JP2021075036A - Film defect detection system - Google Patents

Abstract

To provide a system that can continuously and stably detect defects, especially cracks, in a resin film.SOLUTION: The system detects defects in the resin film in a tenter-type stretching system that grasps both ends of the resin film, transports it, and stretches it. The system has an irradiation section that radiates ultraviolet light and a sensor section that detects the ultraviolet light, and the system detects defects in the resin film by irradiating the resin film with the ultraviolet light and detecting the ultraviolet light transmitted through the resin film by the sensor section.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a system for detecting film defects, especially crack defects.

In flexible display devices, a transparent resin film that replaces glass is required. As the material of such a transparent resin film, a material having high transparency and mechanical strength is preferable, and for example, a polyimide resin and a polyamide resin are known (Patent Document 1).

In the production of such a transparent resin film, a heat treatment of the resin film may be performed in order to obtain a desired quality, for example, a heat treatment may be performed using a tenter type stretching device.

Japanese Unexamined Patent Publication No. 2009-286826

When the resin film is continuously processed by the tenter type stretching apparatus, the processing is performed by grasping both ends of the resin film with the tenter clip and continuously transporting the resin film. At this time, the resin film may be cracked at the portion gripped by the tenter clip. If such cracks are left unattended, the resin film carried out from the tenter type stretching apparatus may break starting from the cracks. If such a break occurs during continuous processing, economic loss such as a decrease in film yield and a decrease in the operating rate of the apparatus occurs. On the other hand, if the cracks at both ends are monitored by constantly visually monitoring the presence or absence of cracks in the resin film, the human burden increases.

The present disclosure has been proposed in view of such circumstances, and an object of the present disclosure is to provide a system capable of continuously and stably detecting defects in a resin film, particularly crack defects as described above. ..

The disclosure provides:
[1] A system for detecting defects in a resin film in a tenter-type stretching apparatus that grips, conveys, and stretches both ends of the resin film.
It has an irradiation unit that irradiates ultraviolet light and a sensor unit that detects the ultraviolet light.
A system for detecting defects in a resin film by irradiating the resin film with the ultraviolet light and detecting the ultraviolet light transmitted through the resin film with the sensor unit.
[2] A system for detecting defects in a resin film in a tenter-type stretching device that grips, conveys, and stretches both ends of a resin film between a pedestal of a gripping tool and a gripping portion.
It has an irradiation unit that irradiates light and a sensor unit that detects the light.
The irradiation unit and the sensor unit are arranged so as to face each other with the resin film interposed therebetween.
The irradiation portion is located on the surface side where the resin film is in contact with the pedestal, and the sensor portion is located on the surface side where the resin film is in contact with the grip portion.
A system for detecting defects in a resin film by irradiating the resin film with the light and detecting the light transmitted through the resin film with the sensor unit.
[3] The system according to the above [2], wherein the light is ultraviolet light.
[4] The system according to the above [1] or [3], wherein the wavelength of the maximum intensity of the ultraviolet light is in the range of 200 to 380 nm.
[5] The item according to any one of [1] to [4] above, which is installed between a portion where the resin film is released from the gripper after stretching and a portion where the resin film is wound. system.
[6] The angle formed by the irradiation axis connecting the irradiation portion and the center portion and the main surface of the resin film is 10 to 80 °, according to any one of the above [1] to [5]. Described system.
[7] The angle formed by the irradiation axis connecting the irradiation unit and the sensor unit with a surface parallel to the transport direction of the resin film and perpendicular to the main surface of the resin film is 0 to 15 °, as described above [1]. ] To the system according to any one of [6].
[8] The system according to any one of [1] to [7] above, wherein the distance between the irradiation unit and the main surface of the resin film along the irradiation axis is 1 to 250 mm.
[9] The system according to any one of [1] to [8] above, wherein the distance between the sensor unit and the main surface of the resin film along the irradiation axis is 1 to 250 mm.
[10] The system according to any one of [1] to [9] above, wherein the gripped resin film is irradiated with ultraviolet light at a portion released from the gripper.
[11] The system according to any one of [1] to [10] above, wherein the resin film is a resin film selected from the group consisting of a polyimide resin and a polyamide resin.
[12] The system according to any one of the above [1] to [11], wherein the resin film contains an ultraviolet absorber.
[13] A tenter type stretching apparatus having the system according to any one of the above [1] to [12].
[14] A method for producing a resin film using the tenter type stretching apparatus according to the above [13].
[15] A method for detecting defects in a resin film, using the system according to any one of the above [1] to [12].
[16] A method for producing a resin film in which a resin film is heat-treated using a tenter type stretching device.
The process of gripping both ends of the resin film,
The process of transporting the resin film tenter type stretching device into the furnace,
The process of releasing the resin film from the device from the gripper,
A sensor unit that detects ultraviolet light is provided with a detection unit that receives light emitted from an irradiation unit that irradiates ultraviolet light, which is provided in a tenter type stretching device, and a resin film passes between the detection units. Process,
A method for producing a resin film, which comprises a step of passing ultraviolet light through the defective portion and receiving the ultraviolet light by the light receiving portion when the resin film has a defect.
[17] A method for producing a resin film, wherein the resin film is dried by using a tenter type stretching device provided with a gripping tool for gripping the resin film between the pedestal and the grip portion.
The process of gripping both ends of the resin film,
The process of transporting the resin film tenter type stretching device into the furnace,
The process of releasing the resin film from the device from the gripper,
The light emitted from the irradiation portion installed on the main surface side of the resin film that was in contact with the pedestal of the gripping tool provided in the tenter type stretching device is the resin film that is in contact with the gripping portion of the gripping tool. A step in which a sensor unit for detecting light provided on the main surface side is provided with a detection unit that receives light, and a resin film passes between the detection units.
A method for producing a resin film, which comprises a step of passing light through the defective portion and receiving the light by the light receiving portion when the resin film has a defect.
[18] The production method according to the above [17], wherein the light is ultraviolet light.
[19] The item according to any one of [16] to [18] above, wherein the angle formed by the irradiation axis connecting the irradiation unit and the sensor and the main surface of the resin film is 10 to 80 °. Manufacturing method.
[20] The angle formed by the irradiation axis connecting the irradiation unit and the sensor unit with a surface parallel to the transport direction of the resin film and perpendicular to the main surface of the resin film is 0 to 15 °. ] To [19] according to any one of the manufacturing methods.
[21] The production method according to any one of [16] to [20] above, wherein the distance between the irradiation unit and the main surface of the resin film along the irradiation axis is 1 to 250 mm.
[22] The manufacturing method according to any one of [16] to [21] above, wherein the distance between the sensor unit and the main surface of the resin film along the irradiation axis is 1 to 250 mm.
[23] In a tenter-type stretching apparatus provided with a plurality of tenter clips, which grips, conveys, and stretches both ends of the resin film, the resin films continuously conveyed and stretched are subjected to the above [1] to [1]. A defective clip detection method for identifying defective clips by continuously monitoring with the system according to any one of 12] and comparing the period in which defects in the resin film are detected with the period in which the tenter clip is detected.

The present disclosure provides a system for detecting defects in a resin film, which can detect defects in the resin film, particularly cracked defects, continuously and with high accuracy.

FIG. 1 is a schematic view showing the system of the present disclosure, and illustrates a cross section of a cracked portion of the resin film. FIG. 2 is a cross-sectional view schematically showing a gripping state of the resin film in the tenter type stretching apparatus. FIG. 3 is a diagram schematically showing the stretching mechanism of the film. FIG. 4 is an image showing the light transmitted through the cracked portion of the resin film in the example.

The materials, dimensions, etc. exemplified in the following description are examples, and the present invention is not necessarily limited thereto, and the present invention can be appropriately modified without changing the gist thereof.

The present disclosure is a system for detecting a crack defect (hereinafter, may be abbreviated as a defect) of a resin film in a tenter type stretching apparatus that grips, conveys, and stretches both ends of the resin film, and emits ultraviolet light. The resin film has an irradiation unit for irradiating and a sensor unit for detecting the ultraviolet light, irradiating the resin film with the ultraviolet light, and detecting the ultraviolet light transmitted through the resin film with the sensor unit. Provide a system for detecting defects in the film.

Further, the present disclosure relates to a tenter type stretching device in which both ends of a resin film are gripped between a pedestal of a gripping tool (hereinafter, also referred to as “tenter clip” or “clip”) and the gripping portion, conveyed, and stretched. A system for detecting defects in a resin film, which comprises an irradiation unit that irradiates light and a sensor unit that detects the light, and the irradiation unit and the sensor unit face each other with the resin film interposed therebetween. The irradiation unit is located on the surface side where the resin film is in contact with the pedestal, the sensor unit is located on the surface side where the resin film is in contact with the grip portion, and the light is emitted from the resin film. Is provided, and the light transmitted through the resin film is detected by the sensor unit to detect defects in the resin film.

[Irradiated part]
The irradiation unit used in the system of the present disclosure is a so-called light source, and is not particularly limited as long as it can irradiate light having a predetermined wavelength, preferably ultraviolet light. For example, examples of the irradiation unit include a mercury lamp (for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, and an ultra-high-pressure mercury lamp), a metal halide lamp, and an ultraviolet light laser such as KrF or ArF.

