JP2023113584A - Imidized resin composition production method and imidized resin composition - Google Patents

Abstract

To provide a method of producing an imidized resin composition which gives a film having a good appearance and less generation of wrinkles in a TD direction during longitudinal stretching (for example, shape defects having relatively small width in the TD direction) especially called "transverse dan" during longitudinal stretching, and to provide an imidized resin composition that can be produced by the method.SOLUTION: The imidized polymer composition is produced by melt-kneading, in an extruder, an imidized resin that contains a glutarimide unit and a (meth)acrylate ester unit and that contains no or a small amount of an aromatic vinyl unit and a master batch and containing a predetermined small amount of a lubricant.SELECTED DRAWING: None

Description

The present invention relates to a method for producing an imidized resin composition and an imidized resin composition.

Optical lenses such as virtual space (VR) lenses and augmented reality (AR) lenses, as well as optical components such as in-vehicle displays, are required to use materials with a small phase difference in order to improve image quality. there is On the other hand, conventionally, materials with small retardation have been used for polarizer protective films and the like.

As a resin useful as a material for a polarizer protective film, etc., an imidized resin containing a glutarimide unit and a styrene unit obtained by treating a methyl methacrylate-styrene copolymer with an imidizing agent has been proposed. (See, for example, Patent Document 1). However, the imidized resin containing a relatively large amount of styrene units as disclosed in Patent Document 1 has problems such as low solvent resistance and high cost derived from the styrene units.

In order to solve such problems, an imidized resin containing a glutarimide unit and a methyl methacrylate unit and not containing a styrene unit, having a specific imidization rate and acid value, and an acrylic ester An imidized resin having a unit amount of less than 1% by weight has been proposed (see, for example, Patent Document 2).

Japanese Patent No. 5787571 Japanese Patent No. 5574787

However, as a result of investigation by the present inventors, when the imidized resin does not contain styrene units or contains only a small amount of styrene units, wrinkles in the TD direction during longitudinal stretching, which are called "transverse wrinkles" (for example, relatively It has become clear that there is a problem that narrow width streaks, which are shape defects in the TD direction, are likely to occur, and that there is a problem that it is difficult to produce a film with a good appearance.

The present invention has been made in view of the above problems, and has a good appearance, especially wrinkles in the TD direction during longitudinal stretching called "horizontal corrugation" (for example, a relatively thin shape in the TD direction) An object of the present invention is to provide a method for producing an imidized resin composition that gives a film with less generation of defective streaks, etc., and an imidized resin composition that can be produced by the production method.

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides the following [1] to [7].

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、又は炭素原子数１～８のアルキル基を示し、Ｒ^３は、炭素原子数１～１８のアルキル基、炭素原子数３～１２のシクロアルキル基、又は炭素原子数５～１５の芳香族基含有基を示す。）

（式（２）中、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、又は炭素原子数１～８のアルキル基を示し、Ｒ^６は、炭素原子数１～１８のアルキル基、炭素原子数３～１２のシクロアルキル基、炭素原子数６～１０のアリール基、又は炭素原子数７～１２のアラルキル基を示す。）

（式（３）中、Ｒ^７は、水素原子、又は炭素原子数１～８のアルキル基を示し、Ｒ^８は、炭素原子数６～１０のアリール基を示す。）
［２］基材が、熱可塑性樹脂、及び／又は、紫外線吸収剤である、［１］に記載のイミド化樹脂組成物の製造方法。
［３］基材が、紫外線吸収剤である、［２］に記載のイミド化樹脂組成物の製造方法。
［４］紫外線吸収剤が、トリアジン化合物である、［３］に記載のイミド化樹脂組成物の製造方法。
［５］イミド化樹脂（Ａ）及び滑剤（Ｂ）を含み、
イミド化樹脂（Ａ）が、下記式（１）で表される単位と、下記式（２）で表される単位とを含み、下記式（３）で表される単位を含んでいてもよく、
イミド化樹脂（Ａ）の質量に対する式（３）で表される単位の質量の比率が５質量％以下であり、
イミド化樹脂（Ａ）の質量に対して０．００１５質量％以上０．０１質量％以下の滑剤（Ｂ）を含む、イミド化樹脂組成物。

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、又は炭素原子数１～８のアルキル基を示し、Ｒ^３は、炭素原子数１～１８のアルキル基、炭素原子数３～１２のシクロアルキル基、又は炭素原子数５～１５の芳香族基含有基を示す。）

（式（２）中、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、又は炭素原子数１～８のアルキル基を示し、Ｒ^６は、炭素原子数１～１８のアルキル基、炭素原子数３～１２のシクロアルキル基、炭素原子数６～１０のアリール基、又は炭素原子数７～１２のアラルキル基を示す。）

（式（３）中、Ｒ^７は、水素原子、又は炭素原子数１～８のアルキル基を示し、Ｒ８は、炭素原子数６～１０のアリール基を示す。）
［６］紫外線吸収剤を含む、［５］に記載のイミド化樹脂組成物。
［７］紫外線吸収剤が、トリアジン化合物である、［６］に記載のイミド化樹脂組成物。
［８］［５］～［７］のいずれか１つに記載のイミド化樹脂組成物からなるフィルム。
［９］光学フィルムである、［８］に記載のフィルム。 [1] A method for producing an imidized resin composition containing an imidized resin (A) and a lubricant (B),
Supplying the imidized resin (A) into the extruder from the main feed port of the extruder;
Adding a lubricant (B) to the molten imidized resin (A) in the extruder;
kneading the imidized resin (A) and the lubricant (B) in an extruder;
Collecting the imidized resin composition discharged from within the extruder;
including
The imidized resin (A) contains a unit represented by the following formula (1) and a unit represented by the following formula (2), and may contain a unit represented by the following formula (3). ,
The ratio of the mass of the unit represented by formula (3) to the mass of the imidized resin (A) is 5% by mass or less,
The imidized resin composition contains a lubricant (B) in an amount of 0.0015% by mass or more and 0.01% by mass or less with respect to the mass of the imidized resin (A),
Lubricant (B) is fed into the extruder as a masterbatch comprising lubricant (B) and base material,
A method for producing an imidized resin composition, wherein the masterbatch is fed into the extruder from a side feed port positioned downstream in the extrusion direction from the main feed port.

(In formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 18 carbon atoms, a carbon atom represents a cycloalkyl group having 3 to 12 carbon atoms or an aromatic group-containing group having 5 to 15 carbon atoms.)

(In formula (2), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁶ represents an alkyl group having 1 to 18 carbon atoms, a carbon atom represents a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.)

