, -S-, -CH ₂ -, -CH _2- CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ -, -CO- or -N(Q)-. Here, Q represents a monovalent hydrocarbon group with 1 to 12 carbons which may be substituted with a halogen atom. ] As the monovalent hydrocarbon group having 1 to 12 carbon atoms, the groups described ^{above for R 9 can be exemplified.} One example is that V ¹ and V ³ are single bonds, -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 independent of each other, preferably meta or para, and more preferably para.

In the base represented by formulas (10) to (18), from the viewpoint of easily improving the impact resistance, elastic modulus, and bending resistance of the optical film, formulas (13), (14), and formulas are preferred The groups represented by (15), formula (16) and formula (17) are more preferably groups represented by formula (14), formula (15) and formula (16). In addition, from the viewpoint of easily improving the impact resistance, elastic modulus, and flexibility of the optical film, V ¹ , V ² and V ³ are independently of each other preferably a single bond, -O- or -S-, more preferably a single bond Key or -O-.

[式(4)中，R¹⁰ ～R¹⁷ 彼此獨立地表示氫原子、碳數1～6之烷基、碳數1～6之烷氧基或碳數6～12之芳基，R¹⁰ ～R¹⁷ 中所包含之氫原子彼此獨立地可經鹵素原子取代，*表示鍵結鍵] 若式(1)及式(2)所表示之複數個結構單元中之X之至少一部分為式(4)所表示之結構，則容易提高光學膜之耐衝擊性、彈性模數及透明性。In a preferred embodiment of the present invention, the polyamide resin, as X in formula (1) or X in formula (2), includes the structure represented by formula (4): [化9]

[In formula (4), R ¹⁰ to R ¹⁷ independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, or an aryl group with 6 to 12 carbons, R ¹⁰ to The hydrogen atoms contained in R ¹⁷ can be independently substituted by halogen atoms, and * represents a bonding bond] If at least a part of X in the plural structural units represented by formula (1) and formula (2) is formula (4) The structure represented by) can easily improve the impact resistance, elastic modulus and transparency of the optical film.

In formula (4), R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbons, and a carbon number of 1 to Alkoxy group of 6 or aryl group of 6-12 carbons. Examples of alkyl groups having 1 to 6 carbons, alkoxy groups having 1 to 6 carbons, or aryl groups having 6 to 12 carbons include the alkyl groups having 1 to 6 carbons in formula (3), The group exemplified by the alkoxy group having 1 to 6 or the aryl group having 6 to 12 carbon atoms. R ¹⁰ to R ¹⁷ independently of each other preferably represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Here, R ¹⁰ to R ¹⁷ are The included hydrogen atoms can be substituted by halogen atoms independently of each other. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. From the viewpoint of impact resistance, elastic modulus, transparency, and bending resistance of the optical film, it is more preferred that R ¹⁰ to R ¹⁷ independently of each other represent a hydrogen atom, a methyl group, a fluorine group, a chlorine group, or a trifluoride group. Methyl group, more preferably R ¹⁰ , R ¹² , R ¹³ , R ¹⁴ , R ^15, and R ¹⁶ represent a hydrogen atom, and R ¹¹ and R ¹⁷ represent a hydrogen atom, a methyl group, a fluoro group, a chloro group, or a trifluoromethyl group It is particularly preferable that R ¹¹ and R ¹⁷ represent methyl or trifluoromethyl.

即，式(1)及式(2)所表示之複數個結構單元中之X之至少一部分為式(4')所表示之結構單元。於該情形時，藉由含有氟元素之骨架，容易提高聚醯胺系樹脂於溶劑中之溶解性，容易提昇含有該樹脂之清漆之保管穩定性，並且容易降低該清漆之黏度，容易提昇光學膜之加工性。又，藉由含有氟元素之骨架，容易提昇光學膜之光學特性。In a preferred embodiment of the present invention, the structural unit represented by formula (4) is the structural unit represented by formula (4'): [化10]

That is, at least a part of X in the plural structural units represented by formula (1) and formula (2) is a structural unit represented by formula (4'). In this case, it is easy to improve the solubility of the polyamide resin in the solvent by the skeleton containing the fluorine element, and it is easy to improve the storage stability of the varnish containing the resin, and it is easy to reduce the viscosity of the varnish, and it is easy to improve the optics. The processability of the film. In addition, the fluorine-containing skeleton makes it easy to improve the optical properties of the optical film.

In a preferred embodiment of the present invention, X in the polyamide resin is preferably 30 mol% or more, more preferably 50 mol% or more, and more preferably 70 mol% or more. (4) Especially expressed by formula (4'). When X in the above-mentioned range in the polyamide-based resin is represented by formula (4), especially formula (4'), the obtained optical film has a fluorine-containing skeleton, which makes it easy to improve the resin’s The solubility in the solvent can easily improve the storage stability of the varnish containing the resin, and it is easy to reduce the viscosity of the varnish, and it is easy to improve the processability of the optical film. In addition, it is easy to improve the optical properties of the optical film by the skeleton containing the fluorine element. Furthermore, it is preferable that 100 mol% or less of X in the polyamide resin is represented by formula (4), especially formula (4'). X in the above resin may be formula (4), especially formula (4'). The ratio of the structural unit represented by the formula (4) of X in the above resin can ^{be measured, for example, using 1} H-NMR, or can also be calculated based on the addition ratio of the raw materials.

In formula (1), Y represents a tetravalent organic group, preferably a tetravalent organic group having 4 to 40 carbons, and more preferably a tetravalent organic group having 4 to 40 carbons having a cyclic structure. The cyclic structure may, for example, be an alicyclic ring, an aromatic ring, or a heterocyclic structure. From the viewpoint of easy improvement in impact resistance and elastic modulus, an aromatic ring may be preferably mentioned. The above-mentioned organic groups are those in which the hydrogen atoms in the organic groups may be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. In this case, the carbon number of the hydrocarbon group and the fluorine-substituted hydrocarbon group is preferably 1-8. In one embodiment of the present invention, the polyamide resin is a polyamide resin, and the polyamide resin may include a plurality of types of Y, and the plurality of types of Y may be the same or different from each other. Examples of Y include: the following formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28) and the group represented by the formula (29); the hydrogen atom in the group represented by the formula (20) to the formula (29) is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; and A tetravalent chain hydrocarbon group with a carbon number of 6 or less.

[化11]

In formulas (20) to (29), * 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 arylene group having 6 to 20 carbon atoms in which a hydrogen atom can be substituted with a fluorine atom, and as a specific example, a phenylene group may be mentioned.

In the base represented by formulas (20) to (29), from the viewpoint of easily improving the impact resistance, elastic modulus, and bending resistance of the optical film, formulas (26), (28) or formulas are preferred The group represented by (29) is more preferably the group represented by formula (26). And, based on easy to improve the impact resistance of the optical film, the elastic modulus and the bending resistance of view, and tends to decrease yellowness of polyamide resin powder, and the optical film, W ¹ is independently preferably a single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -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, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -, more preferably a single bond or -C(CF ₃ ) ₂ -.

In a preferred embodiment of the present invention, Y in the polyimide resin is preferably 50 mol% or more, more preferably 60 mol% or more, and more preferably 70 mol% or more. Formula (26) represents. If Y in the above-mentioned range in the polyamide imide resin is represented by formula (26), preferably W ¹ is a single bond, -C(CH ₃ ) ₂ -or -C(CF ₃ ) _2- 26). More preferably, W ¹ is a single bond or -C(CF ₃ ) ₂ -represented by the formula (26), it is easy to improve the impact resistance, elastic modulus and bending resistance of the optical film, and it is easy to reduce the polyamide The yellowness of amine resin powder and optical film. The ratio of the structural unit represented by formula (26) for Y in the polyamide imide resin can ^{be measured, for example, using 1} H-NMR, or can also be calculated based on the addition ratio of the raw materials.