The light emitted from the irradiation unit has a light transmittance for the target resin film, particularly a light transmittance at a specific wavelength, preferably 5% or less, more preferably 3% or less, still more preferably 2% or less. Is selected.

The light transmittance can be measured by a spectroscopic measuring device or a spectroradiophotometer. For example, in accordance with JIS K 7373: 2006, light of 200 to 800 nm using an ultraviolet-visible near-infrared spectrophotometer. The light transmittance for is measured.

The light emitted from the irradiation unit is preferably ultraviolet light. The wavelength of the maximum intensity of the ultraviolet light is preferably 200 to 380 nm, more preferably 250 to 380 nm, still more preferably 280 to 380 nm, even more preferably 300 to 380 nm, and particularly preferably 350 to 380 nm.

[Sensor section]
The sensor unit is not particularly limited as long as it has a function of detecting ultraviolet light emitted from the irradiation unit. For example, the sensor unit includes a camera, for example, an ultraviolet light camera, a CCD camera, a CMOS camera, or the like. Examples include a semiconductor optical sensor.

[Resin film]
The resin film is not particularly limited as long as it can be processed by a tenter type stretching apparatus. Since the resin film has high transparency and mechanical strength, it is preferably from at least one resin material selected from the group consisting of a polyimide resin and a polyamide resin, and more preferably from a polyimide resin. Examples thereof include films formed using at least one resin material selected from the above group.

[Polyimide-based resin, polyamide-based resin]
In the present specification, the polyimide-based resin represents at least one resin selected from the group consisting of a polyimide resin, a polyamide-imide resin, a polyimide precursor resin, and a polyamide-imide precursor resin. The polyimide resin is a resin containing a repeating structural unit containing an imide group, and the polyamide-imide resin is a resin containing a repeating structural unit containing both an imide group and an amide group. The polyimide precursor resin and the polyamide-imide precursor resin are pre-imidization precursors that give the polyimide resin and the polyamide-imide resin by imidization, respectively, and are also called polyamic acids. Further, in the present specification, the polyamide-based resin is a resin containing a repeating structural unit containing an amide group. The resin film, typically the optical film, related to the present invention may contain one type of polyimide resin or polyamide-based resin, or a combination of two or more types of polyimide-based resin and / or polyamide-based resin. It may be included. The resin film preferably contains a polyimide-based resin from the viewpoint of easily achieving both chemical stability and impact resistance of the resin film, and the polyimide-based resin is preferably a polyimide resin or a polyamideimide resin. A polyamideimide resin is preferable.

In a preferred embodiment of the present invention, the polyimide resin and the polyamide resin are preferably aromatic resins from the viewpoint of easily enhancing the chemical stability and impact resistance of the resin film. In the present specification, the aromatic resin refers to a resin in which the constituent unit contained in the polyimide resin and the polyamide resin is mainly an aromatic constituent unit.

In one preferred embodiment described above, from the viewpoint of easily enhancing the chemical stability and impact resistance of the resin film, the structural unit derived from the aromatic monomer with respect to all the structural units contained in the polyimide resin and the polyamide resin. The ratio is preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 85 mol% or more, and preferably 100 mol% or less. Here, the structural unit derived from the aromatic monomer is derived from a monomer having an aromatic structure, for example, an aromatic ring in at least a part thereof, and contains an aromatic structure, for example, an aromatic ring in at least a part. It is a structural unit. Examples of the aromatic monomer include aromatic tetracarboxylic acid compounds, aromatic diamines, and aromatic dicarboxylic acids.

［式（１）中、Ｙは４価の有機基を表し、Ｘは２価の有機基を表し、＊は結合手を表す］
で表される構成単位を有するポリイミド樹脂であるか、又は、式（１）で表される構成単位及び式（２）：

［式（２）中、Ｚ及びＸは、互いに独立に、２価の有機基を表し、＊は結合手を表す］
で表される構成単位を有するポリアミドイミド樹脂であることが好ましい。また、ポリアミド系樹脂は、式（２）で表される構成単位を有するポリアミド樹脂であることが好ましい。以下において式（１）及び式（２）について説明するが、式（１）についての説明は、ポリイミド樹脂及びポリアミドイミド樹脂の両方に関し、式（２）についての説明は、ポリアミド樹脂及びポリアミドイミド樹脂の両方に関する。 In one preferred embodiment of the present invention, the polyimide resin is based on the formula (1):

[In formula (1), Y represents a tetravalent organic group, X represents a divalent organic group, and * represents a bond]
It is a polyimide resin having a structural unit represented by, or a structural unit represented by the formula (1) and the formula (2):

[In formula (2), Z and X represent divalent organic groups independently of each other, and * represents a bond]
It is preferable that the polyamide-imide resin has a structural unit represented by. Further, the polyamide resin is preferably a polyamide resin having a structural unit represented by the formula (2). The formulas (1) and (2) will be described below, but the description of the formula (1) relates to both the polyimide resin and the polyamide-imide resin, and the description of the formula (2) describes the polyamide resin and the polyamide-imide resin. Regarding both.

The structural unit represented by the formula (1) is a structural unit formed by reacting a tetracarboxylic acid compound and a diamine compound, and the structural unit represented by the formula (2) is a dicarboxylic acid compound and a diamine compound. Is a structural unit formed by the reaction of and.

［式（２０）〜式（２９）中、Ｗ^１は、単結合、−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−又は−Ａｒ−ＳＯ_２−Ａｒ−を表し、ここで、Ａｒは、互いに独立に、水素原子がフッ素原子で置換されていてもよい炭素数６〜２０のアリーレン基（例えばフェニレン基）を表し、＊は結合手を表す］
で表される基の結合手のうち、隣接しない２つが水素原子に置き換わった基及び炭素数６以下の２価の鎖式炭化水素基が例示され、Ｚのヘテロ環構造としてはチオフェン環骨格を有する基が例示される。樹脂フィルムの黄色度（以下、ＹＩ値と略す）を抑制又は低減しやすい観点から、式（２０）〜式（２９）で表される基、及び、チオフェン環骨格を有する基が好ましく、式（２６）、式（２８）及び式（２９）で表される基がより好ましい。 In the formula (2), Z is a divalent organic group, preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms (these groups). The hydrogen atom in the above is a divalent organic group having 4 to 40 carbon atoms, more preferably 1 to 6 carbon atoms, which may be substituted with a halogen atom, preferably a fluorine atom). It may be substituted with an alkyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms (the hydrogen atom in these groups may be substituted with a halogen atom, preferably a fluorine atom). It is a good divalent organic group having a cyclic structure and having 4 to 40 carbon atoms. Examples of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms include examples relating to ^{R 3a} and R ^{3b in the formula (3) described later.} The same applies. Examples of the cyclic structure include an alicyclic ring, an aromatic ring, and a heterocyclic structure. As the organic group of Z, the formula (20), the formula (21), the formula (22), the formula (23), the formula (24), the formula (25), the formula (26), the formula (27), the formula (28). And equation (29):

Wherein (20) to Formula (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-, Represents -Ar-C (CH ₃ ) _2- Ar- or -Ar-SO _2- Ar-, where Ar has 6 to 6 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom independently of each other. Represents 20 arylene groups (eg phenylene groups), * represents a bond]
Of the group bonds represented by, a group in which two non-adjacent groups are replaced with hydrogen atoms and a divalent chain hydrocarbon group having 6 or less carbon atoms are exemplified, and the heterocyclic structure of Z is a thiophene ring skeleton. The group having is exemplified. From the viewpoint of easily suppressing or reducing the yellowness of the resin film (hereinafter abbreviated as YI value), the groups represented by the formulas (20) to (29) and the groups having a thiophene ring skeleton are preferable, and the formula (hereinafter, abbreviated as YI value) is preferable. 26), the groups represented by the formula (28) and the formula (29) are more preferable.

［式（２０’）〜式（２９’）中、Ｗ^１及び＊は、式（２０）〜式（２９）において定義した通りである］
で表される２価の有機基がより好ましい。なお、式（２０）〜式（２９）及び式（２０’）〜式（２９’）における環上の水素原子は、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、又は炭素数６〜１２のアリール基（これらの基における水素原子はハロゲン原子（好ましくはフッ素原子）で置換されていてもよい）で置換されていてもよい。 Examples of the organic group of Z include the formula (20'), the formula (21'), the formula (22'), the formula (23'), the formula (24'), the formula (25'), the formula (26'), and the formula. (27'), equation (28') and equation (29'):

In formula (20 ') to formula (29'), ^{W 1} and * are as defined in formula (20) to (29)]
The divalent organic group represented by is more preferable. The hydrogen atom on the ring in the formulas (20) to (29) and the formulas (20') to (29') is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. It may be substituted with an aryl group having 6 to 12 carbon atoms (the hydrogen atom in these groups may be substituted with a halogen atom (preferably a fluorine atom)).