(In formula (3), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁸ represents an aryl group having 6 to 10 carbon atoms.)
[2] The method for producing an imidized resin composition according to [1], wherein the substrate is a thermoplastic resin and/or an ultraviolet absorber.
[3] The method for producing an imidized resin composition according to [2], wherein the substrate is an ultraviolet absorber.
[4] The method for producing an imidized resin composition according to [3], wherein the ultraviolet absorber is a triazine compound.
[5] containing an imidized resin (A) and a lubricant (B),
The imidized resin (A) contains a unit represented by the following formula (1) and a unit represented by the following formula (2), and may contain a unit represented by the following formula (3). ,
The ratio of the mass of the unit represented by formula (3) to the mass of the imidized resin (A) is 5% by mass or less,
An imidized resin composition containing a lubricant (B) in an amount of 0.0015% by mass or more and 0.01% by mass or less based on the mass of the imidized resin (A).

(In formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 18 carbon atoms, a carbon atom represents a cycloalkyl group having 3 to 12 carbon atoms or an aromatic group-containing group having 5 to 15 carbon atoms.)

(In formula (2), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁶ represents an alkyl group having 1 to 18 carbon atoms, a carbon atom represents a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.)

(In formula (3), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R 8 represents an aryl group having 6 to 10 carbon atoms.)
[6] The imidized resin composition according to [5], which contains an ultraviolet absorber.
[7] The imidized resin composition according to [6], wherein the ultraviolet absorber is a triazine compound.
[8] A film made of the imidized resin composition according to any one of [5] to [7].
[9] The film of [8], which is an optical film.

According to the present invention, the appearance is good, and in particular, there is little occurrence of wrinkles in the TD direction during longitudinal stretching (e.g., streaks that are relatively narrow in width and are defective in shape in the TD direction), which are called "transverse wrinkles". It is possible to provide a method for producing an imidized resin composition that gives a film, and an imidized resin composition that can be produced by the production method.

<<Method for producing imidized resin composition>>
According to the method for producing an imidized resin composition, an imidized resin composition containing the imidized resin (A) and the lubricant (B) is produced. Here, the content of the lubricant (B) in the resulting imidized resin composition is 0.0015% by mass or more and 0.01% by mass or less with respect to the mass of the imidized resin (A).

The imidized resin (A) contains a unit represented by the following formula (1) and a unit represented by the following formula (2), and may contain a unit represented by the following formula (3). Use good resin. The mass ratio of the unit represented by the formula (3) to the mass of the imidized resin (A) is 5% by mass or less.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、又は炭素原子数１～８のアルキル基を示し、Ｒ^３は、炭素原子数１～１８のアルキル基、炭素原子数３～１２のシクロアルキル基、又は炭素原子数５～１５の芳香族基含有基を示す。）

(In formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 18 carbon atoms, a carbon atom represents a cycloalkyl group having 3 to 12 carbon atoms or an aromatic group-containing group having 5 to 15 carbon atoms.)

（式（２）中、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、又は炭素原子数１～８のアルキル基を示し、Ｒ^６は、炭素原子数１～１８のアルキル基、炭素原子数３～１２のシクロアルキル基、炭素原子数６～１０のアリール基、又は炭素原子数７～１２のアラルキル基を示す。）

(In formula (2), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁶ represents an alkyl group having 1 to 18 carbon atoms, a carbon atom represents a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.)

（式（３）中、Ｒ^７は、水素原子、又は炭素原子数１～８のアルキル基を示し、Ｒ８は、炭素原子数６～１０のアリール基を示す。）

(In formula (3), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R 8 represents an aryl group having 6 to 10 carbon atoms.)

The method for producing the imidized resin composition comprises:
Supplying the imidized resin (A) into the extruder from the main feed port of the extruder;
Adding a lubricant (B) to the molten imidized resin (A) in the extruder;
kneading the imidized resin (A) and the lubricant (B) in an extruder;
Collecting the imidized resin composition discharged from within the extruder;
including.

The unit represented by formula (3) is a unit derived from an aromatic vinyl monomer such as styrene. As described above, when a film is formed using an imidized resin that does not contain units derived from an aromatic vinyl monomer such as styrene, or contains only a small amount of units, the film tends to show lateral sagging. On the other hand, when an imidized resin containing a relatively large amount of units derived from an aromatic vinyl monomer is used, the film is less likely to have lateral dandruff.

The inventors of the present invention conducted extensive studies on this point, and found that in imidized resins containing a relatively large amount of units derived from aromatic vinyl monomers, the units have a lubricating effect, thereby stabilizing the film. We have come to speculate that it is manufactured by using

Based on this conjecture, the present inventors have found that the imidized resin (A) containing no or only a small amount of units derived from the aromatic vinyl monomer represented by formula (3) has a lubricant ( B) and optimization of the added amount of the lubricant (B) were investigated. It was found that the generation can be suppressed.

However, the amount of the lubricant (B) added is very small. Therefore, when the imidized resin composition is produced by an extruder, it is difficult to stably supply a desired amount of the lubricant (B) to the imidized resin (A) in the extruder.

Therefore, the present invention uses the lubricant (B) as a masterbatch containing the base material and the lubricant (B), and uses the masterbatch as a side feed port located downstream in the extrusion direction from the main feed port of the extruder. A method of melt-kneading the imidized resin (A) and the resin (B) in the extruder while feeding them into the extruder was found. According to this method, it is possible to produce an imidized resin composition having a desired composition while suppressing variations in the content of the small amount of lubricant (B).

Hereinafter, raw materials such as the imidized resin (A) and the masterbatch will be described for the method for producing the imidized resin composition, and then each step constituting the method for producing the imidized resin composition will be explained.

<Imidized resin (A)>
The imidized resin (A) includes a unit represented by the above formula (1), a unit represented by the above formula (2), and a unit represented by the above formula (3). Use a resin that can be used. The mass ratio of the unit represented by the formula (3) to the mass of the imidized resin (A) is 5% by mass or less.

A unit represented by formula (1) has a glutarimide skeleton and is generally called a glutarimide unit. A glutarimide unit is a unit having a glutarimide skeleton. Hereinafter, the unit represented by formula (1) is also referred to as a glutarimide unit.

a glutarimide unit in which R ¹ and R ² in formula (1) are each independently a hydrogen atom or a methyl group, and R ³ is a hydrogen atom, a methyl group, an n-butyl group, or a cyclohexyl group; is preferred. More preferably, R ¹ in formula (1) is a methyl group, R ² is a hydrogen atom, and R ³ is a methyl group.
The imidized resin (A) may contain only one type of glutarimide unit, or may contain two or more types of glutarimide units in combination.

A glutarimide unit can be formed by imidating a unit represented by formula (2). Also, acid anhydrides such as maleic anhydride, or half esters of such acid anhydrides with linear or branched alcohols having 1 to 20 carbon atoms; acrylic acid, methacrylic acid, maleic acid, maleic anhydride Glutarimide units can also be formed by imidizing acids, α,β-ethylenically unsaturated carboxylic acids such as itaconic acid, itaconic anhydride, crotonic acid, fumaric acid, citraconic acid; and the like.

The unit represented by formula (2) is a unit derived from an unsaturated aliphatic carboxylic acid ester such as (meth)acrylic acid ester. Hereinafter, the unit represented by formula (2) is also referred to as a (meth)acrylic acid ester unit.