[式(5)中，R¹⁸ ～R²⁵ 彼此獨立地表示氫原子、碳數1～6之烷基、碳數1～6之烷氧基或碳數6～12之芳基，R¹⁸ ～R²⁵ 中所包含之氫原子彼此獨立地可經鹵素原子取代，*表示鍵結鍵]， 及/或由式(9)表示 [化13]

[式(9)中，R³⁵ ～R⁴⁰ 彼此獨立地表示氫原子、碳數1～6之烷基或碳數6～12之芳基，R³⁵ ～R⁴⁰ 中所包含之氫原子彼此獨立地可經鹵素原子取代，*表示鍵結鍵] 若式(1)中之複數種Y之至少一部分由式(5)表示，及/或由式(9)表示，則容易提昇光學膜之耐衝擊性、彈性模數及光學特性。In a preferred embodiment of the present invention, at least a part of the plural kinds of Y in formula (1) is represented by formula (5): [化12]

[In formula (5), R ¹⁸ to R ²⁵ independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, or an aryl group with 6 to 12 carbons, R ¹⁸ to The hydrogen atoms contained in R ²⁵ can be substituted by halogen atoms independently of each other, * represents a bonding bond], and/or is represented by formula (9) [formation 13]

[In formula (9), R ³⁵ to R ⁴⁰ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbons or an aryl group having 6 to 12 carbons, and the hydrogen atoms contained in ^{R 35} to R ^{40 are independent of each other} The ground can be substituted by a halogen atom, * represents a bonding bond] If at least a part of the plurality of Y in the formula (1) is represented by the formula (5), and/or is represented by the formula (9), the durability of the optical film is easily improved Impact, elastic modulus and optical properties.

In formula (5), R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbons, and a carbon number of 1 to Alkoxy group of 6 or aryl group of 6-12 carbons. Examples of alkyl groups having 1 to 6 carbons, alkoxy groups having 1 to 6 carbons, or aryl groups having 6 to 12 carbons include the above-mentioned alkyl groups having 1 to 6 carbons in formula (3), The alkoxy group having 1 to 6 carbons or the aryl group having 6 to 12 carbons are exemplified. R ¹⁸ ~ R each independently preferably represents a hydrogen atom or an alkyl group with ^1-25 carbon atoms of 1 to 6, more preferably represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, the where, R ¹⁸ ~ R ²⁵ as The included hydrogen atoms can be substituted by halogen atoms independently of each other. As this halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. From the viewpoint of easy improvement of the impact resistance, elastic modulus, and bending resistance of the optical film, and the viewpoint of easy improvement of transparency and easy maintenance of the transparency, it is further preferred that R ¹⁸ to R ²⁵ independently represent hydrogen. Atom, methyl group, fluoro group, chloro group or trifluoromethyl group, more preferably R ¹⁸ , R ¹⁹ , R ²⁰ , R ²³ , R ²⁴ and R ²⁵ represent a hydrogen atom and R ²¹ and R ²² represent a hydrogen atom, A methyl group, a fluoro group, a chloro group or a trifluoromethyl group, particularly preferably, R ²¹ and R ²² represent a methyl group or a trifluoromethyl group.

In formula (9), R ³⁵ ~ R ⁴⁰ preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and still more preferably represents a hydrogen atom. Here, ^{the hydrogen atoms contained in R 35} to R ⁴⁰ may be independently substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As the alkyl group having 1 to 6 carbons and the aryl group having 6 to 12 carbons in ^{R 35} to R ^{40, those exemplified above can be mentioned, respectively.}

即，複數種Y之至少一部分由式(5')及/或式(9')表示。於該情形時，容易提高光學膜之耐衝擊性、彈性模數及耐彎曲性。進而，於式(5)由式(5')表示之情形時，藉由含有氟元素之骨架，容易提高聚醯胺系樹脂於溶劑中之溶解性，容易提昇含有該樹脂之清漆之保管穩定性，並且容易降低該清漆之黏度，容易提昇光學膜之加工性。又，藉由含有氟元素之骨架，容易提昇光學膜之光學特性。In a preferred embodiment of the present invention, formula (5) is represented by formula (5'), and formula (9) is represented by formula (9'): [化14]

That is, at least a part of the plural kinds of Y is represented by the formula (5') and/or the formula (9'). In this case, it is easy to improve the impact resistance, elastic modulus, and bending resistance of the optical film. Furthermore, in the case where the formula (5) is represented by the formula (5'), the fluorine-containing skeleton can easily improve the solubility of the polyamide resin in the solvent, and it is easy to improve the storage stability of the varnish containing the resin It is easy to reduce the viscosity of the varnish, and it is easy to improve the processability of the optical film. In addition, the fluorine-containing skeleton makes it easy to improve the optical properties of the optical film.

In a preferred embodiment of the present invention, Y in the polyimide resin is preferably 50 mol% or more, more preferably 60 mol% or more, and more preferably 70 mol% or more. It is represented by formula (5), especially formula (5'). If Y in the above-mentioned range in the polyamide resin is represented by formula (5), especially formula (5'), it is easy to improve the polyamide resin in the solvent by the skeleton containing the fluorine element. Solubility, easy to reduce the viscosity of varnish containing the resin, easy to improve the processability of the optical film. In addition, the fluorine-containing skeleton makes it easy to improve the optical properties of the optical film. Furthermore, it is preferable that 100 mol% or less of Y in the polyimide resin is represented by formula (5), especially formula (5'). Y in the polyimide resin may be formula (5), especially formula (5'). The ratio of the structural unit represented by formula (5) of Y in the polyamide imide resin can ^{be measured, for example, using 1} H-NMR, or can also be calculated based on the addition ratio of the raw materials.

In a preferred embodiment of the present invention, the plurality of structural units represented by formula (1) preferably comprise a structural unit represented by formula (5), and further comprise a structural unit represented by formula (9). . When the structural unit represented by formula (9) is further included, it is easy to further improve the impact resistance and elastic modulus of the optical film.

The polyimide imine resin may include the structural unit represented by formula (30) and/or the structural unit represented by formula (31), in addition to the structural unit represented by formula (1) and optionally included In addition to the structural unit represented by the formula (2), the structural unit represented by the formula (30) and/or the structural unit represented by the formula (31) are also included. [化15]

In the formula (30), Y ¹ represents a tetravalent organic group, and preferably represents an organic group in which the hydrogen atom in the organic group can be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. As Y ¹ , formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula ( 28) and the group represented by the formula (29); the hydrogen atom in the group represented by the formula (20) to the formula (29) is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; and carbon A tetravalent chain hydrocarbon group with a number of 6 or less. In one embodiment of the present invention, the polyamide resin may include a plurality of Y ¹ , and the plurality of Y ¹ may be the same as each other or different from each other.

In formula (31), Y ² represents a trivalent organic group, and preferably represents an organic group in which the hydrogen atom in the organic group can be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. As Y ² , the above formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28) A group in which any one of the bonding bonds of the group represented by the formula (29) is substituted with a hydrogen atom; and a trivalent chain hydrocarbon group with 6 or less carbon atoms. In an embodiment of the present invention, the polyimide resin may include multiple types of Y ² , and the multiple types of Y ² may be the same or different from each other.

In formula (30) and formula (31), X ¹ and X ² independently represent a divalent organic group, and preferably represent an organic group in which a hydrogen atom in the organic group can be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. Examples of X ¹ and X ² include the above-mentioned formula (10), formula (11), formula (12), formula (13), formula (14), formula (15), formula (16), and formula (17) ) And the group represented by the formula (18); the hydrogen atom in the group represented by the formula (10) to the formula (18) is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; and the number of carbons Chain hydrocarbon group of 6 or less.

In one embodiment of the present invention, the polyamide resin includes the structural unit represented by formula (1) and/or formula (2), and optionally includes the structural unit represented by formula (30) and/or formula (31) Structural units. In addition, based on the viewpoints of easily improving the optical properties, impact resistance, elastic modulus, and bending resistance of the optical film, in the above-mentioned polyamide-based resin, based on the structural units represented by formulas (1) and (2), And as the case may include all the structural units represented by formula (30) and formula (31), the ratio of the structural units represented by formula (1) and formula (2) is preferably 80 mol% or more, more preferably 90 Mole% or more, more preferably 95 mole% or more. Furthermore, in the polyamide-based resin, based on the structural units represented by formula (1) and formula (2), and all the structural units represented by formula (30) and formula (31) included as appropriate, the formula ( The ratio of the structural unit represented by 1) and formula (2) is usually 100% or less. In addition, the above-mentioned ratio can ^{be measured using 1} H-NMR, for example, or it can also be calculated based on the addition ratio of raw materials.