［式（ｄ１）中、Ｒ^２４は後述する式（３）中のＲ^３ａについて定義する基又は水素原子であり、Ｒ^２５は、Ｒ^２４又は−Ｃ（＝Ｏ）−＊を表し、＊は結合手を表す］
で表されるカルボン酸由来の構成単位をさらに有することが、ワニスの成膜性を高めやすく、樹脂フィルムの均一性を高めやすい観点から好ましい。構成単位（ｄ１）としては、具体的には、Ｒ^２４及びＲ^２５がいずれも水素原子である構成単位（ジカルボン酸化合物に由来する構成単位）、Ｒ^２４がいずれも水素原子であり、Ｒ^２５が−Ｃ（＝Ｏ）−＊を表す構成単位（トリカルボン酸化合物に由来する構成単位）等が挙げられる。 When the polyamide-based resin or the polyamide-imide resin has a structural unit in which Z in the formula (2) is represented by any of the above formulas (20') to (29'), particularly in the formula (2). When Z has a structural unit represented by the formula (3') described later, the polyamide-based resin or the polyamide-imide resin is added to the structural unit and has the following formula (d1):

[In the formula (d1), R ²⁴ is a group or a hydrogen atom defining ^{R 3a} in the formula (3) described later ^{, R 25} represents R ²⁴ or −C (= O) − *, and * represents R 24 or −C (= O) − *. Representing a join hand]
It is preferable to further have a carboxylic acid-derived structural unit represented by (1) from the viewpoint of easily improving the film-forming property of the varnish and improving the uniformity of the resin film. Specifically, as the structural unit (d1), R ²⁴ and R ²⁵ are both hydrogen atoms (constituent units derived from a dicarboxylic acid compound), and R ²⁴ is a hydrogen atom and R ^25. Examples thereof include a structural unit (a structural unit derived from a tricarboxylic acid compound) representing −C (= O) − *.

［式（３）中、Ｒ^３ａ及びＲ^３ｂは、互いに独立に、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、又は炭素数６〜１２のアリール基を表し、Ｒ^３ａ及びＲ^３ｂに含まれる水素原子は、互いに独立に、ハロゲン原子で置換されていてもよく、
Ｗは、互いに独立に、単結合、−Ｏ−、−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−ＳＯ_２−、−Ｓ−、−ＣＯ−又は−Ｎ（Ｒ^９）−を表し、Ｒ^９は水素原子、ハロゲン原子で置換されていてもよい炭素数１〜１２の１価の炭化水素基を表し、
ｓは０〜４の整数であり、ｔは０〜４の整数であり、ｕは０〜４の整数であり、＊は結合手を表す］
、より好ましくは式（３’）：

［式（３’）中、Ｒ^３ａ、Ｒ^３ｂ、ｓ、ｔ、ｕ、Ｗ及び＊は、式（３）において定義した通りである］
で表される構成単位を少なくとも有することが好ましい。なお、本明細書において、ポリアミド系樹脂又はポリアミドイミド樹脂が式（２）中のＺが式（３）で表される構成単位を有することと、ポリアミド系樹脂又はポリアミドイミド系樹脂が式（２）中のＺとして式（３）で表される構造を有することとは、同様の意味を有し、ポリアミド系樹脂又はポリアミドイミド樹脂に含まれる複数の式（２）で表される構成単位のうち、少なくとも一部の構成単位におけるＺが式（３）で表されることを意味する。当該記載は、他の同様の記載にもあてはまる。 The polyamide-based resin or the polyamide-imide resin may contain a plurality of types of Z as Z in the formula (2), and the plurality of types of Z may be the same as or different from each other. In particular, Z in the formula (2) is preferably the formula (3): from the viewpoint of easily improving the chemical stability and impact resistance of the resin film and easily improving the optical characteristics.

[In the formula (3), R ^3a and R ^3b independently represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R ^3a. And the ^{hydrogen atoms contained in R 3b} may be substituted with halogen atoms independently of each other.
W, independently of one another, 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)} - represents, ^{R 9} is a hydrogen atom, monovalent 1-12 carbon atoms which may be substituted with a halogen atom Represents a hydrocarbon group
s is an integer from 0 to 4, t is an integer from 0 to 4, u is an integer from 0 to 4, and * represents a bond.]
, More preferably equation (3'):

[In equation (3'), R ^3a , R ^3b , s, t, u, W and * are as defined in equation (3)]
It is preferable to have at least a structural unit represented by. In the present specification, the polyamide-based resin or the polyamide-imide resin has a structural unit in which Z in the formula (2) is represented by the formula (3), and the polyamide-based resin or the polyamide-imide resin has the formula (2). ) Has the same meaning as having a structure represented by the formula (3) as Z, and is a structural unit represented by a plurality of formulas (2) contained in the polyamide-based resin or the polyamide-imide resin. Of these, it means that Z in at least a part of the constituent units is represented by the equation (3). This statement also applies to other similar statements.

In formulas (3) and (3 '), W, independently of one another, 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 )-, preferably from the viewpoint of bending resistance of the resin film. It represents −O− or −S−, more preferably −O−.
R ^3a and R ^3b independently represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and 2-methyl-. Butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl group and the like can be mentioned. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group and a cyclohexyloxy group. Can be mentioned. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, a biphenyl group and the like. From the viewpoint of the surface hardness and flexibility of the resin film, R ^3a and R ^3b independently represent an alkyl group having 1 to 6 carbon atoms, and more preferably 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 monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a halogen atom. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. 2-Methyl-butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl, n-heptyl group, n-octyl group, tert-octyl group, n-nonyl group, n-decyl group and the like. These may be substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

T and u in the formula (3) and the formula (3') are independently integers of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. is there.

The s in the formula (3) and the formula (3') is an integer in the range of 0 to 4, and when s is in this range, the chemical stability, impact resistance, elastic modulus and resistance of the resin film are satisfied. It is easy to improve the flexibility. S in the formula (3) and the formula (3') is preferably an integer in the range of 0 to 3, more preferably 0, from the viewpoint of more easily improving the impact resistance, elastic modulus and bending resistance of the resin film. An integer in the range ~ 2, more preferably 0 or 1, even more preferably 0. The structural unit represented by the formula (3) or the formula (3') in which s is 0 is, for example, a structural unit derived from terephthalic acid or isophthalic acid, and the structural unit is particularly the formula (3) or the formula (3). It is preferable that s in 3') is 0 and u is 0. From the viewpoint of easily improving the chemical stability, impact resistance, elastic modulus and bending resistance of the resin film, the polyamide-imide resin or the polyamide-based resin preferably contains a structural unit derived from terephthalic acid. The polyamide-imide resin or the polyamide-based resin may contain one or more structural units represented by the formula (3) or the formula (3') in Z. From the viewpoint of improving the chemical stability, impact resistance, elastic modulus and bending resistance of the resin film, and reducing the YI value, the polyamide-imide resin or the polyamide-based resin is in Z in the formula (3) or in the formula (3'). ) It is preferable to include two or more kinds of structural units having different values of s, and it is more preferable to include two or three kinds of structural units having different values of s in the formula (3) or the formula (3'). preferable. In this case, the polyamide-imide resin or the polyamide-based resin is formulated from the viewpoint of easily increasing the chemical stability, impact resistance, elastic modulus and bending resistance of the resin film, and easily reducing the YI value of the resin film. As Z in the structural unit represented by 2), the structure represented by the formula (3) in which s is 0 is contained, and the structural unit including the structure is represented by the formula (3) in which s is 1. It is more preferable to further contain a structural unit containing the structure to be formed. Further, in addition to the structural unit represented by the formula (2) having Z represented by the formula (3) in which s is 0, it is also preferable to further have the structural unit represented by the above formula (d1). ..

で表される構成単位を有する。この場合、樹脂フィルムの化学的安定性、耐衝撃性、弾性率及び耐屈曲性を向上させやすいと共に、ＹＩ値を低減しやすい。 In a preferred embodiment of the present invention, the polyamide-imide resin or the polyamide-based resin is a structural unit represented by the formula (3) or the formula (3'), in which s = 0 and u = 0. Has. In a more preferable embodiment of the present invention, the polyamide-imide resin or the polyamide-based resin has a configuration in which s = 0 and u = 0 as a structural unit represented by the formula (3) or the formula (3'). Unit and formula (3 "):

It has a structural unit represented by. In this case, it is easy to improve the chemical stability, impact resistance, elastic modulus and bending resistance of the resin film, and it is easy to reduce the YI value.

When the polyamideimide resin or the polyamide-based resin has a structural unit represented by the formula (3) or the formula (3'), the ratio thereof is the configuration represented by the formula (1) of the polyamideimide resin or the polyamide-based resin. When the total of the units and the constituent units represented by the formula (2) is 100 mol%, it is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, still more preferably. It is 50 mol% or more, particularly preferably 60 mol% or more, preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less. When the ratio of the structural units represented by the formula (3) or the formula (3') is at least the above lower limit, it is easy to improve the chemical stability, impact resistance, elastic modulus and bending resistance of the resin film. When the ratio of the structural units represented by the formula (3) or the formula (3') is not more than the above upper limit, the increase in the viscosity of the resin-containing varnish due to the hydrogen bond between the amide bonds derived from the formula (3) is suppressed, and the film is formed. It is easy to improve the workability of.