(Meth)acrylic acid is generally a generic term for acrylic acid and methacrylic acid. That is, the (meth)acrylic acid unit is usually a unit in which ^R4 in formula (2) is a hydrogen atom and ^R5 is a hydrogen atom or a methyl group. However, in the specification of the present application, for the unit in which R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms in formula (2), (meth)acrylic acid Ester unit.

The raw material that gives the (meth)acrylic acid ester unit is not particularly limited as long as it can form the unit represented by formula (2). Preferred examples of raw materials that provide (meth)acrylate units include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate. , benzyl (meth)acrylate, cyclohexyl (meth)acrylate and the like. Among these, methyl methacrylate is particularly preferred.
The imidized resin (A) may contain only one type of (meth)acrylic acid ester unit, or may contain two or more types of (meth)acrylic acid ester units in combination.

The imidized resin (A) may contain units represented by the formula (3) within a range of 5% by mass or less relative to the mass of the imidized resin (A). Units represented by formula (3) are generally called aromatic vinyl units. Hereinafter, the unit represented by formula (3) is also referred to as an aromatic vinyl unit.

The raw material that gives the aromatic vinyl unit is not particularly limited as long as it can form the unit represented by formula (3). Suitable examples of raw materials that provide aromatic vinyl units include styrene and α-methylstyrene, with styrene being preferred.
The imidized resin (A) may contain only one type of aromatic vinyl unit, or may contain a combination of two or more types of aromatic vinyl units.

The content of the glutarimide unit in the imidized resin (A) depends on the type of R ³ in the formula (1), but is preferably 20% by mass or more relative to the mass of the imidized resin (A). 95 mass % is more preferred, 40 to 90 mass % is even more preferred, and 50 to 80 mass % is particularly preferred.
When the content of the glutarimide unit is within the above range, the imidized resin (A) is excellent in all of the heat resistance, transparency, and mechanical properties at a high level, and the imidized resin (A) melts. When the viscosity is within a range suitable for molding, the imidized resin composition tends to have particularly excellent moldability.

The content of the aromatic vinyl unit represented by formula (3) in the imidized resin (A) is, as described above, 5% by mass or less with respect to the mass of the imidized resin (A), and 3% by mass. The following are preferable, and 1 mass % or less is more preferable. It is also preferred that the imidized resin (A) does not contain aromatic vinyl units.

Various physical properties of the imidized resin (A) can be adjusted by adjusting the contents of glutarimide units, (meth)acrylic acid ester units, and aromatic vinyl units in the imidized resin (A).
For example, after polymerizing a (meth)acrylic acid ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer, the (meth)acrylic acid ester-aromatic vinyl copolymer is imidized to obtain an imidized resin. When producing (A), by adjusting the content of the aromatic vinyl units in the (meth)acrylic acid ester-aromatic vinyl copolymer, the amount of the aromatic vinyl units contained in the imidized resin (A) You can adjust the content. Further, during imidization, by adjusting the addition amount of the imidizing agent such as primary amine, the content of the glutarimide unit and the content of the (meth)acrylic acid ester unit in the imidized resin (A) can be adjusted.

The imidized resin (A) may contain units other than the aforementioned glutarimide units, (meth)acrylic acid ester units, and aromatic vinyl units as long as the desired effects are not impaired.
Preferable examples of monomers that provide other units include nitrile-based monomers such as acrylonitrile and methacrylonitrile; maleimide-based monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; etc.

When producing the imidized resin (A), typically, (meth)acrylic acid ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer, or (meth)acrylic acid ester such as methyl methacrylate polymer An acrylate polymer is subjected to imidization.
(Meth)acrylic acid ester-aromatic vinyl copolymers and (meth)acrylic acid ester polymers are linear polymers, block polymers, core-shell polymers, branched polymers, as long as imidization reactions are possible. It may be either a ladder polymer or a crosslinked polymer. The block polymer may be AB type, ABC type, ABA type, or any other type of block polymer. For core-shell polymers, each of the core and shell may be composed of only one layer, or may be composed of two or more layers.

The weight average molecular weight of the imidized resin (A) is not particularly limited as long as the desired effects are not impaired. The weight average molecular weight of the imidized resin (A) is preferably, for example, 1×10 ⁴ or more and 5×10 ⁵ or less. When the weight average molecular weight of the imidized resin (A) is within the above range, the melt viscosity of the imidized resin is within a range particularly suitable for molding, so that molding of the imidized resin composition is particularly easy. In addition, there is a tendency to easily obtain a molded article such as a film having sufficiently high mechanical strength using the imidized resin composition.

The glass transition temperature of the imidized resin (A) is not particularly limited as long as the desired effects are not impaired. The glass transition temperature of the imidized resin (A) is preferably 110°C or higher, more preferably 120°C or higher. When the glass transition temperature is within the above range, it is easy to apply products such as films produced using the imidized resin composition to applications requiring heat resistance.

The method for producing the imidized resin (A) is not particularly limited. The imidized resin (A) is typically a (meth)acrylic acid ester-aromatic vinyl copolymer such as a methyl methacrylate-styrene copolymer, or a (meth)acrylic acid such as a methyl methacrylate polymer. It can be produced by a method of imidizing an ester polymer by treating it with an imidizing agent. As the imidizing agent, an amine compound corresponding to the type of ^R3 in formula (1) is used. For example, when ^R3 is a methyl group, methylamine is used as the imidating agent.
The imidization by the imidization agent may be performed using an extruder or the like, or may be performed using a batch reaction tank (pressure vessel) or the like.

When the imidized resin (A) is produced using an extruder, for example, a single-screw extruder, a twin-screw extruder, or a multi-screw extruder with three or more screws can be used.
A twin-screw extruder is preferable as the extruder in that it can facilitate mixing of the imidizing agent with the raw material polymer.
Types of twin-screw extruders include a non-intermeshing co-rotating type, an intermeshing co-rotating type, a non-intermeshing counter-rotating type, and an intermeshing counter-rotating type. The system of the twin-screw extruder may be any of these systems.
As the system of the twin-screw extruder, an intermeshing co-rotating system is preferable in that it can rotate at a high speed and facilitates the mixing of the imidizing agent with the raw material polymer.
One extruder may be used alone, or two or more extruders may be used by connecting in series.

The extruder is preferably equipped with a vent port to remove unreacted imidizing agents, by-products such as methanol, and unreacted monomers. It is preferable that the vent port can be pressure-reduced to atmospheric pressure or less.

The imidized resin (A) can be used in a horizontal twin-screw reactor such as Vivolac (registered trademark) manufactured by Sumitomo Heavy Industries Process Equipment Co., Ltd. It can also be manufactured using an apparatus.

When the imidized resin (A) is produced using a batch type reaction tank (pressure vessel), the raw material polymer can be melted by heating, the molten raw material polymer can be sufficiently stirred, and the imidizing agent and the ring closure accelerator can be used. The structure of the reaction vessel is not particularly limited as long as it can be added to the reaction vessel.
Considering that the viscosity of the polymer increases as the reaction progresses, it is preferable that the reactor has a stirring device with good stirring efficiency. As a stirring device having good stirring efficiency, Maxblend (registered trademark) manufactured by Sumitomo Heavy Industries Process Equipment Co., Ltd., and the like can be mentioned.