In one embodiment of the present invention, relative to 100 parts by mass of the base material layer constituting the optical film, the content of the polyamide resin in the base material layer contained in the optical film is preferably 10 parts by mass or more, more preferably It is 30 parts by mass or more, more preferably 50 parts by mass or more, and preferably 99.5 parts by mass or less, more preferably 95 parts by mass or less. If the content of the polyamide resin is within the above range, it is easy to adjust the thickness and ratio (A/B) of the intermediate layer of the optical film to the above range, it is easy to improve the bending resistance, and it is easy to improve the optical properties of the optical film. Impact resistance and elastic modulus.

Based on the viewpoint that it is easy to adjust the thickness and ratio (A/B) of the intermediate layer of the optical film to the above range, and based on the viewpoint that it is easy to improve impact resistance, elastic modulus and bending resistance, the weight of polyamide resin is average The molecular weight is calculated in terms of standard polystyrene, and is preferably 200,000 or more, more preferably 230,000 or more, still more preferably 250,000 or more, still more preferably 270,000 or more, and particularly preferably 280,000 or more. In addition, from the viewpoint that it is easier to improve the solubility of the polyamide resin powder in the preparation of varnishes, and from the viewpoint that it is easier to improve the extensibility and processability of the optical film, the weight average molecular weight of the polyamide resin is preferably 1,000,000 or less, more preferably 800,000 or less, still more preferably 700,000 or less, and still more preferably 500,000 or less. The weight average molecular weight can be measured by gel permeation chromatography (hereinafter, sometimes referred to as GPC), and can be calculated by standard polystyrene conversion, and can be calculated, for example, by the method described in the examples.

In a preferred embodiment of the present invention, when the polyamide resin is a polyamide resin, relative to 1 mol of the structural unit represented by formula (1), the polyamide resin The content of the structural unit represented by the formula (2) in the amine resin is preferably 0.1 mol or more, more preferably 0.5 mol or more, still more preferably 1.0 mol or more, and even more preferably 1.5 mol or more, and It is preferably 6.0 mol or less, more preferably 5.0 mol or less, and still more preferably 4.5 mol or less. If the content of the structural unit represented by formula (2) is more than the above lower limit, it is easy to improve the impact resistance and elastic modulus of the optical film. Moreover, if the content of the structural unit represented by the formula (2) is below the above upper limit, it is easy to suppress the increase in viscosity due to the hydrogen bonding between the amide bonds in the formula (2), and it is easy to improve the processability of the optical film.

In a preferred embodiment of the present invention, the polyamide-based resin may include, for example, halogen atoms such as fluorine atoms that can be introduced by the above-mentioned fluorine-containing substituents and the like. When the polyamide resin contains halogen atoms, it is easy to increase the elastic modulus of the optical film, and it is easy to reduce the yellowness of the polyamide resin powder and the optical film. If the elastic modulus of the optical film is high, it is easy to suppress the occurrence of damage and wrinkles. In addition, if the yellowness of the optical film is low, the transparency and visibility of the film can be easily improved. The halogen atom is preferably a fluorine atom. As a preferable fluorine-containing substituent for making the polyamide resin contain a fluorine atom, a fluorine group and a trifluoromethyl group can be mentioned, for example.

Based on the quality of the polyamide resin as a reference, the content of halogen atoms in the polyamide resin is preferably 1-40% by mass, more preferably 5-40% by mass, and still more preferably 5-30% by mass . If the content of halogen atoms is above the above lower limit, it is easy to further increase the elastic modulus of the optical film, reduce the water absorption rate, further reduce the yellowness of the polyamide resin powder and the optical film, and further improve the transparency and visibility. If the content of halogen atoms is less than the above upper limit, synthesis is easy.

The imidization rate of the polyimide resin is preferably 90% or more, more preferably 93% or more, and still more preferably 96% or more. From the viewpoint that it is easy to improve the optical properties of the optical film, the imidization rate is preferably at least the above lower limit. In addition, the upper limit of the imidization rate is 100% or less. The rate of imidization means that the molar amount of the amide bond in the polyamide resin is 2 times the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyamide resin. The ratio of the value. Furthermore, in the case where the polyamide resin contains a tricarboxylic acid compound, the imidization rate represents the molar amount of the amide bond in the polyamide resin relative to the polyamide resin The ratio of the value of twice the molar amount of the structural unit derived from the tetracarboxylic acid compound to the total molar amount of the structural unit derived from the tricarboxylic acid compound in the amine resin. In addition, the imidization rate can be obtained by IR (infrared radiation) method, NMR (nuclear magnetic resonance, nuclear magnetic resonance) method, or the like.

Commercially available products can be used for the polyamide resin. As a commercially available product of polyamide resin, for example, Neopulim (registered trademark) manufactured by Mitsubishi Gas Chemical Co., Ltd., KPI-MX300F manufactured by Kawamura Sangyo Co., Ltd., etc. may be mentioned.

[式(3'')中，R¹ ～R⁸ 彼此獨立地表示氫原子、碳數1～6之烷基、碳數1～6之烷氧基或碳數6～12之芳基，R¹ ～R⁸ 中所包含之氫原子彼此獨立地可經鹵素原子取代， A表示單鍵、-O-、-CH₂ -、-CH₂ -CH₂ -、-CH(CH₃ )-、-C(CH₃ )₂ -、-C(CF₃ )₂ -、-SO₂ -、-S-、-CO-或-N(R⁹ )-， R⁹ 表示氫原子、可經鹵素原子取代之碳數1～12之一價烴基， m為0～4之整數， R³¹ 及R³² 彼此獨立地表示羥基、甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第二丁氧基、第三丁氧基或氯原子。]<Method for producing resin> Polyamide resin can be produced, for example, from a diamine compound and a dicarboxylic acid compound as main raw materials. The polyamide imide resin and the polyamide imide precursor resin can be produced, for example, from a tetracarboxylic acid compound, a dicarboxylic acid compound, and a diamine compound as main raw materials. Here, the dicarboxylic acid compound preferably contains at least the compound represented by formula (3''). [化16]

[In formula (3''), R ¹ to R ⁸ independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, or an aryl group with 6 to 12 carbons, R ^{The hydrogen atoms contained in 1} to R ⁸ can be independently substituted by halogen atoms, and A represents a single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-,- C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ -, -S-, -CO- or -N(R ⁹ )-, R ⁹ represents a hydrogen atom, which can be substituted by a halogen atom A monovalent hydrocarbon group with 1 to 12 carbon atoms, m is an integer of 0 to 4, R ³¹ and R ³² independently represent hydroxyl, methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy Group, isobutoxy group, second butoxy group, third butoxy group or chlorine atom. ]

In a preferred embodiment of the present invention, the dicarboxylic acid compound is a compound represented by formula (3") where m is 0. As the dicarboxylic acid compound, in addition to the compound represented by the formula (3'') in which m is 0, it is more preferable to use the compound represented by the formula (3'') in which A is an oxygen atom. Furthermore, in another preferred embodiment, the dicarboxylic acid compound is a compound represented by formula (3") in which ^{R 31} and R ^{32 are chlorine atoms.} In addition, a diisocyanate compound may be used instead of the diamine compound.

As the diamine compound used when manufacturing resin, for example, aliphatic diamine, aromatic diamine, and mixtures of these can be mentioned. Furthermore, in this embodiment, "aromatic diamine" means a diamine in which an amine group is directly bonded to an aromatic ring, and a part of its structure may include an aliphatic group or other substituents. The aromatic ring may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a sulphur ring, but are not limited to these. Among them, a benzene ring is preferred. In addition, "aliphatic diamine" refers to a diamine in which an amine group is directly bonded to an aliphatic group, and a part of its structure may include an aromatic ring or other substituents.