Further, when the polyamideimide resin or the polyamide-based resin has a structural unit represented by the formula (3) or the formula (3') in which s = 1 to 4, the formula (3) or the formula in which s is 1 to 4 is obtained. As for the ratio of the structural units represented by (3'), the total of the structural units represented by the formula (1) and the structural units represented by the formula (2) of the polyamideimide resin or the polyamide-based resin is 100 mol%. When it is, it is preferably 3 mol% or more, more preferably 5 mol% or more, further preferably 7 mol% or more, still more preferably 9 mol% or more, preferably 90 mol% or less, more preferably 70 mol. % Or less, more preferably 50 mol% or less, even more preferably 30 mol% or less. When the ratio of the structural units represented by the formula (3) or the formula (3') in which s is 1 to 4 is equal to or more than the above lower limit, the chemical stability, impact resistance, elastic modulus and resistance of the resin film are satisfied. Easy to increase flexibility. When the ratio of the structural unit represented by the formula (3) in which s is 1 to 4 is not more than the above upper limit, the hydrogen between amide bonds derived from the structural unit represented by the formula (3) or the formula (3') It is easy to improve the processability of the film by suppressing the increase in viscosity of the resin-containing varnish due to bonding. The ratio of the structural units represented by the formula (1), the formula (2), the formula (3) or the formula (3') ^{can be measured by using, for example, 1 1} H-NMR, or the raw material is charged. It can also be calculated from the ratio.

In a preferred embodiment of the present invention, preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 45 mol% or more, still more preferably 50 mol% of Z in the polyamide-imide resin or the polyamide-based resin. % Or more is a structural unit represented by the formula (3) or the formula (3') in which s is 0 to 4. When the above lower limit of Z or more is a structural unit represented by the formula (3) or the formula (3') in which s is 0 to 4, the impact resistance, elastic modulus and bending resistance of the resin film are enhanced. Cheap. Further, 100 mol% or less of Z in the polyamide-imide resin or the polyamide-based resin may be a structural unit represented by the formula (3) or the formula (3') in which s is 0 to 4. The ratio of the structural units represented by the formula (3) or the formula (3') in which s is 0 to 4 in the resin ^{can be measured by using, for example, 1 1} H-NMR, or the raw material. It can also be calculated from the charge ratio.

In a preferred embodiment of the present invention, preferably 5 mol% or more, more preferably 8 mol% or more, still more preferably 10 mol% or more, still more preferably 12 mol% of Z in the polyamide-imide resin or the polyamide-based resin. % Or more is represented by the formula (3) or the formula (3') in which s is 1 to 4. When the above lower limit or more of Z of the polyamide-imide resin or the polyamide-based resin is represented by the formula (3) or the formula (3') in which s is 1 to 4, the impact resistance, elastic modulus and resistance of the resin film Easy to increase flexibility. Further, the formula (3) or the formula (3) in which s is 1 to 4 in Z, preferably 90 mol% or less, more preferably 70 mol% or less, still more preferably 50 mol% or less, still more preferably 30 mol% or less. It is represented by the formula (3'). When the above upper limit or less of Z is represented by the formula (3) in which s is 1 to 4, it is derived from the structural unit represented by the formula (3) or the formula (3') in which s is 1 to 4. It is easy to improve the processability of the film by suppressing the increase in viscosity of the resin-containing varnish due to the hydrogen bond between the amide bonds. The ratio of the structural units represented by the formula (3) or the formula (3') in which s is 1 to 4 in the resin ^{can be measured by using, for example, 1 1} H-NMR, or the raw material charging ratio. It can also be calculated from.

In formulas (1) and (2), X is a divalent organic group, preferably a divalent organic group having 4 to 40 carbon atoms, more preferably a cyclic structure having 4 to 40 carbon atoms, independently of each other. Represents a divalent organic group of. Examples of the cyclic structure include an alicyclic ring, an aromatic ring, and a heterocyclic structure. In the organic group, the hydrogen atom in the organic group may be substituted with a hydrocarbon group or a hydrocarbon group substituted with fluorine, in which case the number of carbon atoms of the hydrocarbon group and the hydrocarbon group substituted with fluorine is preferable. Is 1 to 8. In one embodiment of the present invention, the polyamide-imide resin may contain a plurality of types of X, and the plurality of types of X may be the same as or different from each other. X is represented by the formula (10), the formula (11), the formula (12), the formula (13), the formula (14), the formula (15), the formula (16), the formula (17) and the formula (18). Groups; Groups in which the hydrogen atom in the groups represented by the formulas (10) to (18) is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; and a chain having 6 or less carbon atoms. The formula hydrocarbon group is exemplified.

In equations (10) to (18), * represents a bond,
V ^{1, V 2} and ^{V 3} independently of one another, a single _{bond, -O -, - S -,} - CH 2 -, - CH 2 -CH 2 -, - CH (CH 3) -, - C (CH ₃ ) _{Represents 2-} , -C (CF ₃ ) _2- , -SO _2- , -CO- or -N (Q)-. Here, Q represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include the groups mentioned above for R ^9.
In one example, 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 positions of V 1} and V ² with respect to each ring and the bonding positions of V ² and V ³ with respect to each ring are independent of each other, preferably in the meta position or para position with respect to each ring, and more preferably in the para position. It is a place.

Among the groups represented by the formulas (10) to (18), the formulas (13) and (14) are used from the viewpoint of easily increasing the chemical stability, impact resistance, elastic modulus and bending resistance of the resin film. , The groups represented by the formulas (15), (16) and (17) are preferable, and the groups represented by the formulas (14), (15) and (16) are more preferable. Further, V ¹ , V ² and V ³ are independent of each other, preferably single bond, -O- or -S-, more preferably, from the viewpoint of easily increasing the impact resistance, elastic modulus and flexibility of the resin film. Single bond or -O-.

［式（４）中、Ｒ^１０〜Ｒ^１７は、互いに独立に、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基又は炭素数６〜１２のアリール基を表し、Ｒ^１０〜Ｒ^１７に含まれる水素原子は、互いに独立に、ハロゲン原子で置換されていてもよく、＊は結合手を表す］
で表される構造を含む。式（１）及び式（２）で表される複数の構成単位中のＸの少なくとも一部が式（４）で表される構造であると、樹脂フィルムの化学的安定性、耐衝撃性、弾性率及び透明性を高めやすい。 In a preferred embodiment of the present invention, the polyamide-based resin and the polyimide-based resin are represented by X in the formula (1) or X in the formula (2), and the formula (4):

[In formula (4), R ^{10 to} R ¹⁷ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. The ^{hydrogen atoms contained in R 10 to} R ¹⁷ may be substituted with halogen atoms independently of each other, and * represents a bond.]
Includes the structure represented by. When at least a part of X in the plurality of structural units represented by the formulas (1) and (2) has a structure represented by the formula (4), the chemical stability and impact resistance of the resin film are determined. It is easy to increase the elastic modulus and transparency.

In formula (4), R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are independent of each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and 1 carbon atom. Represents an alkoxy group of ~ 6 or an aryl group of 6-12 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms include the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms in the formula (3). Examples thereof include groups exemplified as groups or aryl groups having 6 to 12 carbon atoms. R ^{10 to} R ¹⁷ represent independently of each other, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably an hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and here, R ^{10 to} R ¹⁷ The hydrogen atoms contained in the above may be substituted with halogen atoms independently of each other. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R ^{10 to} R ¹⁷ are more preferably hydrogen atoms, methyl groups, fluoro groups, chloro groups or trifluoromethyl groups independently of each other from the viewpoint of impact resistance, elasticity, transparency and bending resistance of the resin film. R ¹⁰ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen atoms, and R ¹¹ and R ¹⁷ are hydrogen atoms, methyl groups, fluoro groups, chloro groups or trifluoromethyl groups. Of particular preference are R ¹¹ and R ¹⁷ being methyl or trifluoromethyl groups.

で表される構成単位であり、すなわち、式（１）及び式（２）で表される複数の構成単位中のＸの少なくとも一部は、式（４’）で表される構成単位である。この場合、フッ素元素を含有する骨格によりポリイミド系樹脂又はポリアミド系樹脂の溶媒への溶解性を高め、該樹脂を含有するワニスの保管安定性を向上しやすいと共に、該ワニスの粘度を低減しやすく、樹脂フィルムの加工性を向上しやすい。また、フッ素元素を含有する骨格により、樹脂フィルムの光学特性を向上しやすい。 In one preferred embodiment of the present invention, the structural unit represented by the formula (4) is the formula (4'):

That is, at least a part of X in the plurality of structural units represented by the equations (1) and (2) is the structural unit represented by the equation (4'). .. In this case, the skeleton containing a fluorine element enhances the solubility of the polyimide resin or the polyamide resin in the solvent, 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. , It is easy to improve the processability of the resin film. Further, the skeleton containing a fluorine element makes it easy to improve the optical characteristics of the resin film.