When producing the imidized resin (A), modification with an esterifying agent may be carried out for the purpose of reducing by-produced carboxy groups and acid anhydride groups.

Specific examples of the esterifying agent include dimethyl carbonate, 2,2-dimethoxypropane, dimethyl sulfoxide, triethyl orthoformate, trimethyl orthoacetate, trimethyl orthoformate, diphenyl carbonate, dimethyl sulfate, methyltoluene sulfonate, methyltri Fluoromethylsulfonate, methyl acetate, methanol, ethanol, methyl isocyanate, p-chlorophenyl isocyanate, dimethylcarbodiimide, dimethyl-tert-butylsilyl chloride, isopropenyl acetate, dimethylurea, tetramethylammonium hydroxide, dimethyldiethoxysilane, tetra- N-butoxysilane, dimethyl(trimethylsilane) phosphite, trimethyl phosphite, trimethyl phosphate, tricresyl phosphate, diazomethane, ethylene oxide, propylene oxide, cyclohexene oxide, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and benzyl glycidyl ether and the like.

<Masterbatch>
The imidized resin composition contains a lubricant (B), which will be described later, in a small amount of 0.0015% by mass (15 mass ppm) or more and 0.01 mass% (100 mass ppm) or less with respect to the mass of the imidized resin (A). include. For this reason, when using an extruder to melt-knead the imidized resin (A) and the lubricant (B) to produce an imidized resin composition, stable supply of the lubricant (B) into the extruder and , it is difficult to uniformly disperse the lubricant (B) in the imidized resin composition. In this regard, by supplying the lubricant (B) to the extruder as a masterbatch containing the base material and the lubricant (B), the small amount of the lubricant (B) can be stably added while suppressing the variation in the amount added. can be blended into the imidized resin (A), and the lubricant (B) can be easily dispersed uniformly in the imidized resin composition.

The content of the lubricant (B) in the masterbatch is not particularly limited as long as the imidized resin composition containing the desired amount of the lubricant (B) can be produced.
The content of the lubricant (B) in the masterbatch is preferably 0.1 mass% (1,000 mass ppm) to 10 mass% (100,000 mass ppm) relative to the mass of the masterbatch, and 0.2 mass%. (2,000 ppm by mass) to 5% by mass (50,000% by mass) is more preferable.
When the content of the lubricant (B) in the masterbatch is within the above range, the masterbatch contains a sufficient amount of the lubricant (B) and the lubricant (B) is sufficiently diluted with the base material. Therefore, it is particularly easy to stably supply a desired amount of the lubricant (B) to the imidized resin (A) in the extruder.

The form of the masterbatch is not particularly limited as long as the masterbatch can be quantitatively fed into the extruder. The form of the masterbatch may be either liquid or solid, preferably solid. The solid masterbatch is preferably in the form of powder, granules, or pellets.

The method for producing the masterbatch is not particularly limited as long as the base material and the lubricant (B) can be uniformly mixed.
For example, a masterbatch may be produced as a powder mixture in which a powdery lubricant (B) and a powdery base material are uniformly mixed.
Alternatively, the powdery lubricant (B) and the powdery base material are uniformly mixed and granulated by a known method or pelletized by a method such as tableting to produce a masterbatch. You may
When producing granules or pellets using a powdery lubricant (B) and a powdery base material, known binders and excipients are used as long as the properties of the imidized resin composition are not adversely affected. agent may be used.

Further, after uniformly mixing the melted base material and the powdery or melted lubricant (B), the resulting mixture is cooled and solidified while being granulated or pelletized by a known method. A masterbatch may be produced by Examples of a method for uniformly mixing the melted base material and the powdery or melted lubricant (B) include a method using an extruder such as a single-screw extruder or a twin-screw extruder.

〔Base material〕
The base material is particularly limited as long as it does not excessively adversely affect the physical properties such as transparency of the imidized resin composition and is difficult to thermally decompose in the melt-kneading when the masterbatch is mixed with the imidized resin. not.
Examples of the base material include additives such as thermoplastic resins, ultraviolet absorbers, antioxidants, and the like, which are conventionally added to various resins. As the additive, an ultraviolet absorber is preferable. That is, a thermoplastic resin and/or an ultraviolet absorber are preferable as the base material.
It may be difficult to quantitatively supply an ultraviolet absorber to an extruder due to its properties. Ultraviolet absorbers tend to cause bridging and blocking, and often have poor fluidity as powder. In this respect, powder characteristics such as fluidity of the ultraviolet absorbent can be improved by mixing the ultraviolet absorbent and the lubricant (B) to form a masterbatch. As a result, by using a masterbatch containing an ultraviolet absorber as a base material and a lubricant (B), it is possible to quantitatively supply not only the lubricant (B) but also the ultraviolet absorber to the imidized resin (A). become easier.

The masterbatch may contain only one base material, or may contain two or more base materials. For example, the masterbatch may contain a combination of a thermoplastic resin and an ultraviolet absorber as a base material.

Examples of thermoplastic resins include the imidized resins described above; polyolefins such as low-density polyethylene, high-density polyethylene, polypropylene, ethylene-propylene copolymer, poly-1-butene and poly-4-methyl-1-pentene; (Meth) acrylic resins such as (meth) acrylate; polystyrene; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PNE), polylactic acid (PLA); nylon 6, nylon Polyamide resins such as 6,6, nylon 12, nylon 6,12, and MXD nylon; polycarbonate resins; and the like can be used.
Among these thermoplastic resins, the imidized resin composition has little adverse effect on the physical properties of the imidized resin composition, and the lubricant (B) is easily dispersed uniformly in the imidized resin composition. A (meth)acrylic resin such as meth)acrylate is preferred.

The ultraviolet absorber is not particularly limited, and ultraviolet absorbers conventionally blended in various resins can be used. Examples of UV absorbers that can be used include benzotriazole compounds, triazine compounds, oxalic acid anilide compounds, cyanoacrylate compounds, salicylate compounds, and benzophenone compounds. Among these, triazine compounds are preferred from the viewpoint of light resistance of the imidized resin composition.

Examples of triazine compounds include 2,4-diphenyl-6-(2-hydroxyphenyl-4-hexyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethyl Phenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[( hexyl)oxy]phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4, 6-tris(2-hydroxy-4-alkoxy-3-methylphenyl)-1,3,5-triazine is preferred.
The alkoxy group of 2,4,6-tris(2-hydroxy-4-alkoxy-3-methylphenyl)-1,3,5-triazine is a linear or branched chain having 1 to 10 carbon atoms. Alkoxy groups are preferred. 2,4,6-tris(2-hydroxy-4-alkoxy-3-methylphenyl)-1,3,5-triazine includes 2,4,6-tris(2-hydroxy-4-hexyloxy-3 -methylphenyl)-1,3,5-triazine is preferred.