As aliphatic diamines, for example, acyclic aliphatic diamines such as hexamethylene diamine; and 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(amino) Cycloaliphatic diamines such as methyl)cyclohexane, noralkylene diamine and 4,4'-diaminodicyclohexylmethane, etc. These can be used individually or in combination of 2 or more types.

As aromatic diamines, for example, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene and other aromatic diamines with one aromatic ring; 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4' -Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3, 4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-amino) Phenoxy) benzene, bis[4-(4-aminophenoxy)phenyl] ash, bis[4-(3-aminophenoxy)phenyl] ash, 2,2-bis[4- (4-aminophenoxy)phenyl)propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2'-dimethylbenzidine, 2,2 '-Bis(trifluoromethyl)-4,4'-diaminodiphenyl (sometimes referred to as TFMB), 4,4'-bis(4-aminophenoxy)biphenyl, 9,9 -Bis (4-aminophenyl) pyrene, 9,9-bis(4-amino-3-methylphenyl) pyrene, 9,9-bis(4-amino-3-chlorophenyl) pyrene , 9,9-bis(4-amino-3-fluorophenyl) pyridine and other aromatic diamines with more than two aromatic rings. These can be used individually or in combination of 2 or more types.

As the aromatic diamine, preferably, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl Ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 1,4-bis(4-amine Phenyloxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfuric acid, bis[4-(3-aminophenoxy)phenyl]sulfuric acid, 2,2-bis[4 -(4-Aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2'-dimethylbenzidine, TFMB, 4,4'-bis(4-aminophenoxy)biphenyl, more preferably, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane , 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, bis[4-(4- Aminophenoxy) phenyl] chrysene, 2,2-bis[4-(4-aminophenoxy) phenyl] propane, 2,2'-dimethylbenzidine, TFMB, 4,4' -Bis(4-aminophenoxy)biphenyl. These can be used individually or in combination of 2 or more types.

Among the above-mentioned diamine compounds, from the viewpoints of high elastic modulus, high transparency, high flexibility, high bending resistance, and low coloring properties of the optical film, it is preferable to use aromatic compounds having a biphenyl structure. One or more of the group consisting of diamines. More preferably, use selected from 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-bis(4-aminophenoxy)biphenyl and At least one of the group consisting of 4,4'-diaminodiphenyl ether, and it is more preferable to use TFMB.

Examples of the tetracarboxylic acid compound used in the production of the resin include aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic dianhydride; and aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic dianhydride. The tetracarboxylic acid compound may be used alone or in combination of two or more kinds. In addition to the dianhydride, the tetracarboxylic acid compound may also be a tetracarboxylic acid compound related product such as a chlorine compound.

Specific examples of aromatic tetracarboxylic dianhydrides include: non-condensed polycyclic aromatic tetracarboxylic dianhydrides, monocyclic aromatic tetracarboxylic dianhydrides, and condensed polycyclic aromatic tetracarboxylic dianhydrides anhydride. Examples of non-condensed polycyclic aromatic tetracarboxylic dianhydrides include 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid Dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (sometimes referred to as BPDA), 2, 2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl 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)diphthalic dianhydride (sometimes referred to as 6FDA), 1,2-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis( 2,3-Dicarboxyphenyl)ethane dianhydride, 1,2-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane Alkyl dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 4,4'-(p-phenylenedioxy)diphthalate Formic acid dianhydride, 4,4'-(isophthalic acid dianhydride). In addition, as the monocyclic aromatic tetracarboxylic dianhydride, for example, 1,2,4,5-benzenetetracarboxylic dianhydride can be exemplified, and as the condensed polycyclic aromatic tetracarboxylic dianhydride, for example, 2,3,6,7-Naphthalenetetracarboxylic dianhydride.

Among them, preferred examples include 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3, 3'-benzophenone tetracarboxylic dianhydride, BPDA, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic acid 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, 6FDA, 1,2-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl) Ethane dianhydride, 1,2-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(3,4 -Dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 4,4'-(terephthaloxy)diphthalic dianhydride and 4,4'- (Isophthalenedioxy)diphthalic dianhydride, more preferably 4,4'-oxydiphthalic dianhydride, BPDA, 2,2',3,3'-biphenyl Tetracarboxylic dianhydride, 6FDA, bis(3,4-dicarboxyphenyl)methane dianhydride, and 4,4'-(terephthalic acid) dianhydride. These can be used individually or in combination of 2 or more types.

The aliphatic tetracarboxylic dianhydride may, for example, be a cyclic or acyclic aliphatic tetracarboxylic dianhydride. Cycloaliphatic tetracarboxylic dianhydride is a tetracarboxylic dianhydride having an alicyclic hydrocarbon structure. Specific examples include: 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1 ,2,3,4-Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride and other cycloalkane tetracarboxylic dianhydrides; Bicyclo[2.2.2]oct-7 -En-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl-3,3',4,4'-tetracarboxylic dianhydride and their positional isomers. These can be used individually or in combination of 2 or more types. As a specific example of acyclic aliphatic tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride and 1,2,3,4-pentane tetracarboxylic dianhydride, etc. may be mentioned These can be used alone or in combination of two or more kinds. Moreover, cycloaliphatic tetracarboxylic dianhydride and acyclic aliphatic tetracarboxylic dianhydride can also be used in combination.

Among the above-mentioned tetracarboxylic dianhydrides, the optical film is more preferable in terms of high impact resistance, high modulus of elasticity, high surface hardness, high transparency, high flexibility, high bending resistance and low colorability. Examples are: 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, BPDA, 2,2',3,3' -Biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 6FDA and These mixtures are further preferably exemplified: BPDA and 6FDA and their mixtures, and more preferably, 6FDA and BPDA can be exemplified.

As the dicarboxylic acid compound used in the production of the resin, it is preferable to use terephthalic acid, isophthalic acid, 4,4'-oxydibenzoic acid, or these chlorinated compounds. In addition to terephthalic acid, isophthalic acid, 4,4'-oxybisbenzoic acid or these chlorinated compounds, other dicarboxylic acid compounds may also be used. Examples of other dicarboxylic acid compounds include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and these related chlorinated compounds, acid anhydrides, etc., and two or more of them can be used in combination. Specific examples include: isophthalic acid; naphthalenedicarboxylic acid; 4,4'-biphenyldicarboxylic acid; 3,3'-biphenyldicarboxylic acid; A dicarboxylic acid compound, and a compound in which two benzoic acids are _{linked via a single bond, -CH 2} -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ -or phenylene, and These chlorinated compounds. As a specific example, 4,4'-oxybis(benzoic acid chloride) (sometimes referred to as OBBC), terephthalic acid chloride (sometimes referred to as TPC) or isophthalic acid chloride is preferred, and further Preferably, OBBC and TPC are used in combination.

Furthermore, the polyamide imide resin can also be used in addition to the above-mentioned tetracarboxylic acid compounds within the range of not damaging the various physical properties of the optical film, and further the tetracarboxylic acid, tricarboxylic acid, and these anhydrides and derivatives The reaction becomes.

Examples of the tetracarboxylic acid include water adducts of the anhydrides of the above-mentioned tetracarboxylic acid compounds.

The tricarboxylic acid compound may, for example, be aromatic tricarboxylic acid, aliphatic tricarboxylic acid, and these related chlorinated compounds, acid anhydrides, etc., and two or more of them may be used in combination. As a specific example, anhydrides of 1,2,4-benzenetricarboxylic acid; anhydrides of 1,3,5-benzenetricarboxylic acid; 2,3,6-naphthalenetricarboxylic acid-2,3- Anhydride; Phthalic anhydride and benzoic acid are linked via single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ -or phenylene The compound.

When manufacturing the resin, the usage amount of the diamine compound, the tetracarboxylic acid compound and/or the dicarboxylic acid compound can be appropriately selected according to the required ratio of each structural unit of the polyamide resin.