In a preferred embodiment of the present invention, the formula (4), preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, of X in the polyimide resin or the polyamide resin. In particular, it is represented by the equation (4'). When X in the above range in the polyimide resin or the polyamide resin is represented by the formula (4), particularly the formula (4'), the obtained resin film is dissolved in a resin solvent by a skeleton containing a fluorine element. It is easy to improve the property and improve the storage stability of the varnish containing the resin, and it is easy to reduce the viscosity of the varnish and improve the processability of the resin film. In addition, the skeleton containing a fluorine element makes it easy to improve the optical characteristics of the resin film. It should be noted that preferably, 100 mol% or less of X in the polyimide resin or the polyamide resin is represented by the formula (4), particularly the formula (4'). X in the resin may be of formula (4), especially of formula (4'). The ratio of the structural unit represented by the formula (4) of X in the resin ^{can be measured by using, for example, 1 1} H-NMR, or can be calculated from the charging ratio of the raw materials.

In the formula (1), Y represents a tetravalent organic group, preferably a tetravalent organic group having 4 to 40 carbon atoms, and more preferably a tetravalent organic group having a cyclic structure and having 4 to 40 carbon atoms. Represent. Examples of the cyclic structure include an alicyclic ring, an aromatic ring, and a heterocyclic structure, and an aromatic ring is preferably used from the viewpoint of easily increasing impact resistance and elastic modulus. The organic group is an organic group in which the hydrogen atom in the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group, in which case the hydrocarbon group and the fluorine-substituted hydrocarbon group The number of carbon atoms is preferably 1-8. In one embodiment of the present invention, the polyimide resin may contain a plurality of types of Y, and the plurality of types of Y may be the same as or different from each other. As Y, the following formulas (20), formulas (21), formulas (22), formulas (23), formulas (24), formulas (25), formulas (26), formulas (27), formulas (28) And a group represented by the formula (29); a group in which the hydrogen atom in the groups represented by the formulas (20) to (29) is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; In addition, a chain hydrocarbon group having 4 or less valences of 6 carbon atoms is exemplified.

In the formula (20) to (29), * represents a bond, ^{W 1} is 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) represents a 2 -Ar- or _-Ar-SO 2 -Ar-. Ar represents an arylene group having 6 to 20 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom, and specific examples thereof include a phenylene group.

Among the groups represented by the formulas (20) to (29), the formulas (26) and (28) are used from the viewpoint of easily increasing the chemical stability, impact resistance, elastic modulus and bending resistance of the resin film. Alternatively, the group represented by the formula (29) is preferable, and the group represented by the formula (26) is more preferable. Further, W ¹ is independent of each other, preferably single bond, from the viewpoint of easily increasing the chemical stability, impact resistance, elasticity and bending resistance of the resin film and easily reducing the YI value of the resin film. _{-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 single bond, -C (CH ₃ ) _{2- or-} C (CF ₃ ) _2- , particularly preferably 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, still more preferably 70 mol% or more, represented by the formula (26). Y is the formula within the above range in the polyimide resin (26), preferably ^{W 1} is a single bond, -C _{(CH 3) 2} - or -C _{(CF 3) 2} - a is the formula (26), more preferably When W ¹ is represented by the formula (26) which is a single bond or −C (CF ₃ ) _2−, it is easy to improve the chemical stability, impact resistance, elastic modulus and bending resistance of the resin film, and the resin. It is easy to reduce the YI value of the film. The ratio of the structural unit in which Y in the polyimide resin is represented by the formula (26) ^{can be measured using, for example, 1 1} H-NMR, or can be calculated from the charging ratio of the raw materials.

［式（５）中、Ｒ^１８〜Ｒ^２５は、互いに独立に、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基又は炭素数６〜１２のアリール基を表し、Ｒ^１８〜Ｒ^２５に含まれる水素原子は、互いに独立に、ハロゲン原子で置換されていてもよく、＊は結合手を表す］
及び／又は式（９）

［式（９）中、Ｒ^３５〜Ｒ^４０は、互いに独立に、水素原子、炭素数１〜６のアルキル基又は炭素数６〜１２のアリール基を表し、Ｒ^３５〜Ｒ^４０に含まれる水素原子は、互いに独立に、ハロゲン原子で置換されていてもよく、＊は結合手を表す］
で表される。複数の式（１）中のＹの少なくとも一部が式（５）で表される、及び／又は、式（９）で表されると、樹脂フィルムの化学的安定性、耐衝撃性、弾性率及び光学特性を向上させやすい。 In a preferred embodiment of the present invention, at least a part of Y in the plurality of formulas (1) is the formula (5) :.

[In formula (5), R ^{18 to} R ²⁵ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. The ^{hydrogen atoms contained in R 18 to} R ²⁵ may be substituted with halogen atoms independently of each other, and * represents a bond.]
And / or formula (9)

[In the formula (9), R ^{35 to} R ⁴⁰ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and hydrogen contained in ^{R 35 to} R ^40. Atoms may be substituted with halogen atoms independently of each other, with * representing a bond]
It is represented by. When at least a part of Y in the plurality of formulas (1) is represented by the formula (5) and / or the formula (9), the chemical stability, impact resistance, and elasticity of the resin film It is easy to improve the modulus and optical characteristics.

In formula (5), R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are independent of each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and 1 carbon atom. Represents an alkoxy group of ~ 6 or an aryl group of 6-12 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, or the aryl group having 6 to 12 carbon atoms include the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms in the formula (3). Examples of groups or aryl groups having 6 to 12 carbon atoms can be mentioned above. R ^{18 to} R ²⁵ represent independently of each other, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably an hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and here, R ^{18 to} R ^25. The hydrogen atoms contained in the above may be substituted with halogen atoms independently of each other. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R ^{18 to} R ²⁵ are more preferable from the viewpoint of easily increasing the impact resistance, elastic coefficient and bending resistance of the resin film, and easily increasing the transparency and maintaining the transparency independently of each other. Is a hydrogen atom, a methyl group, a fluoro group, a chloro group or a trifluoromethyl group, and more preferably R ¹⁸ , R ¹⁹ , R ²⁰ and R ²³ , R ²⁴ and R ²⁵ are hydrogen atoms, R ²¹ and R ^22. Is a hydrogen atom, a methyl group, a fluoro group, a chloro group or a trifluoromethyl group, and particularly preferably R ²¹ and R ²² are a methyl group or a trifluoromethyl group.

In the formula (9), from the viewpoint of easily increasing the chemical stability, impact resistance, elasticity and bending resistance of the resin film, and easily increasing the transparency and maintaining the transparency, R ³⁵ ~ R ⁴⁰ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and further preferably a hydrogen atom. Here, the ^{hydrogen atoms contained in R 35 to} R ⁴⁰ may be substituted with halogen atoms independently of each other, and examples of the halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. .. Examples of the alkyl group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms in R ^{35 to} R ^{40 are exemplified above.}

で表される。すなわち、複数のＹの少なくとも一部は、式（５’）及び／又は式（９’）で表される。この場合、樹脂フィルムの耐衝撃性、弾性率及び耐屈曲性を高めやすい。さらに、式（５）が式（５’）で表される場合、フッ素元素を含有する骨格によりポリイミド系樹脂の溶媒への溶解性を高め、該樹脂を含有するワニスの保管安定性を向上しやすいと共に、該ワニスの粘度を低減しやすく、樹脂フィルムの加工性を向上しやすい。また、フッ素元素を含有する骨格により、樹脂フィルムの光学特性を向上しやすい。 In a preferred embodiment of the present invention, formula (5) is represented by formula (5'), and formula (9) is represented by formula (9') :.

It is represented by. That is, at least a part of the plurality 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 resin film. Further, when the formula (5) is represented by the formula (5'), the skeleton containing a fluorine element enhances the solubility of the polyimide resin in the solvent and improves the storage stability of the varnish containing the resin. In addition to being easy, it is easy to reduce the viscosity of the varnish and improve the processability of the resin film. Further, the skeleton containing a fluorine element makes it easy to improve the optical characteristics of the resin 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, still more preferably 70 mol% or more, according to the formula (5), particularly the formula (5). It is represented by'). When Y in the above range in the polyimide resin is represented by the formula (5), particularly the formula (5'), the skeleton containing a fluorine element enhances the solubility of the polyimide resin in the solvent and contains the resin. It is easy to reduce the viscosity of the varnish and improve the processability of the resin film. Further, the skeleton containing a fluorine element makes it easy to improve the optical characteristics of the resin film. It should be noted that preferably, 100 mol% or less of Y in the polyimide resin is represented by the formula (5), particularly the formula (5'). Y in the polyimide resin may be of the formula (5), particularly the formula (5'). The ratio of the structural units represented by the formula (5) of Y in the polyimide resin ^{can be measured using, for example, 1 1} H-NMR, or can be calculated from the charging ratio of the raw materials.

In a preferred embodiment of the present invention, the plurality of structural units represented by the formula (1) have a configuration in which Y is represented by the formula (9) in addition to the structural unit in which Y is represented by the formula (5). It is preferable to include more units. When Y further contains the structural unit represented by the formula (9), the impact resistance and elastic modulus of the resin film can be further improved.

The polyimide-based resin may contain a structural unit represented by the formula (30) and / or a structural unit represented by the formula (31), and may be represented by the formula (1) and, in some cases, the formula (2). In addition to the structural unit represented by the formula (30), the structural unit represented by the formula (30) and / or the structural unit represented by the formula (31) may be included.