Among the triazine compounds described above, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2 ,4,6-tris(2-hydroxy-4-alkoxy-3-methylphenyl)-1,3,5-triazine is preferred.

2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol is ADEKA STAB LA-46 (manufactured by ADEKA Corporation) available as 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine is available as ADEKA STAB LA-F70 (manufactured by ADEKA Corporation).

When an ultraviolet absorber is used as the base material, the content of the ultraviolet absorber in the imidized resin composition is not particularly limited as long as the desired effects are not impaired. The ultraviolet absorber is preferably contained in an amount of 0.1% by mass to 3% by mass, more preferably 0.2% by mass to 2% by mass, based on the mass of the imidized resin (A).
When the imidized resin composition contains an ultraviolet absorber in an amount within the above range, it is possible to satisfactorily suppress deterioration of the imidized resin composition due to ultraviolet rays, and a film formed using the imidized resin composition. There is particularly little adverse effect on the transparency, mechanical properties, etc. of molded products such as.
When a masterbatch is used so that the desired amount of the lubricant (B) is contained in the imidized resin composition, if the content of the ultraviolet absorber in the imidized resin composition is less than the desired amount, the masterbatch Alternatively, an ultraviolet absorber may be added to the imidized resin composition.

[Lubricant (B)]
As the lubricant (B), thermoplastic resins, particularly acrylic resins, and lubricants generally blended with imidized resins can be used without particular limitation.
Preferable examples of the lubricant (B) include fatty acid amide lubricants, fatty acid ester lubricants, metal soap lubricants, polymer lubricants, aliphatic hydrocarbon lubricants, aliphatic alcohol lubricants, and aliphatic acid lubricants. is mentioned.
As the lubricant (B), one type may be used alone, or two or more types may be used in combination.

Fatty acid amide-based lubricants are amide compounds in which fatty acids are condensed with ammonia, amines, or urea. The fatty acid may be a polyvalent carboxylic acid having a valence of 2 or more. The amine may be a divalent or higher polyvalent amine.
Preferred specific examples of fatty acid amide lubricants include stearamide, oleic acid amide, erucic acid amide, behenic acid amide, stearyl erucic acid amide, ethylene bis erucic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, N-oleyl palmitoamide, N-stearyl erucamide, polycondensate of ethylenediamine/stearic acid/sebacic acid and the like.

Fatty acid ester-based lubricants are compounds in which fatty acids and alcohols are condensed. The fatty acid may be a polyvalent carboxylic acid having a valence of 2 or more. The alcohol may be a dihydric or higher polyhydric alcohol. Fatty acid ester lubricants include higher fatty acid esters of monohydric alcohols, higher fatty acid (partial) esters of polyhydric alcohols, montanic acid esters, partially saponified montanic acid esters, and complex montanic acid esters.
Preferred specific examples of fatty acid ester lubricants include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate, and isopropyl myristate. , isopropyl palmitate, octyl palmitate, coconut fatty acid octyl ester, octyl stearate, bovine fatty acid octyl ester, lauryl laurate, stearyl stearate, behenyl behenate, cetyl myristate, neopentyl polyol long chain fatty acid ester, pentaerythritol fatty acid Condensed ester, trimethylolpropane fatty acid ester, trimethylolpropane trioleate, trimethylolpropane trifatty acid ester, pentaerythritol fatty acid ester, neopentyl glycol diolate, pentaerythritol tetraoleate, pentaerythritol tetraoleic acid ester, dipentaerythritol fatty acid ester , neopentyl glycol dicaprate, trimethylolpropane dicaprate, dipentaerythritol hexaisononanoate, trimethylolpropane fatty acid condensed ester, and the like.

Any known metallic soap-based lubricant can be used as the metallic soap-based lubricant. Metal soap lubricants are metal salts of fatty acids such as stearic acid, lauric acid, myristic acid and castor oil fatty acid. Metal salts include aluminum salts, calcium salts, zinc salts, magnesium salts, barium salts and the like.
Preferred specific examples of metal soap-based lubricants include calcium stearate, zinc stearate and magnesium stearate. Among these, zinc stearate is more preferred.

Any known polymeric lubricant can be used as the polymeric lubricant.
Preferred specific examples of polymeric lubricants include alkyl acrylate/alkyl methacrylate/styrene copolymers.

Any known aliphatic hydrocarbon lubricant can be used as the aliphatic hydrocarbon lubricant.
Preferred specific examples of aliphatic hydrocarbon-based lubricants include polyolefin waxes such as polyethylene wax, C16 or higher liquid paraffin, microcrystalline wax, natural paraffin, synthetic paraffin, and partial oxides, fluorides, and chlorides thereof. etc.

Any known fatty alcohol-based lubricant can be used as the fatty alcohol-based lubricant.
Preferred specific examples of aliphatic alcohol lubricants include hexanol (caproyl alcohol), octanol (capryl alcohol), decanol (decyl alcohol), dodecanol (lauryl alcohol), tetradecanol (myristyl alcohol), and hexadecanol. (cetyl alcohol), octadecanol (stearyl alcohol), eicosanol (arachidyl alcohol), docosanol (behenyl alcohol), and the like. Among these, octadecanol (stearyl alcohol) is preferred.

Any known fatty acid-based lubricant can be used as the fatty acid-based lubricant.
Preferred specific examples of fatty acid lubricants include saturated fatty acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid, and unsaturated fatty acids such as oleic acid and erucic acid. mentioned.

Among the above lubricants (B), fatty acid amide-based lubricants are preferred, and stearic acid amides are more preferred, since they are highly effective in suppressing transverse dandruff in a film formed using the imidized resin composition.

<Other ingredients>
The imidized resin composition may contain known additives such as stabilizers, plasticizers, ultraviolet absorbers, antioxidants, fillers, and other resins, if necessary. Here, the above additives and other resins are materials that are blended into the imidized resin composition separately from the base material in the masterbatch.

<Method for producing imidized resin composition>
The method for producing the imidized resin composition comprises:
Supplying the imidized resin (A) into the extruder from the main feed port of the extruder;
Adding a lubricant (B) to the molten imidized resin (A) in the extruder;
kneading the imidized resin (A) and the lubricant (B) in an extruder;
Collecting the imidized resin composition discharged from within the extruder;
including.

Supply of the imidized resin (A) into the extruder is performed by supplying the imidized resin (A) from the main feed port of the extruder according to a conventional method.
For example, the imidized resin (A) may be supplied into the extruder by a method of supplying pellets of the imidized resin (A) using a quantitative feeder or the like.
In addition, when producing the imidized resin (A) using an extruder or the like according to the above-described method, from the outlet of the imidized resin (A) production apparatus such as an extruder, to produce the imidized resin composition The molten imidized resin (A) may be fed directly into the main feed port of the extruder used. In this case, usually, the outlet of the imidized resin (A) manufacturing apparatus and the main feed port of the extruder used for manufacturing the imidized resin composition are connected by a pipe.