When the resin is produced, the reaction temperature of the diamine compound, the tetracarboxylic acid compound, and the dicarboxylic acid compound is not particularly limited, and is, for example, 5 to 350°C, preferably 20 to 200°C, and more preferably 25 to 100°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 atmosphere or under reduced pressure as needed. In a preferred embodiment, the reaction is carried out with stirring under normal pressure and/or an inert gas atmosphere. In addition, the reaction is preferably carried out in a solvent having reaction inertness. The solvent is not particularly limited, as long as it does not affect the reaction. Examples include water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, and ethylene glycol butyl ether. , 1-methoxy-2-propanol, 2-butoxyethanol, propylene glycol monomethyl ether and other alcoholic solvents; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, GBL, γ-pentan Lactone, propylene glycol methyl ether acetate, ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone and other ketone solvents; Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; tetrahydrofuran and dimethoxyethane Ether solvents; chlorinated solvents such as chloroform and chlorobenzene; amide solvents such as DMAc and DMF; sulfur-containing solvents such as dimethyl sulfide, DMSO, and cyclobutyl sulfide; carbonic acid such as ethylene carbonate and propylene carbonate Ester solvents; and combinations of these. Among them, from the viewpoint of solubility, amide-based solvents are suitably used.

In the imidization step in the production of the polyimidimide resin, the imidization can be carried out in the presence of an imidization catalyst. As the imidization catalyst, for example, aliphatic amines such as tripropylamine, dibutylpropylamine, and ethyldibutylamine; N-ethylpiperidine, N-propylpiperidine, Alicyclic amines (monocyclic) such as N-butylpyrrolidine, N-butylpiperidine, and N-propylhexahydroazepine; azabicyclo[2.2.1]heptane, azabicyclo[3.2. 1] Octane, azabicyclo[2.2.2]octane and azabicyclo[3.2.2]nonane and other alicyclic amines (polycyclic); and pyridine, 2-picoline (2-picoline) , 3-picoline, 4-picoline, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2,4-lutidine, Aromatic amines such as 2,4,6-trimethylpyridine, 3,4-cyclopentenopyridine, 5,6,7,8-tetrahydroisoquinoline and isoquinoline. In addition, from the viewpoint that it is easy to promote the imidization reaction, it is preferable to use an acid anhydride together with the imidization catalyst. As the acid anhydride, commonly used acid anhydrides used in the imidization reaction may be mentioned, and specific examples thereof may include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride; aromatic acid anhydrides such as phthalic acid and the like.

Polyamide resins can be separated and purified by conventional methods, such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography and other separation methods, or a combination of these separation methods. In the form, a large amount of alcohol such as methanol is added to the reaction liquid containing the transparent polyamide-based resin to precipitate the resin, and the separation can be performed by performing concentration, filtration, drying, etc.

The polyamide resin powder produced by the production method of the present invention can be used, for example, as an optical member. As an optical member, an optical film can be mentioned, for example. Since this optical member is excellent in flexibility, bending resistance, and surface hardness, it is suitable as a window film that is a front panel of an image display device, particularly a front panel of a flexible display. The optical member may be a single layer or a multiple layer. When the optical member is a multiple layer, each layer may have the same composition or different compositions.

When the polyamide-based resin powder produced by the manufacturing method of the present invention is used as an optical member, the content of the polyamide-based resin in the optical member is preferably 40 relative to the total mass of the optical member. Mass% or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, especially 90% by mass or more. If the content of the polyamide-based resin is greater than or equal to the above lower limit, the bending resistance of the optical member is good. Furthermore, relative to the total mass of the optical member, the content of the polyamide resin in the optical member is usually 100% by mass or less.

(Inorganic materials) In addition to the polyamide-based resin, the optical member may further contain inorganic materials such as inorganic particles. Examples of the inorganic material include inorganic particles such as titanium oxide particles, aluminum oxide particles, zirconium oxide particles, and silica particles; and silicon compounds such as quaternary alkoxysilanes such as tetraethyl orthosilicate. From the viewpoint of the stability of the varnish containing the polyamide-based resin used to manufacture the optical member, the inorganic material is preferably inorganic particles, and particularly preferably silica particles. Inorganic particles can be bonded to each other via molecules with siloxane bonds.

From the viewpoints of the transparency of the optical member, the mechanical properties, and the inhibition of the aggregation of inorganic particles, the average primary particle size of the inorganic particles is usually 1-100 nm, preferably 5-80 nm, more preferably 7-50 nm, More preferably, it is 10 to 30 nm. In the present invention, the average primary particle size can be determined by measuring the 10-point average of the orientation diameter using a transmission electron microscope.

Based on the total mass of the optical component, the content of the inorganic material in the optical component is preferably 0 mass% or more and 90 mass% or less, more preferably 0.01 mass% or more and 60 mass% or less, and more preferably 5 mass% or more 40% by mass or less. If the content of the inorganic material is within the above range, it tends to be easy to balance the transparency and mechanical properties of the optical member.

(Ultraviolet absorber) The optical member may contain one kind or two or more kinds of ultraviolet absorbers. The ultraviolet absorber can be appropriately selected from those generally used as ultraviolet absorbers in the field of resin materials. The ultraviolet absorber may include a compound that absorbs light with a wavelength below 400 nm. As the ultraviolet absorber, for example, at least one compound selected from the group consisting of a benzophenone-based compound, a salicylate-based compound, a benzotriazole-based compound, and a triazole-based compound may be mentioned. Since the optical member contains the ultraviolet absorber, the deterioration of the polyamide-based resin is suppressed, and therefore the visibility of the optical member can be improved. In addition, in this specification, the "system compound" refers to a derivative of the compound accompanying the "system compound". For example, "benzophenone-based compound" refers to a compound having benzophenone as a parent skeleton and a substituent bonded to benzophenone.

When the optical member contains an ultraviolet absorber, relative to the total mass of the optical member, the content of the ultraviolet absorber is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more, And it is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 6% by mass or less. The appropriate content rate varies according to the UV absorber used, but if the content rate of the UV absorber is adjusted so that the light transmittance of 400 nm becomes about 20-60%, the light resistance of the optical member can be improved, and it can be obtained. Optical components with high transparency.

(Other additives) The optical member may further contain other additives. Examples of other components include antioxidants, release agents, stabilizers, bluing agents, flame retardants, pH adjusters, silica dispersants, lubricants, thickeners, and levelers.

When other additives are contained, relative to the mass of the optical member, the content is preferably from 0.001% by mass to 20% by mass, and more preferably from 0.001% by mass to 10% by mass.

For example, the thickness of the optical member as an optical film can be appropriately adjusted according to the application, and is usually 10 to 1,000 μm, preferably 15 to 500 μm, more preferably 20 to 400 μm, and still more preferably 25 to 300 μm. Furthermore, in the present invention, the thickness can be measured by a contact type digital gauge.

In the optical component, the total light transmittance Tt according to JIS K 7105:1981 is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, and still more preferably 90% or more. If the total light transmittance Tt of the optical member is more than the above lower limit, it is easy to ensure sufficient visibility when the optical member is assembled to the image display device. Furthermore, the upper limit of the total light transmittance Tt of the optical component is usually 100% or less. The haze of the optical component is measured by a direct reading haze meter (model HGM-2DP) manufactured by Suga Testing Machine Co., Ltd., preferably 1.0% or less, more preferably 0.8% or less, and even more preferably 0.5% Below, more preferably 0.3% or less. If the haze of the optical member is below the above upper limit, it is easy to ensure sufficient visibility when the optical member is assembled into a flexible electronic device such as an image display device. In addition, the lower limit of the haze is not particularly limited, as long as it is 0% or more. The polyamide-based resin dissolved in the polyamide-based resin solution (a) used in the production method of the present invention and/or the powder of the polyamide-based resin obtained by the production method of the present invention are preferred It has the above-mentioned total light transmittance Tt and/or haze. The total light transmittance Tt and/or haze of the polyamide resin and the polyamide resin powder is measured by the shape of the molded body (for example, film). The preparation method of the measurement sample and the details of the measurement method are as described in the examples.