In the formula (30), Y ¹ is a tetravalent organic group, preferably an organic group in which the hydrogen atom in the organic group may be substituted with a hydrocarbon group or a hydrocarbon group substituted with fluorine. Examples of Y ¹ include formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28) and A group represented by the formula (29), a group in which the hydrogen atom in the groups represented by the formulas (20) to (29) is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group, and a group. A chain hydrocarbon group having a tetravalent carbon number of 6 or less is exemplified. In one embodiment of the present invention, a polyimide resin may include a plurality of kinds of Y ^1, Y ¹ of the plurality of kinds may identical to one another or may be different.

In the formula (31), Y ² is a trivalent organic group, preferably an organic group in which the hydrogen atom in the organic group may be substituted with a hydrocarbon group or a hydrocarbon group substituted with fluorine. Examples of Y ² include the above equations (20), (21), (22), (23), (24), (25), (26), (27), and (28). ) And a group in which any one of the bonds of the group represented by the formula (29) is replaced with a hydrogen atom, and a chain hydrocarbon group having a trivalent carbon number of 6 or less are exemplified. In one embodiment of the present invention, a polyimide resin may include a plurality of kinds of Y ^2, Y ² of plural types may identical to one another or may be different.

In formulas (30) and (31), X ¹ and X ² are divalent organic groups independently of each other, and preferably a hydrocarbon group in which a hydrogen atom in the organic group is substituted with a hydrocarbon group or fluorine. It is an organic group that may be substituted with. Examples of X ¹ and X ² include the above equations (10), (11), (12), (13), (14), (15), (16), (17) and A group represented by the formula (18); a group in which a hydrogen atom in the groups represented by the formulas (10) to (18) is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; A chain hydrocarbon group having 6 or less carbon atoms is exemplified.

In one embodiment of the present invention, the polyimide resin is a structural unit represented by the formulas (1) and / or the formula (2), and optionally a configuration represented by the formulas (30) and / or the formula (31). It consists of units. Further, from the viewpoint of easily improving the optical characteristics, impact resistance, elastic modulus and bending resistance of the resin film, the ratio of the structural units represented by the formulas (1) and (2) in the above-mentioned polyimide resin is expressed by the formula. Based on (1) and the formula (2), and optionally all the structural units represented by the formulas (30) and / or the formula (31), preferably 80 mol% or more, more preferably 90 mol% or more, and further. It is preferably 95 mol% or more, and usually 100% or less. The above ratio can be measured using, for example, ^{1 1} H-NMR, or can be calculated from the raw material charging ratio.

In one embodiment of the present invention, the content of the polyimide resin and / or the polyamide resin in the resin film is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, based on 100 parts by mass of the resin film. It is more preferably 50 parts by mass or more, preferably 99.5 parts by mass or less, and more preferably 95 parts by mass or less. When the content of the polyimide resin and / or the polyamide resin is within the above range, it is easy to improve the chemical stability, optical properties, impact resistance and elastic modulus of the resin film.

The weight average molecular weight of the polyimide resin and the polyamide resin (hereinafter, may be abbreviated as Mw) is converted to standard polystyrene from the viewpoint of easily increasing the chemical stability, impact resistance, elastic modulus and bending resistance of the resin film. It is preferably 200,000 or more, more preferably 230,000 or more, still more preferably 250,000 or more, even more preferably 270,000 or more, and particularly preferably 280,000 or more. Further, the polyimide resin and the Mw of the polyamide resin are preferably 1,000,000 or less from the viewpoints that the solubility of the resin in a solvent is easily improved and the stretchability and processability of the resin film are easily improved. It is more preferably 800,000 or less, still more preferably 700,000 or less, and even more preferably 500,000 or less. Mw can be obtained by, for example, GPC measurement and converted to standard polystyrene, and may be calculated by, for example, the method described in Examples.

In the polyamide imide resin, the content of the structural unit represented by the formula (2) is preferably 0.1 mol or more, more preferably 0.5 mol or more, with respect to 1 mol of the structural unit represented by the formula (1). More than mol, more preferably 1.0 mol or more, even more preferably 1.5 mol or more, preferably 6.0 mol or less, more preferably 5.0 mol or less, still more preferably 4.5 mol or less. is there. When the content of the structural unit represented by the formula (2) is at least the above lower limit, the impact resistance and elastic modulus of the resin film can be easily increased. Further, when the content of the structural unit represented by the formula (2) is not more than the above upper limit, the thickening due to the hydrogen bond between the amide bonds in the formula (2) is suppressed and the processability of the resin film is improved. Easy to make.

In a preferred embodiment of the present invention, the polyimide resin and / or the polyamide resin contained in the resin film may contain a halogen atom such as a fluorine atom which can be introduced by, for example, the above-mentioned fluorine-containing substituent or the like. .. When the polyimide resin and / or the polyamide resin contains a halogen atom, the elastic modulus of the resin film can be easily improved and the YI value can be easily reduced. When the elastic modulus of the resin film is high, it is easy to suppress the occurrence of scratches and wrinkles. Further, when the YI value of the resin film is low, it becomes easy to improve the transparency and visibility of the film. The halogen atom is preferably a fluorine atom. Preferred fluorine-containing substituents for containing a fluorine atom in the polyimide resin include, for example, a fluoro group and a trifluoromethyl group.

The content of halogen atoms in the polyimide resin and the polyamide resin is preferably 1 to 40% by mass, more preferably 5 to 40% by mass, still more preferably 5 to 40% by mass, based on the mass of the polyimide resin and the polyamide resin, respectively. It is 5 to 30% by mass. When the content of the halogen atom is at least the above lower limit, the elastic modulus of the resin film is further improved, the water absorption rate is lowered, the YI value is further reduced, and the transparency and visibility are more likely to be improved. When the content of halogen atoms is not more than the above upper limit, synthesis becomes easy.

The imidization ratio of the polyimide resin and the polyamide-imide resin is preferably 90% or more, more preferably 93% or more, still more preferably 96% or more, and usually 100% or less. From the viewpoint of easily improving the optical characteristics of the resin film, the imidization ratio is preferably at least the above lower limit. The imidization ratio indicates the ratio of the molar amount of the imide bond in the polyimide resin to twice the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyimide resin. When the polyimide resin contains a tricarboxylic acid compound, the value is twice the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyimide resin, and the molar amount of the structural unit derived from the tricarboxylic acid compound. The ratio of the molar amount of the imide bond in the polyimide resin to the total of the above is shown. The imidization rate can be determined by an IR method, an NMR method, or the like.

Commercially available products may be used as the polyimide resin and the polyamide resin. Examples of commercially available polyimide resins include Neoprim (registered trademark) manufactured by Mitsubishi Gas Chemical Company, Ltd., KPI-MX300F manufactured by Kawamura Sangyo Co., Ltd., and the like.

In the present invention, the resin film may contain a polyamide-based resin. The polyamide-based resin according to this embodiment is a polymer mainly composed of a repeating structural unit represented by the formula (2). Preferred examples and specific examples of Z in the formula (2) in the polyamide-based resin are the same as preferable examples and specific examples of Z in the polyimide-based resin. The polyamide-based resin may contain two or more types of repeating structural units represented by the formula (2) having different Z's.

［式（３”）中、Ｒ^１〜Ｒ^８は、互いに独立に、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、又は炭素数６〜１２のアリール基を表し、Ｒ^１〜Ｒ^８に含まれる水素原子は、互いに独立に、ハロゲン原子で置換されていてもよく、
Ａは、単結合、−Ｏ−、−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−ＳＯ_２−、−Ｓ−、−ＣＯ−又は−Ｎ（Ｒ^９）−を表し、
Ｒ^９は水素原子、ハロゲン原子で置換されていてもよい炭素数１〜１２の１価の炭化水素基を表し、
ｍは０〜４の整数であり、
Ｒ^３１及びＲ^３２は、互いに独立に、ヒドロキシル基、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基又は塩素原子を表す。］ (Resin manufacturing method)
The polyimide resin and the polyimide precursor resin can be produced, for example, using a tetracarboxylic acid compound and a diamine compound as main raw materials, and the polyamide-imide resin and the polyamide-imide precursor resin can be produced, for example, by a tetracarboxylic acid compound, a dicarboxylic acid compound and a diamine compound. Can be produced as a main raw material, and the polyamide resin can be produced, for example, using a diamine compound and a dicarboxylic acid compound as main raw materials. Here, the dicarboxylic acid compound preferably contains at least a compound represented by the formula (3 ").

[In the formula (3 ″), R ^{1 to} R ⁸ independently contain a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Represented, the ^{hydrogen atoms contained in R 1 to} R ⁸ may be substituted with halogen atoms independently of each other.
A represents a single _{bond, -O -, - CH 2 -} , - CH 2 -CH 2 -, - CH (CH 3) -, - C (CH 3) 2 -, - C (CF 3) 2 -, - Represents SO _2- , -S-, -CO- or -N (R ⁹ )-
R ⁹ represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a halogen atom.
m is an integer from 0 to 4
R ³¹ and R ³² independently represent a hydroxyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group or a chlorine atom. ]

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

Examples of the diamine compound used in the production of the resin include aliphatic diamines, aromatic diamines and mixtures thereof. In addition, in this embodiment, "aromatic diamine" represents a diamine in which an amino group is directly bonded to an aromatic ring, and an aliphatic group or other substituent may be contained in a part of the structure. The aromatic ring may be a monocyclic ring or a condensed ring, and examples thereof include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring. Among these, a benzene ring is preferably exemplified. Further, the "aliphatic diamine" represents a diamine in which an amino group is directly bonded to an aliphatic group, and an aromatic ring or other substituent may be contained as a part of the structure thereof.