The amount of imidized resin (A) supplied into the extruder is not particularly limited. The amount of the imidized resin (A) to be fed into the extruder is appropriately determined in consideration of the size of the extruder, the residence time of the imidized resin (A) in the extruder, and the like.

The imidized resin (A) fed into the extruder is melted and kneaded with a masterbatch containing the lubricant (B) in the extruder in a molten state. The screw configuration of the extruder is not particularly limited as long as the lubricant (B) can be uniformly dispersed in the imidized resin composition.

The masterbatch is fed into the extruder from a side feed port positioned downstream in the extrusion direction of the main feed port in the extruder. This suppresses the thermal decomposition and volatilization of the lubricant (B), and facilitates the addition of a desired amount of the lubricant (B) to the imidized resin composition.

In the masterbatch, the content of the lubricant (B) in the resulting imidized resin composition is 0.0015% by mass (15 ppm by mass) or more and 0.02% by mass ( 200 mass ppm) or less.
The content of the lubricant (B) in the imidized resin composition is 0.0020% by mass (20% by mass) or more and 0.02% by mass (200% by mass) or less with respect to the mass of the imidized resin (A). Preferably, 0.0025% by mass (25% by mass) or more and 0.015% by mass (150% by mass) or less, more preferably 0.0030% by mass (30% by mass) or more and 0.010% by mass (100% by mass) or less is more preferred.

If the content of the lubricant (B) in the imidized resin composition is excessive, volatile matter due to the lubricant (B) is likely to be generated by heating during molding of the imidized resin composition. If a large amount of volatile matter is generated due to the lubricant (B), a moldable device such as a roll is likely to be contaminated by the adhesion of the volatile matter. The problem that the production efficiency of the molded product is lowered occurs due to the frequent operation. When the content of the lubricant (B) in the imidized resin composition is too small, it is difficult to obtain the desired effect of suppressing the generation of lateral sag by using the lubricant (B).

When the imidized resin (A) and the lubricant (B) are melt-kneaded in an extruder, considering the volatilization of the lubricant (B) according to the melt-kneading conditions, the desired amount in the imidized resin composition A larger amount of lubricant (B) than the amount of lubricant (B) used may be used. For example, an amount of the lubricant that is 1.01 to 10 times, preferably 1.05 to 5 times, more preferably 1.1 to 3 times the content of the lubricant (B) in the imidized resin composition (B) may be fed into the extruder.

When the imidized resin (A) and the lubricant (B) are melt-kneaded in the extruder, the residence time of the lubricant (B) in the extruder is to suppress excessive thermal decomposition and volatilization of the lubricant (B). From the viewpoint of allowing the imidized resin composition to contain a desired amount of the lubricant (B), the time is preferably 50 seconds or more and 300 seconds or less, more preferably 70 seconds or more and 200 seconds or less.

When the imidized resin (A) and the lubricant (B) are melt-kneaded in the extruder, the barrel temperature of the extruder is not particularly limited as long as the imidized resin (A) melts. Further, when the masterbatch containing the lubricant (B) contains a thermoplastic resin as a base material, from the viewpoint of uniformly dispersing the lubricant (B) in the imidized resin composition, the barrel temperature of the extruder is A temperature at which the resin melts is preferred.
While suppressing thermal decomposition and thermal deterioration of the imidized resin (A) and the components contained in the masterbatch, the melt-kneading can be performed particularly well, so the barrel temperature of the extruder is typically 180. ° C. or higher and 280 ° C. or lower, and more preferably 200 ° C. or higher and 270 ° C. or lower.

The imidized resin (A) and the lubricant (B) melted and kneaded in the extruder as described above are extruded as an imidized resin composition from the extruder's outlet. A method for recovering the imidized resin composition discharged from the discharge port is not particularly limited. The imidized resin composition discharged from the discharge port is usually collected in the form of strands while being cooled, and pelletized by being cut by a pelletizer.

<Film>
A film made of the imidized resin composition is provided by forming a film from the imidized resin composition described above. Such films may be used as monolayer films or as laminated films. One layer or two or more layers in the laminated film are films made of the aforementioned imidized resin composition.
The thickness of the monolayer film made of the imidized resin composition is not particularly limited, and is appropriately selected according to the use of the film. The thickness of the monolayer film made of the imidized resin composition is preferably 10 μm or more and 100 μm or less, more preferably 20 μm or more and 60 μm or less.
The film described above can be suitably used, for example, as an optical film for displays. Examples of optical films for displays include protective films such as polarizer protective films.

The above film may be a stretched film. A stretched film is obtained by stretching an unstretched film (also referred to as a raw film). By stretching an unstretched film, a stretched film having a desired thickness can be produced and the mechanical properties of the stretched film can be improved. A conventionally known method can be used as the stretching method. For example, an unstretched original film formed by melt extrusion can be uniaxially stretched or biaxially stretched to produce a stretched film having a predetermined thickness.

The polarizer protective film is desired to have excellent transparency. When the above film is used as a polarizer protective film, it is preferred that the haze of the film is small. The haze of the film is preferably 0.4 or less, preferably 0.3 or less, and more preferably 0.2 or less.
Here, the film haze is the haze value of a stretched film obtained by stretching a 40 μm-thick film produced by the T-die method at a temperature of 135° C. at a magnification of 2 in both the MD and TD directions. The haze value can be measured, for example, using a haze meter "NDH2000" manufactured by Nippon Denshoku Industries.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited by these examples.

[Production Example 1]
(Production of imidized resin)
A resin was produced using a tandem type extrusion reactor in which two extruders were arranged in series, the first extruder and the second extruder. As the first extruder and the second extruder, co-meshing twin-screw extruders with a diameter of 75 mm and L/D (ratio of length L to diameter D of the extruder) of 74 were used. The first extruder and the second extruder were connected by a pipe with a diameter of 38 mm and a length of 2 m. A constant flow pressure valve was used as a component internal pressure control mechanism that connects the resin discharge port of the first extruder and the raw material supply port of the second extruder.

A raw material resin was supplied to the raw material supply port of the first extruder using a constant weight feeder (manufactured by Kubota Corporation).
The pressure reduction degree of each vent in the first extruder and the second extruder was -0.095 MPa.
With respect to the first extruder, an imidized resin intermediate 1 was produced using a polymethyl methacrylate resin (Mw: 105,000) as a raw material resin and monomethylamine as an imidizing agent. At this time, the highest temperature part temperature of the extruder was 280° C., the screw rotation speed was 55 rpm, the raw material resin supply amount was 150 kg/hour, and the amount of monomethylamine added was 2.0 parts by mass with respect to 100 parts by mass of the raw material resin. . A constant flow pressure valve was installed immediately before the raw material supply port of the second extruder, and the pressure of the monomethylamine injection section of the first extruder was adjusted to 8 MPa.
The resin (strand) discharged from the second extruder was cooled by a cooling conveyor and then cut by a pelletizer into pellets.
Here, in order to adjust the internal pressure of the part connecting the resin discharge port of the first extruder and the second extruder raw material supply port, or to determine the extrusion fluctuation, the first extruder outlet, the first extruder and the second A resin pressure gauge was provided at the central portion of the connection part with the extruder and at the outlet of the second extruder.