(Method of manufacturing optical components) The polyamide resin powder produced by the production method of the present invention can be used to produce the above-mentioned optical member, such as an optical film. The manufacturing method is not particularly limited. For example, the optical component can be manufactured by a manufacturing method including the following steps: (a) The step of dissolving polyamide-based resin powder in a solvent, and applying the obtained liquid (polyamide-based resin varnish) containing polyamide-based resin to a substrate to form a coating film (coating Cloth step); and (b) The step (forming step) of drying the applied liquid (varnish of polyamide resin) to form an optical member (preferably an optical film or polyamide resin film). Steps (a) and (b) can usually be performed sequentially.

In the coating step, the polyamide-based resin powder is dissolved in a solvent, the above-mentioned ultraviolet absorber and other additives are added as necessary, and stirred, thereby preparing a polyamide-based resin-containing liquid (polyamide-based resin Of varnish).

The solvent used to prepare the varnish is not particularly limited as long as it can dissolve the polyamide resin. Examples of the solvent include amide-based solvents such as DMAc and DMF; lactone-based solvents such as GBL and γ-valerolactone; sulfur-containing solvents such as dimethyl sulfide, DMSO, and cyclobutane; ethylene carbonate Carbonate-based solvents such as esters, propylene carbonate, etc.; and combinations of these. Among these solvents, an amide-based solvent or a lactone-based solvent is preferred. In addition, the varnish may contain water, alcohol-based solvents, ketone-based solvents, acyclic ester-based solvents, ether-based solvents, and the like.

Secondly, for example, by a well-known roll-to-roll or batch method, a polyamide resin varnish can be used on a resin substrate, SUS tape or glass substrate, etc., to form a coating film by casting. .

In the forming step, the coating film can be dried and peeled from the substrate, thereby forming an optical member. After peeling, a drying step of drying the optical member may be further performed. The drying of the coating film can usually be carried out at a temperature of 50 to 350°C. The coating film can be dried in an inert atmosphere or under reduced pressure as needed.

It is also possible to perform a surface treatment step of performing surface treatment on at least one surface of the optical component. The surface treatment may, for example, be UV ozone treatment, plasma treatment, and corona discharge treatment.

As an example of a resin base material, PET film, PEN film, polyamide film, polyamide imide film, etc. are mentioned. Among them, from the viewpoint of excellent heat resistance, PET films, PEN films, polyamide films, and other polyimide films are preferred. Furthermore, from the viewpoint of adhesion to the optical member and cost, a PET film is more preferable.

The polyamide resin powder obtained by the production method of the present invention can be used to produce an optical member. This kind of optical component has high elastic modulus and flexibility. In a suitable embodiment of the present invention, the elastic modulus of the above-mentioned optical member is preferably 3.0 GPa or more, more preferably 4.0 GPa or more, still more preferably 5.0 GPa or more, still more preferably 6.0 GPa or more, and preferably Below 10.0 GPa. If the elastic modulus of the optical member is less than or equal to the above upper limit, when the flexible display is bent, it is possible to suppress damage to other members due to the above optical member. The modulus of elasticity can be, for example, Autograph AG-IS manufactured by Shimadzu Corporation. For a test piece with a width of 10 mm, the stress-strain curve can be measured under the conditions of a distance between the chucks of 50 mm and a tensile speed of 20 mm/min. It is determined based on its slope. The polyamide-based resin dissolved in the polyamide-based resin solution (a) used in the production method of the present invention and/or the powder of the polyamide-based resin obtained by the production method of the present invention are preferred To have the above-mentioned modulus of elasticity. The elastic modulus of polyamide resin and polyamide resin powder is measured by the shape of the molded body (for example, film). The preparation method of the measurement sample and the details of the measurement method are as described in the examples.

The above-mentioned optical member has excellent bending resistance. In a suitable embodiment of the present invention, the number of reciprocating bendings to break when the optical member is measured at R=1 mm under a load of 0.75 kgf at a speed of 175 cpm at 135° is preferably 10,000 or more, more preferably 20,000 or more , More preferably 30,000 times or more, still more preferably 40,000 times or more, and particularly preferably 50,000 times or more. If the number of reciprocating bending of the optical member is more than the above lower limit, the creases that may be generated when the optical member is bent can be further suppressed. Furthermore, there is no limit to the number of reciprocating bending of the optical member, and it is fully practical if it can be bent 1,000,000 times in general. The number of reciprocating bending can be obtained, for example, by using a test piece (optical member) having a thickness of 50 μm and a width of 10 mm using an MIT bending fatigue tester (model 0530) manufactured by Toyo Seiki Seisakusho Co., Ltd. The polyamide-based resin dissolved in the polyamide-based resin solution (a) used in the production method of the present invention and/or the powder of the polyamide-based resin obtained by the production method of the present invention are preferred To have the above-mentioned bending resistance. The bending resistance of the polyamide resin and the polyamide resin powder is measured by the shape of the molded body (for example, film).

The above-mentioned optical member can express excellent transparency. Therefore, the above-mentioned optical member is very useful as an image display device, especially a window film. In a suitable embodiment of the present invention, the yellowness YI of the optical member according to JIS K 7373:2006 is preferably 5 or less, more preferably 3 or less, still more preferably 2.5 or less, and still more preferably 2.0 or less. An optical member whose yellowness YI is below the above upper limit can contribute to high visibility of display devices and the like. Furthermore, the yellowness of the above-mentioned optical member is preferably 0 or more. The polyamide-based resin dissolved in the polyamide-based resin solution (a) used in the production method of the present invention and/or the powder of the polyamide-based resin obtained by the production method of the present invention are preferred It has the above-mentioned yellowness YI. The yellowness YI of polyamide resin and polyamide resin powder is measured by the shape of a molded body, such as a film.

The above-mentioned optical member may include functional layers such as an ultraviolet absorbing layer, an adhesive layer, a hue adjustment layer, and a refractive index adjustment layer, and a hard coat layer.

An optical member, such as an optical film, manufactured using the polyamide resin powder of the present invention can be used as a front panel of an image display device, especially a window film. The above-mentioned optical member can be used as a front panel to be arranged on the visible side surface of an image display device, especially a flexible display. The front panel has the function of protecting the image display elements in the flexible display. The image display device equipped with the above-mentioned optical member has high flexibility and bending resistance, and at the same time has a high surface hardness, so it will not damage other members when bending, and the optical member itself is not easy to produce creases, and thus can Beneficially inhibit surface damage.

Examples of image display devices include televisions, smart phones, mobile phones, car navigation, tablet PCs (personal computers), portable game consoles, electronic paper, indicators, indicator boards, clocks, and smarts Wearable devices such as type watches, etc. Examples of flexible displays include: image display devices with flexible characteristics, such as TVs, smart phones, mobile phones, car navigation, tablet PCs, portable game consoles, electronic paper, indicators, and instructions Boards, clocks and wearable devices, etc. [Example]

Hereinafter, the present invention will be explained in more detail with examples. The "%" and "parts" in the examples mean mass% and parts by mass unless otherwise stated.

[Determination of resin properties]

[Weight average molecular weight] The weight average molecular weight is measured using GPC. The preparation method and measurement conditions of the measurement sample are as follows. (1) Sample adjustment method Weigh 20 mg of resin powder and add 10 mL of DMF (add 10 mmol/L lithium bromide) to completely dissolve it. The solution was filtered through a chromatography disc (pore size 0.45 μm) to obtain a sample solution. (2) Measurement conditions Device: HLC-8020GPC Column: protection column + TSKgelα-M(300×7.8 mm)×2 pieces+α-2500(300×7.8 mm)×1 pieces Eluent: DMF (add 10 mmol/L lithium bromide) Flow rate: 1.0 mL/min Detector: RI detector Column temperature: 40℃ Injection volume: 100 μL Molecular weight standard: standard polystyrene

[Production example: Preparation of polyimide resin] A reaction vessel equipped with a stirrer and a thermometer was replaced with nitrogen, cooled to 10°C, and DMAc as a solvent was added to the vessel. Furthermore, TFMB, 6FDA, OBBC, and TPC were added at the molar ratio shown in Condition 1 in Table 1 to prepare a solution 1 containing polyamide acid 1. [Table 1] Polyamide Molby TFMB 6FDA OBBC TPC Condition 1 1 1.0000 0.3078 0.1026 0.6156 Condition 2 2 0.3020 0.1007 0.6039