Examples of the aliphatic diamine include acyclic aliphatic diamines such as hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, norbornanediamine and 4,4'. − Examples thereof include cyclic aliphatic diamines such as diaminodicyclohexylmethane. These can be used alone or in combination of two or more.

Examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylene diamine, p-xylylene diamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene and the like. , 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'- Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4) -Aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 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 (with TFMB) (May be described), 4,4'-bis (4-aminophenoxy) biphenyl, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene , 9,9-bis (4-amino-3-chlorophenyl) fluorene, 9,9-bis (4-amino-3-fluorophenyl) fluorene, and other aromatic diamines having two or more aromatic rings. These can be used alone or in combination of two or more.

The aromatic diamines are preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3 , 3'-diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 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 (TFMB), 4,4'-bis (4-aminophenoxy) biphenyl, more preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl. Propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2- Bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl (TFMB), 4,4'- Biphenyl (4-aminophenoxy) biphenyl. These can be used alone or in combination of two or more.

Among the above diamine compounds, one or more selected from the group consisting of aromatic diamines having a biphenyl structure are selected from the viewpoints of high elastic modulus, high transparency, high flexibility, high bending resistance and low coloring property of the resin film. It is preferable to use it. One selected from the group consisting of 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine, 4,4'-bis (4-aminophenoxy) biphenyl and 4,4'-diaminodiphenyl ether. It is more preferable to use the above, and it is even more preferable to use 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl (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. Be done. The tetracarboxylic acid compound may be used alone or in combination of two or more. The tetracarboxylic dian compound may be a tetracarboxylic dian compound analog such as an acid chloride compound in addition to the dianhydride.

Specific examples of aromatic tetracarboxylic dianhydrides include non-condensed polycyclic aromatic tetracarboxylic dianhydrides, monocyclic aromatic tetracarboxylic dianhydrides, and condensed polycyclic aromatic tetraides. Examples include carboxylic dianhydride. Examples of the non-condensed polycyclic aromatic tetracarboxylic dianhydride include 4,4'-oxydiphthalic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride and 2,2. ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride , 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-di) Describe as carboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenoxyphenyl) propane dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic acid dianhydride (6FDA). There are), 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) Examples thereof include −dicarboxyphenyl) methane dianhydride, 4,4'-(p-phenylenedioxy) diphthalic acid dianhydride, and 4,4'-(m-phenylenedioxy) diphthalic acid dianhydride. Examples of the monocyclic aromatic tetracarboxylic dianhydride include 1,2,4,5-benzenetetracarboxylic dianhydride, and the condensed polycyclic aromatic dianhydride dianhydride. Examples thereof include 2,3,6,7-naphthalenetetracarboxylic dianhydride.

Among these, preferably 4,4'-oxydiphthalic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride. Anhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenyl Sulfontetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2- Bis (3,4-dicarboxyphenoxyphenyl) propanedianhydride, 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydride (6FDA), 1,2-bis (2,3-dicarboxyphenyl) Etan 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'-(p-) Examples thereof include phenylenedioxy) diphthalic dianhydride and 4,4'-(m-phenylenedioxy) diphthalic dianhydride, more preferably 4,4'-oxydiphthalic dianhydride, 3,3',. 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydride (6FDA) , Bis (3,4-dicarboxyphenyl) methane dianhydride and 4,4'-(p-phenylenedioxy) diphthalic dianhydride. These can be used alone or in combination of two or more.

Examples of the aliphatic tetracarboxylic dianhydride include cyclic or acyclic aliphatic tetracarboxylic dianhydride. The cyclic aliphatic tetracarboxylic dianhydride is a tetracarboxylic dianhydride having an alicyclic hydrocarbon structure, and specific examples thereof include 1,2,4,5-cyclohexanetetracarboxylic dianhydride. Cycloalkanetetracarboxylic dianhydride such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bicyclo [2.2] .2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl-3,3', 4,4'-tetracarboxylic dianhydride and their positional isomers are listed. Be done. These can be used alone or in combination of two or more. Specific examples of the acyclic aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride and the like. These can be used alone or in combination of two or more. Further, a cyclic aliphatic tetracarboxylic dianhydride and an acyclic aliphatic tetracarboxylic dianhydride may be used in combination.

Among the above tetracarboxylic dianhydrides, 4,4'from the viewpoints of high impact resistance, high elasticity, high surface hardness, high transparency, high flexibility, high bending resistance, and low coloring property of the resin film. -Oxydiphthalic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3, 3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propanedianhydride, 4 , 4'-(hexafluoroisopropyridene) diphthalic acid dianhydride, and mixtures thereof are preferred, 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-(hexafluoroisopropi). Liden) diphthalic dianhydrides, and mixtures thereof, are more preferred, with 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydrides (6FDA) and 3,3', 4,4'-biphenyltetracarboxylic acids. Dihydrate (BPDA) is even more preferred.

As the dicarboxylic acid compound used in the production of the resin, terephthalic acid, isophthalic acid, 4,4'-oxybis benzoic acid or an acid chloride compound thereof is preferably used. In addition to terephthalic acid, isophthalic acid, 4,4'-oxybis benzoic acid or their acid chloride compounds, other dicarboxylic acid compounds may be used. Examples of other dicarboxylic acid compounds include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, acid chloride compounds related thereto, acid anhydrides, and the like, and two or more of them may be used in combination. Specific examples include a dicarboxylic acid compound of isophthalic acid; naphthalenedicarboxylic acid; 4,4'-biphenyldicarboxylic acid; 3,3'-biphenyldicarboxylic acid; a chain hydrocarbon having 8 or less carbon atoms, and two benzoic acids. Examples thereof include compounds in which is single-bonded, -CH _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -SO _2- or phenylene groups, and their acid chloride compounds. As a specific example, 4,4'-oxybis (benzoyl chloride), terephthaloyl chloride or isophthaloyl chloride are preferable, and 4,4'-oxybis (benzoyl chloride) and terephthaloyl chloride can be used in combination. More preferred.

The polyimide resin is obtained by further reacting tetracarboxylic acid and tricarboxylic acid and their anhydrides and derivatives in addition to the tetracarboxylic acid compound as long as the various physical properties of the resin film are not impaired. May be good.

Examples of the tetracarboxylic acid include a water adduct of the anhydride of the tetracarboxylic acid compound.

Examples of the tricarboxylic acid compound include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, acid chloride compounds related thereto, acid anhydrides, and the like, and two or more of them may be used in combination. Specific examples include an anhydride of 1,2,4-benzenetricarboxylic acid; an anhydride of 1,3,5-benzenetricarboxylic acid; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; phthalic acid. A compound in which an anhydride and benzoic acid are single-bonded, -O-, -CH _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -SO _2- or a phenylene group is linked. Can be mentioned.

In the production of the resin, the amount of the diamine compound, the tetracarboxylic acid compound and / or the dicarboxylic acid compound used can be appropriately selected according to the ratio of each structural unit of the desired polyimide resin.

In the production of the resin, the reaction temperature of the diamine compound, the tetracarboxylic acid compound and the dicarboxylic acid compound is not particularly limited, but 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, but is, for example, about 30 minutes to 10 hours. If necessary, the reaction may be carried out under conditions of an inert atmosphere or reduced pressure. In a preferred embodiment, the reaction is carried out under normal pressure and / or an atmosphere of an inert gas with stirring. The reaction is preferably carried out in a solvent inert to the reaction. The solvent is not particularly limited as long as it does not affect the reaction, and for example, water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, etc. Alcohol-based solvents such as 2-butoxyethanol and propylene glycol monomethyl ether; ester-based solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, γ-valerolactone, propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as ethyl cyclohexane; toluene and xylene Aromatic hydrocarbon solvents such as; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; amides such as N, N-dimethylacetamide and N, N-dimethylformamide. Examples thereof include sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide and sulfolane; carbonate solvents such as ethylene carbonate and propylene carbonate; and combinations thereof (mixed solvents). Among these, an amide-based solvent can be preferably used from the viewpoint of solubility.

In the imidization step in the production of the polyimide resin, imidization can be performed in the presence of an imidization catalyst. Examples of imidization catalysts include aliphatic amines such as tripropylamine, dibutylpropylamine, and ethyldibutylamine; N-ethylpiperidin, N-propylpiperidin, N-butylpyrrolidin, N-butylpiperidin, and N-propylhexahydro. Alicyclic amines such as azepine (monocyclic); azabicyclo [2.2.1] heptane, azabicyclo [3.2.1] octane, azabicyclo [2.2.2] octane, and azabicyclo [3.2. 2] Alicyclic amines such as nonane (polycyclic); and pyridine, 2-methylpyridine (2-picolin), 3-methylpyridine (3-picolin), 4-methylpyridine (4-picolin), 2- Ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 3,4-cyclopentenopyridine, 5,6,7,8-tetrahydroisoquinoline, and Examples include aromatic amines such as isoquinolin. Further, from the viewpoint of easily promoting the imidization reaction, it is preferable to use an acid anhydride together with the imidization catalyst. Examples of the acid anhydride include conventional acid anhydrides used in the imidization reaction, and specific examples thereof include acetic anhydride, propionic anhydride, butyric anhydride and other aliphatic acid anhydrides, and phthalic acid and other aromatics. Acid anhydride and the like can be mentioned.