Regarding the second extruder, after devolatilizing the imidization reaction reagent and by-products remaining in the rear vent and vacuum vent, a mixed solution of dimethyl carbonate and triethylamine is added as an esterification agent to produce an imidized resin. did. At this time, the temperature of each barrel of the extruder was 260° C., and the number of screw revolutions was 55 rpm. The amount of dimethyl carbonate added was 3.2 parts by mass with respect to 100 parts by mass of the starting resin. The amount of triethylamine added was 0.8 parts by mass with respect to 100 parts by mass of the starting resin. Furthermore, after removing the esterifying agent with a vent, the product was extruded through a strand die, cooled in a water tank, and then pelletized with a pelletizer to obtain an imidized resin.
The resulting imidized resin had an imidization rate of 3.7%, an acid value of 0.29 mmol/g, and a carboxylic acid content of 0.05 mmol/g.

[Production Example 2]
powder of 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine (ADEKA STAB LA-F70, manufactured by ADEKA Corporation) as an ultraviolet absorber; and stearic acid amide powder as a lubricant were blended using a powder blender (Super Mixer, manufactured by Kawata Co., Ltd.) to obtain a masterbatch containing an ultraviolet absorber and a lubricant.
The above UV absorbers tend to cause bridging and blocking and are poor in fluidity as powder. In this regard, powder properties such as fluidity have been improved by mixing stearic acid amide as a lubricant with the above ultraviolet absorber to form a masterbatch.
The lubricant content relative to the mass of the masterbatch was 10,000 ppm by mass.

[Production Example 3]
The polymethyl methacrylate resin (PMMA) used in Production Example 1 and stearic acid amide as a lubricant were melt-kneaded by an extruder at a barrel temperature of 280° C. to obtain a masterbatch containing the lubricant. The form of the masterbatch was pellet form.
The lubricant content relative to the mass of the masterbatch was 2,000 ppm by mass.

[Example 1]
For the imidized resin supplied from the first extruder to the second extruder, 1 part by mass of the masterbatch obtained in Production Example 2 is added to 100 parts by mass of the imidized resin, and the side provided by the second extruder Pellets of the imidized resin composition were obtained in the same manner as in Production Example 1, except that the imidized resin composition was supplied from the feed port.
The content of the lubricant in the obtained imidized resin composition was 100 mass ppm with respect to the mass of the imidized resin.
Since the UV absorber itself used in the production of the masterbatch in Production Example 2 is a fine powder with poor fluidity, it is difficult to quantitatively supply the UV absorber from the side feed port to the extruder. In this regard, the masterbatch obtained in Production Example 2 could be quantitatively supplied to the extruder from the side feed port.

[Example 2]
For the imidized resin supplied from the first extruder to the second extruder, the masterbatch obtained in Production Example 2 is 0.5 parts by mass with respect to 100 parts by mass of the imidized resin, and the second extruder is Pellets of the imidized resin composition were obtained in the same manner as in Production Example 1, except that the imidized resin composition was supplied from the provided side feed port.
The content of the lubricant in the obtained imidized resin composition was 50 mass ppm with respect to the mass of the imidized resin.

[Example 3]
For the imidized resin supplied from the first extruder to the second extruder, the masterbatch obtained in Production Example 3 is 5 parts by mass per 100 parts by mass of the imidized resin, and the side provided by the second extruder Pellets of the imidized resin composition were obtained in the same manner as in Production Example 1, except that the imidized resin composition was supplied from the feed port.
The content of the lubricant in the obtained imidized resin composition was 50 mass ppm with respect to the mass of the imidized resin.

[Example 4]
For the imidized resin supplied from the first extruder to the second extruder, the masterbatch obtained in Production Example 3 is 5 parts by mass per 100 parts by mass of the imidized resin, and the side provided by the second extruder Supplying from a feed port, and supplying 1 part by mass of the ultraviolet absorber used in Production Example 2 with respect to 100 parts by mass of the imidized resin from a side feed port different from the side feed port for supplying the masterbatch Except for this, pellets of the imidized resin composition were obtained in the same manner as in Production Example 1.
The content of the lubricant in the obtained imidized resin composition was 50 mass ppm with respect to the mass of the imidized resin.
In Example 4, the UV absorber was fed separately from the masterbatch. In Example 4, the masterbatch could be quantitatively supplied to the extruder. It was not possible to supply quantitatively to

[Comparative Example 1]
For the imidized resin supplied from the first extruder to the second extruder, the masterbatch obtained in Production Example 2 is 0.1 parts by mass with respect to 100 parts by mass of the imidized resin, and the second extruder is Pellets of the imidized resin composition were obtained in the same manner as in Production Example 1, except that the imidized resin composition was supplied from the provided side feed port.
The content of the lubricant in the obtained imidized resin composition was 10 mass ppm with respect to the mass of the imidized resin.

[Comparative Example 2]
For the imidized resin supplied from the first extruder to the second extruder, stearic acid amide as a lubricant is added to 50 ppm by mass with respect to the weight of the imidized resin, from the side feed port provided in the second extruder. Pellets of the imidized resin composition were obtained in the same manner as in Production Example 1, except that the imidized resin composition was supplied.
However, because the amount of the lubricant supplied was too small, the imidized resin composition could not be blended with the desired amount of the lubricant quantitatively.

[Comparative Example 3]
For the imidized resin supplied from the first extruder to the second extruder, 10 parts by mass of the masterbatch obtained in Production Example 2 is added to 100 parts by mass of the imidized resin, and the side provided by the second extruder Pellets of the imidized resin composition were obtained in the same manner as in Production Example 1, except that the imidized resin composition was supplied from the feed port.
The content of the lubricant in the obtained imidized resin composition was 1000 mass ppm with respect to the mass of the imidized resin.

[Comparative Example 4]
For the imidized resin supplied from the first extruder to the second extruder, the masterbatch obtained in Production Example 2 is 5 parts by mass per 100 parts by mass of the imidized resin, and the side provided by the second extruder Pellets of the imidized resin composition were obtained in the same manner as in Production Example 1, except that the imidized resin composition was supplied from the feed port.
The content of the lubricant in the obtained imidized resin composition was 500 mass ppm with respect to the mass of the imidized resin.

[Comparative Example 5]
For the imidized resin supplied from the first extruder to the second extruder, the masterbatch obtained in Production Example 2 is 3 parts by mass per 100 parts by mass of the imidized resin, and the side provided by the second extruder Pellets of the imidized resin composition were obtained in the same manner as in Production Example 1, except that the imidized resin composition was supplied from the feed port.
The content of the lubricant in the obtained imidized resin composition was 300 mass ppm with respect to the mass of the imidized resin.