Then, diisopropylethylamine (DIEA), acetic anhydride, and 4-picoline (4-PC) were added to the polyamide acid solution, and the reaction vessel was heated to 70°C, thereby obtaining a reaction solution Polyimide resin solution (a ₀ ). Table 2 shows the molar ratio of each raw material to 1.0000 molar of TFMB. [Table 2] Molby DIEA Acetic anhydride 4-PC Condition 1 0.7182 2.1545 0.7182 Condition 2 0.7046 2.1137 0.7046

The obtained reaction solution was cooled, and when the temperature was lowered to 45°C, relative to TFMB 1.0000 mol, methanol was added at the molar ratio shown in Condition 1 in Table 3 to obtain a polyamide imide resin solution (a1) ( Density: 910 kg/m ³ , the amount obtained is 2,000 kg). The viscosity of the polyimide resin solution (a1) was 1 Pa·s. In the polyimide resin solution (a1), no precipitation of the polyimide resin was found. In addition, based on the total amount of the polyimide resin solution (a1), the amount of the polyimide resin solution (a1) contained in the polyimide resin solution (a1) is 5% by mass, which serves as a good solvent The amount of DMAc is 70% by mass, and the amount of methanol as a poor solvent is 21% by mass. Furthermore, the weight average molecular weight of the polyimide resin contained in the polyimide resin solution (a1) was 330,000. Hereinafter, the polyimide resin solution (a1) is also referred to as the solution (a1). [table 3] Molby Methanol Condition 1 72.32 Condition 2 71.67

The molar ratio of each component was changed to the molar ratio shown in Condition 2 in Tables 1 to 3, except that the polyimide resin solution (a2) was obtained in the same manner as in Condition 1 (Density: 910 kg/m ³ , the amount obtained is 2 kg). The viscosity of the polyimide resin solution (a2) was 5 Pa·s. In the polyimide resin solution (a2), no precipitation of the polyimide resin was found. In addition, based on the total amount of the polyimide resin solution (a2), the amount of the polyimide resin solution (a2) contained in the polyimide resin solution (a2) is 5% by mass, which serves as a good solvent The amount of DMAc is 70% by mass, and the amount of methanol as a poor solvent is 21% by mass. Furthermore, the weight average molecular weight of the polyimide resin contained in the polyimide resin solution (a2) was 600,000. Hereinafter, the polyimide resin solution (a2) is also referred to as the solution (a2).

[Determination of Viscosity] (1) Measurement sample A part of the polyimide resin solution (a1) and the polyimide resin solution (a2) prepared in the above-mentioned production example were taken out as measurement samples, and the viscosity was determined under the following measurement conditions. (2) Measurement conditions Device name: LVDV-II + Pro (manufactured by Brookfield) Measuring temperature: 10℃ Spindle: CPE-52 Sample size: 0.55 mL Rotor speed: 0.3 rpm

[Measurement of particle size of resin powder] Under the measurement conditions shown below, the volume-based median diameter of the wet solid obtained in the examples and comparative examples was obtained by the laser diffraction scattering method, and the obtained The obtained value is used as the particle size of the resin powder. In addition, regarding the parameter δ representing the uniformity of the particle size, the particle size when the frequency in the obtained particle size distribution is x% is taken as dx, and it is calculated by the formula (F). δ=(d _90- d ₁₀ )/d ₅₀ formula (F) (Measurement conditions) Device name: Mastersizer 3000 (manufactured by Malvern) Measurement temperature: Normal temperature Sample volume: 40-50 mL Refractive index: 1.53

Based on the results of the particle size measurement, the particle size, uniformity, and final quality were evaluated according to the following criteria. In addition, in each evaluation standard, ◎ is very good, ○ is good, and × is bad. (Evaluation criteria for particle size) ◎: The particle size is 200 μm or more and less than 500 μm ○: The particle size is less than 200 μm or the particle size is more than 500 μm and less than 1000 μm ×: The particle size is 1000 μm or more (Evaluation criteria for uniformity) ◎: The parameter δ is 1.0 or less ○: The parameter δ is greater than 1.0 and less than 5.0 ×: The parameter δ is greater than 5.0 (Final quality) A: Both particle size and uniformity are ◎ B: One of particle size and uniformity is ◎, and the other is ○ C: Both particle size and uniformity are 〇 D: One of particle size and uniformity is ○ or ◎, and the other is × E: Both particle size and uniformity are × Furthermore, A to C are qualified, and D and E are unqualified.

(Calculation of stirring power) The stirring power (Z [kW/m ³ ]) is calculated by the formula (D). Z=Np×ρ×(n/60) ³ ×d ⁵ /V/1000 Formula (D) In formula (D), Np represents power number, ρ represents liquid density [kg/m ³ ], n represents stirring speed [ rpm], d represents the blade diameter of the stirring blade [m], and V represents the volume of the liquid [m ³ ]. The power number Np is calculated based on the relationship between the power number Np and the Reynolds number Re recorded in the catalog of Kobelco Environmental Shulijing Co., Ltd. The Reynolds number Re is calculated according to formula (E). Re=ρ×n/60×d ² /μ Formula (E) (In formula (E), μ represents liquid viscosity [Pa·s], ρ represents liquid density [kg/m ³ ], n represents stirring speed [rpm ], d represents the blade diameter of the stirring blade [m].)

(Confirmation of the solubility of resin in solvent) For the resin obtained in the above production example, the solubility in the solvent was confirmed by the following method. Measure 9.9 g of solvent in a 30 mL glass spiral tube, and then put it into a magnetic stirrer for stirring. 0.1 g of resin powder was added thereto, stirred at room temperature (24°C) for 3 hours, and the solubility was confirmed. As a result, the resin powder dissolved in DMAc, but did not dissolve in methanol and ion-exchanged water. Therefore, DMAc is a good solvent, and methanol and ion exchange water are poor solvents. Furthermore, in the present examples and comparative examples, the ion-exchanged water is simply referred to as water.

<Example 1> While 870 kg of polyimide resin solution (a1) was stirred with three sweeping blades (d=1.2 m) at a rotation speed of 125 rpm, the solution (a1) was self-sprayed Nozzle (a solid cone nozzle (1/2M JJXP 010S303) manufactured by Ikeuchi Co., Ltd.) continuously add a total of 92 kg of water at an addition rate (Y) of 0.6 kg/min. At this time, the water and solution sprayed from the spray nozzle (a1) The area (X) of the supply interface area at the time of contact is 0.5m ² , and the flux (Y/X) is 1.2 ((kg/min)/m ² ) (added in the first half). 92 kg of water is added After the completion, continue to add 153 kg of water (addition in the second half) from different spray nozzles (a solid cone nozzle manufactured by Ikenei Co., Ltd. (1/2M JJXP 20 S303)) at an addition rate of 5 kg/min. The area of the supply interface area at this time is 0.5m ² , and the addition flux (Y/X) is 10 (kg/min)/m ^2. Furthermore, the weighted average addition rate of the first half of the addition and the second half of the addition is 3.35 kg /Min, the weighted average flux is 6.7 (kg/min)/m ^{2. In} addition, the ratio of the supply interface area to the cross-sectional area of the tank (supply interface area/the cross-sectional area of the tank) in Example 1 is 0.37. The precipitated white solid is captured by pressure filtration at 80 kPa to obtain a wet solid. The wet solid is a granular particle with a particle size of 460 μm, and the parameter δ indicating the uniformity of the particle size is 1.0.

<Example 2> While 680 kg of polyimide resin solution (a1) was stirred with 3 sweeping blades (d=1.2 m) at 114 rpm, the solution (a1) was self-sprayed Nozzle (a solid conical nozzle (1/2M JJXP 20 S303) manufactured by Ikenei Co., Ltd.) intermittently add a total of 71 kg of water at an addition speed (Y) of 5 kg/min (continuous stirring before the end of the water addition, the water The ratio of the addition time to the mixing time is 1:8. Specifically, water is added at an addition speed (Y) of 5 kg/min for 30 seconds, and water is not added and stirred for 4 minutes, and this operation is repeated). The area (X) of the supply interface area at this time is 0.5m ² , and the flux (Y/X) is 10 (kg/min)/m ^2. Moreover, the supply interface area and the cross-sectional area of the tank in Example 2 The ratio (supply interface area/pot cross-sectional area) is 0.37. The precipitated white solid is captured by pressure filtration at 20 to 80 kPa to obtain a wet solid. The wet solid is granular with a particle size of 310 μm, and the parameter δ is 0.8.

<Example 3> While 2,700 g of the polyimide resin solution (a1) was stirred with 3 sweeping blades (d=0.11 m) at a rotation speed of 323 rpm, the solution (a1) was dripped. The liquid nozzle continuously drips a total of 320 g of water at an addition rate (Y) of 1.2 g/min (1.2×10 ^{-3 kg/min).} The area (X) of the supply interface area at this time is 1.4×10 ^-5 m ² , and the added flux (Y/X) is 86 (kg/min)/m ² . The precipitated white solid was captured by filtration under reduced pressure to obtain a wet solid. The wet solid is granular with a particle size of 630 μm, and the parameter δ is 1.3.

<Example 4> While 260 g of the polyimide resin solution (a1) was stirred with 3 sweeping blades (d=0.11 m) at 520 rpm, the solution (a1) was dripped. The liquid nozzle continuously drips a total of 70 g of water at an addition rate (Y) of 9.0 g/min (9.0×10 ^{-3 kg/min).} The area (X) of the supply interface area at this time is 2.8×10 ^-5 m ² , and the added flux (Y/X) is 321 (kg/min)/m ² . The precipitated white solid was captured by filtration under reduced pressure to obtain a wet solid. The wet solid is granular with a particle size of 80 μm, and the parameter δ is 3.1.

<Example 5> While stirring 260 g of the polyimide resin solution (a2) with 3 sweeping blades (d=0.11 m) at a rotation speed of 520 rpm, drip it into the solution (a2). The liquid nozzle continuously drips 70 g of water at an addition rate (Y) of 9.0 g/min (9.0×10 ^{-3 kg/min).} The area (X) of the supply interface area at this time is 2.8×10 ^-5 m ² , and the added flux (Y/X) is 321 (kg/min)/m ² . The precipitated white solid was captured by filtration under reduced pressure to obtain a wet solid. The wet solid is granular with a particle size of 40 μm, and the parameter δ is 2.0.

<Comparative Example 1> While stirring 260 g of the polyimide resin solution (a1) with 3 sweeping blades (d=0.11 m) at a rotation speed of 532 rpm, drip it into the solution (a1). The liquid nozzle continuously drips 75 g of water at an addition rate (Y) of 17.0 g/min (17.0×10 ^{-3 kg/min).} The area (X) of the supply interface area at this time is 2.8×10 ^-5 m ² , and the flux (Y/X) is 607 (kg/min)/m ² . The precipitated white solid was captured by filtration under reduced pressure to obtain a wet solid. The wet solid is a block with a particle size of 1000 μm or more.

The conditions for adding a poor solvent to the polyimide resin solution in the Examples and Comparative Examples and the evaluation results of the obtained powder are shown in Tables 4 and 5.

[Table 4] Add method Solution viscosity [Pa•s] Adding speed (Y) [kg/min] The area of the supply interface area (X) [m ² ] Add flux (Y/X) [(kg/min)/m ² ] Stirring power (Z) [kW/m ³ ] Ratio R [(Y/X)/Z] Example 1 Spray nozzle 1 0.6 0.5 1.2 0.4 3 5 0.5 10 0.4 25 2 Spray nozzle 1 5 0.5 10 (intermittent) 0.4 25 3 Dropping nozzle (1 piece) 1 1.2×10 ^-3 1.4×10- ⁵ 86 0.5 171 4 Dropping nozzle (2 pcs) 1 9.0×10 ^-3 2.8×10 ^-5 321 3.1 104 5 Dropping nozzle (2 pcs) 5 9.0×10 ^-3 2.8×10 ^-5 321 14.1 twenty three Comparative example 1 Dropping nozzle (2 pcs) 1 17.0×10 ^-3 2.8 × 10 ^{- 5} 607 1.7 357

[table 5] Particle size Uniformity Final quality [μm] Evaluation δ Evaluation Example 1 460 ◎ 1.0 ◎ A 2 310 ◎ 0.8 ◎ A 3 630 〇 1.3 〇 C 4 80 〇 3.1 〇 C 5 40 〇 2.0 〇 C Comparative example 1 ＞1000 X 5.6 X E

It was confirmed that, as shown in Examples 1 to 5, the polyamide resin powder obtained by the manufacturing method of the present invention including the following steps has a smaller particle size and a smaller difference in particle size. The polyamide resin solution (a) is brought into contact with a poor solvent solution (b) containing at least one poor solvent for the polyamide resin at an addition flux of 400 or less. In contrast, as shown in Comparative Example 1, when the flux exceeds 400, the obtained polyamide resin powder system has a larger particle size and a larger difference in particle size.

Claims (12)

A method for producing a polyamide resin powder, which at least includes a contact step of contacting a polyamide resin solution (a) with a poor solvent solution (b), and the polyamide resin solution (a) is a The amide resin is dissolved in a good solvent for the polyamide resin, and the poor solvent solution (b) contains at least one poor solvent for the polyamide resin; the supply in the contact step The area of the interface area is set to X m ² , and the addition rate of the polyamide resin solution (a) or the poor solvent solution (b) is set to Y kg/min, the addition flux calculated according to the formula (A) is 400 The following: Adding flux ((kg/min)/m ² )=Y/X formula (A). The manufacturing method of claim 1, wherein the contact step is performed by adding a poor solvent solution (b) to the polyamide resin solution (a). The manufacturing method of claim 1 or 2, wherein in the above-mentioned contact step, the polyamide-based resin solution (a) is stirred when the poor solvent solution (b) is added to the polyamide-based resin solution (a) The power is set to Z kW/m ³ , when the polyamide resin solution (a) is added to the poor solvent solution (b), the stirring power of the poor solvent solution (b) is set to Z kW/m ³ , according to the formula (B) The calculated ratio R of the above-mentioned addition flux to the stirring power is 300 or less: Ratio R=(Y/X)/Z Formula (B). The manufacturing method of claim 1 or 2, wherein the contact step includes at least a first contact step and a second contact step in which the ratio R is different from each other, and the ratio R _{1 in the} first contact step is smaller than the ratio in the second contact step R ₂ . The manufacturing method of claim 4, wherein the ratio R ₁ in the first contact step is 150 or less. Such as the manufacturing method of claim 1 or 2, wherein the viscosity of the polyamide resin solution (a) is 0.5-100 Pa·s. According to the manufacturing method of claim 1 or 2, wherein the polyamide resin is selected from the group consisting of polyamide resin and polyimide resin. The manufacturing method of claim 1 or 2, wherein in the above-mentioned contact step, the addition of the polyamide resin solution (a) or the poor solvent solution (b) is selected from sprayers, drip nozzles, water sprayers, and nozzle dispersions One or more of the group consisting of the board. The manufacturing method of claim 8, wherein the above-mentioned addition is carried out using a sprayer. According to the manufacturing method of claim 1 or 2, wherein the polyamide resin solution (a) further contains at least one poor solvent. According to the manufacturing method of claim 10, which further includes the step of contacting the polyamide resin solution (a ₀ ) with the poor solvent solution (b ₀ ) to obtain the polyamide resin solution (a), the polyamide resin solution (a) The resin solution (a ₀ ) is prepared by dissolving a polyamide resin in a good solvent for the polyamide resin, and the poor solvent solution (b ₀ ) contains at least one of the polyamide resins. Poor solvent. The manufacturing method of claim 11, wherein the area of the supply interface area when the _{polyamide resin solution (a 0} ) is in contact with the poor solvent solution (b ₀ ) in the step of obtaining the polyamide resin solution (a) Set as P m ² and the addition rate of the polyamide resin solution (a ₀ ) or poor solvent solution (b ₀ ) is set to Q kg/min, the addition flux calculated according to the following formula exceeds 400: Addition flux ((kg/minute)/m ² )=Q/P.