Using the obtained imidized resin compositions of Examples and Comparative Examples, films were produced according to the following methods, and evaluation of roll contamination, evaluation of volatile gas amount, evaluation of lateral damping, and haze were performed. evaluated and performed.

<Film production>
Films were produced using a single-screw extruder with a T-die connected to the outlet, equipped with a leaf disk filter with an opening of 5 μm. The set temperature of the temperature control zone of the extruder was set to 260° C., and the screw rotation speed was set to 20 rpm. The pellets of each example and each comparative example were supplied to an extruder at a rate of 10 kg/hr, and the melt-extruded film was taken up by a cast roll to obtain a film having a thickness of 40 μm.

<Roll contamination evaluation>
When the film was produced by the above method, the surface of the cast roll was visually observed, and roll contamination was evaluated according to the following criteria.
0: No deposits on the cast roll by visual evaluation 1: Slight deposits on the cast roll by visual evaluation 2: Deposits on about 1/10 of the area of the film contact portion of the cast roll by visual evaluation Observable 3: Deposits can be seen on about 1/5 of the area of the film contact portion of the cast roll by visual evaluation 4: Deposits are found on almost the entire surface of the cast roll by visual evaluation, but there are only a few places where it is not attached. 5: Deposits are observed on the entire surface of the cast roll by visual evaluation, and no specular gloss is observed on the cast roll.

<Evaluation of volatile gas>
Volatile gas was evaluated according to the following criteria by visually observing the die during film production.
0: There is no volatile gas at all when the resin is discharged from the die by visual evaluation 1: A slight amount of volatile gas is generated intermittently when the resin is discharged from the die by visual evaluation 2: By visual evaluation A slight amount of volatile gas is generated when the resin is extruded from the die. 3: Volatile gas is intermittently generated when the resin is extruded from the die by visual evaluation.
4: Visual evaluation shows that volatile gas is always generated when the resin is discharged from the die 5: Visual evaluation shows that a large amount of volatile gas is always generated when the resin is discharged from the die

<Evaluation of horizontal damping>
The film (original fabric) obtained by the above method was stretched at a magnification of 2 times in both the MD and TD directions at a furnace temperature of 135° C. to obtain a stretched film. The stretched film thus obtained was visually observed, and transverse damping was evaluated according to the following criteria. A transverse wrinkle is a wrinkle (typically a streak) in the TD direction that occurs in a longitudinally stretched film.
〇: No horizontal sagging is observed by visual evaluation ×: Horizontal sagging is observed by visual evaluation

<Haze evaluation>
Using a haze meter "NDH2000" manufactured by Nippon Denshoku Industries, the haze of the stretched film obtained in the same manner as the transverse damping evaluation was measured.

Table 1 shows the method of adding the lubricant, the type of base material contained in the lubricant, the content of the lubricant, the evaluation result of roll contamination, the evaluation result of the amount of volatilized gas, the evaluation result of the lateral damping, and the haze. Write down the evaluation results.
In addition, the content rate of the lubricant in Table 1 is the content rate of the lubricant with respect to the mass of imidized resin.

According to Table 1, for the imidized resin containing a predetermined amount of the above-described predetermined units and not containing an aromatic vinyl unit, 0.0015 of a lubricant is used as a masterbatch with respect to the mass of the imidized resin (A). By blending in an amount of 0.01% by mass (15% by mass ppm) or more and 0.01% by mass (100% by mass) or less, roll contamination that causes poor appearance of molded products such as films and generation of volatile gas are suppressed. , it can be seen that the occurrence of lateral damping can be suppressed.
On the other hand, according to Comparative Example 1, it was found that when the amount of the lubricant compounded was too small, the occurrence of lateral sagging could not be suppressed. It can be seen that roll contamination and volatile gas generation, which cause poor appearance of molded products, are likely to occur.
Further, according to Comparative Example 2, it is found that it is difficult to quantitatively and stably mix a predetermined small amount of lubricant into the imidized resin unless the lubricant is blended as a masterbatch.

Claims (9)

A method for producing an imidized resin composition containing an imidized resin (A) and a lubricant (B),
Supplying the imidized resin (A) into the extruder from a main feed port in the extruder;
adding the lubricant (B) to the molten imidized resin (A) in the extruder;
kneading the imidized resin (A) and the lubricant (B) in the extruder;
Collecting the imidized resin composition discharged from the extruder;
including
The imidized resin (A) may contain a unit represented by the following formula (1) and a unit represented by the following formula (2), and may also contain a unit represented by the following formula (3). often,
The ratio of the mass of the unit represented by the formula (3) to the mass of the imidized resin (A) is 5% by mass or less,
The imidized resin composition contains 0.0015% by mass or more and 0.01% by mass or less of the lubricant (B) with respect to the mass of the imidized resin (A),
The lubricant (B) is supplied into the extruder as a masterbatch containing the lubricant (B) and a base material,
A method for producing an imidized resin composition, wherein the masterbatch is fed into the extruder from a side feed port positioned downstream in the extrusion direction from the main feed port.

(In formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 18 carbon atoms, a carbon atom represents a cycloalkyl group having 3 to 12 carbon atoms or an aromatic group-containing group having 5 to 15 carbon atoms.)

(In formula (2), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁶ represents an alkyl group having 1 to 18 carbon atoms, a carbon atom represents a cycloalkyl group having 3 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms.)

(In formula (3), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁸ represents an aryl group having 6 to 10 carbon atoms.) 2. The method for producing an imidized resin composition according to claim 1, wherein the base material is a thermoplastic resin and/or an ultraviolet absorber. 3. The method for producing an imidized resin composition according to claim 2, wherein the substrate is an ultraviolet absorber. 4. The method for producing an imidized resin composition according to claim 3, wherein the ultraviolet absorber is a triazine compound. containing an imidized resin (A) and a lubricant (B),
The imidized resin (A) may contain a unit represented by the following formula (1) and a unit represented by the following formula (2), and may also contain a unit represented by the following formula (3). often,
The ratio of the mass of the unit represented by the formula (3) to the mass of the imidized resin (A) is 5% by mass or less,
An imidized resin composition comprising the lubricant (B) in an amount of 0.0015% by mass or more and 0.01% by mass or less relative to the mass of the imidized resin (A).

(In formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 18 carbon atoms, a carbon atom represents a cycloalkyl group having 3 to 12 carbon atoms or an aromatic group-containing group having 5 to 15 carbon atoms.)

(In formula (2), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁶ represents an alkyl group having 1 to 18 carbon atoms, a carbon atom represents a cycloalkyl group having 3 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms.)

(In formula (3), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R 8 represents an aryl group having 6 to 10 carbon atoms.) 6. The imidized resin composition according to claim 5, comprising an ultraviolet absorber. 7. The imidized resin composition according to claim 6, wherein said ultraviolet absorber is a triazine compound. A film comprising the imidized resin composition according to any one of claims 5 to 7. 9. The film of claim 8, which is an optical film.