Polyimide-based resins and polyamide-based resins are isolated by separation and purification by conventional methods such as separation means such as filtration, concentration, extraction, crystallization, recrystallization, and column chromatography, or separation means combining these. In a preferred embodiment, a reaction solution containing a transparent polyamideimide resin can be isolated by adding a large amount of alcohol such as methanol to precipitate the resin, and performing concentration, filtration, drying and the like.

[Additive]
The resin film of the present disclosure may further contain additives such as fillers. Examples of such additives include silica particles, UV absorbers, whitening agents, silica dispersants, antioxidants, pH regulators, and leveling agents.

(Silica particles)
The resin film of the present disclosure may further contain silica particles as an additive. The content of the silica particles is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and preferably 60 parts by mass or less, based on 100 parts by mass of the resin film. It is preferably 50 parts by mass or less, more preferably 45 parts by mass or less. Further, the content of the silica particles can be combined by selecting an arbitrary lower limit value and upper limit value among these upper limit values and lower limit values. When the content of the silica particles is within the numerical range of the upper limit value and / or the lower limit value, the silica particles are less likely to aggregate in the resin film of the present disclosure and tend to be uniformly dispersed in the state of the primary particles. It is possible to suppress a decrease in visibility of the resin film in the disclosure.

The average primary particle size of the silica particles is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more, still more preferably 8 nm or more, preferably 30 nm or less, more preferably 28 nm or less, still more preferably 25 nm. Below, it is even more preferably 20 nm or less. The particle size of the silica particles can be combined by selecting any lower limit value and upper limit value among these upper limit values and lower limit values. The average primary particle size of the silica particles in the resin film can be measured by imaging with a transmission electron microscope. Further, the particle size of the silica particles before the resin film is produced, for example, before being added to the varnish can be measured by a laser diffraction type particle size distribution meter.

Examples of the form of the silica particles include a silica sol in which the silica particles are dispersed in an organic solvent and the like, and a silica powder prepared by a vapor phase method. Among these, silica sol is preferable from the viewpoint of workability.

The silica particles may be surface-treated, and may be, for example, silica particles in which a water-soluble alcohol-dispersed silica sol is replaced with a solvent, more specifically, γ-butyrolactone or the like.
The water-soluble alcohol is an alcohol having 3 or less carbon atoms per hydroxy group in one water-soluble alcohol molecule, and examples thereof include methanol, ethanol, 1-propanol, and 2-propanol. Although it depends on the compatibility between the silica particles and the type of polyimide polymer, when the silica particles are surface-treated, the compatibility with the polyimide polymer contained in the resin film is usually improved, and the dispersibility of the silica particles is improved. Therefore, it is possible to suppress a decrease in visibility of the present disclosure.

(UV absorber)
The resin film in the present disclosure may further contain an ultraviolet absorber. For example, a triazine-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a benzoate-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and the like can be mentioned. These may be used alone or in combination of two or more. Suitable commercially available UV absorbers include, for example, Sumisorb® 340 manufactured by Sumika Chemtex Co., Ltd., ADEKA STAB® LA-31 manufactured by ADEKA Corporation, and BASF Japan Ltd. Chinubin (registered trademark) 1577 and the like can be mentioned. The content of the ultraviolet absorber is preferably 1 phr or more and 10 phr or less, more preferably 3 phr or more and 6 phr or less, based on the mass of the resin film in the present disclosure.

As described above, in the system of the present disclosure, with respect to the light emitted from the irradiation unit, preferably ultraviolet light, the light transmittance with respect to the resin film is preferably 5% or less, more preferably 3%, as described above. Hereinafter, it is selected so as to be more preferably 2% or less. For the light transmittance of such a resin film, for example, the type and amount of the above-mentioned ultraviolet absorber can be adjusted, and the structure of the resin, particularly the type and amount of the monomer used as a raw material of the resin, particularly the content of the aromatic ring can be adjusted. By adjusting, it can be within the range.

(Whitening agent)
The resin film in the present disclosure may further contain a whitening agent. The whitening agent can be added to adjust the color when an additive other than the whitening agent is added, for example. Examples of the whitening agent include monoazo dyes, triarylmethane dyes, phthalocyanine dyes, and anthraquinone dyes. Among these, anthraquinone dyes are preferable. Suitable commercially available whitening agents include, for example, Macrolex® Violet B manufactured by LANXESS, Sumiplast® Violet B manufactured by Sumika Chemtex Co., Ltd., and Diaresin manufactured by Mitsubishi Chemical Corporation. (Registered trademark) Blue G and the like can be mentioned. These may be used alone or in combination of two or more. When a whitening agent is contained, the content thereof is preferably 1 to 50 ppm, more preferably 1 to 45 ppm, still more preferably 3 to 40 ppm, still more preferably 5 to 35 ppm, based on the mass of the resin film in the present disclosure. Is.

[system]
As shown in FIG. 1, the system of the present disclosure includes the irradiation unit 1 and the sensor unit 2. The irradiation unit 1 and the sensor unit 2 are arranged so that the light 4 emitted from the irradiation unit 1 is received by the observation unit of the sensor unit 2. The resin film 3 that is the target of this system is located between the irradiation unit and the sensor unit so as to block the light. The light irradiates the portion gripped by the gripper of the tenter type stretching device of the resin film 3, typically both ends of the resin film 3. In the system of the present disclosure, when the resin film is not cracked, the light emitted from the irradiation portion is blocked by the resin film, but when the resin film is cracked, the light transmitted through the cracked portion is emitted. , Detected by the sensor unit. In the system of the present disclosure, defects can be detected by detecting the light transmitted through the cracked portion.

In a preferred embodiment, the irradiation unit and the sensor unit are arranged so as to face each other with the conveyed resin film interposed therebetween, and the irradiation unit is the surface on which the resin film is in contact with the pedestal of the gripper (hereinafter, resin film). The sensor portion is located on the surface (hereinafter, also referred to as the “front surface” of the resin film) in which the resin film is in contact with the grip portion of the gripper. Here, in order to explain the front surface and the back surface, FIG. 2 shows a gripping state of the film 3 in the tenter type stretching apparatus. Both ends of the resin film 3 are gripped by the gripping tool 6. The gripping tool 6 includes a pedestal 7, a support portion 8, and a grip portion 9. The grip portion 9 is movable with the fulcrum 10 as a fulcrum, and grips the film 3 by sandwiching the film 3 between the grip portion 9 and the pedestal 7. At this time, the main surface of the resin film 3 in contact with the grip portion 9 is referred to as the front surface 11, and the main surface of the receiving film 3 in contact with the pedestal 7 is referred to as the back surface 12. As shown in FIG. 1, cracks in the resin film tend to cause edges 5 to stand on the front side of the film at locations where the gripping portions, which are movable portions, come into contact with each other. Such edges can prevent the light from passing through the cracks when illuminated from the surface. By arranging the irradiation unit and the sensor unit as described above, the light is irradiated from the back surface of the resin film having no edge, the light easily passes through the cracks, and the defect detection sensitivity is improved.

In a more preferred embodiment, the irradiation unit is on the downstream side (upper side in FIG. 1) in the transport direction (indicated by an arrow in FIG. 1) with respect to the intersection of the straight line connecting the irradiation unit and the sensor unit and the resin film. The sensor unit is arranged on the upstream side (lower side in FIG. 1) in the transport direction. Since the edge 5 tends to be inclined toward the downstream side in the transport direction, by arranging the irradiation unit and the sensor unit as described above, light can easily pass through the cracks, and the defect detection sensitivity can be improved. improves.

In a preferred embodiment, the irradiation axis connecting the irradiation unit and the sensor unit has an angle of 10 to 80 °, preferably 30 to 70 °, and more preferably 40 to 70 ° with respect to the main surface of the resin film. In other words, such an angle is an angle formed by the irradiation axis of the light emitted from the irradiation unit and the main surface of the film (θ in FIG. 1). By tilting the angle formed by the light irradiation axis and the main surface of the resin film within the above range, the defect detection accuracy is improved.

In a preferred embodiment, the angle formed by the irradiation axis connecting the irradiation unit and the sensor unit and the surface parallel to the transport direction of the resin film and perpendicular to the main surface of the resin film is 0 to 15 °, preferably 0 to 0. It is 10 °, more preferably 0 to 5 °. By setting such an angle within the above range, the defect detection accuracy is improved.

In a more preferred embodiment, the angle formed by the irradiation axis connecting the irradiation unit and the sensor unit and the main surface of the resin film is 10 to 80 °, preferably 30 to 70 °, and more preferably 40 to 70 °. The angle formed by the irradiation axis connecting the irradiation unit and the sensor unit and the surface parallel to the transport direction of the resin film and perpendicular to the main surface of the resin film is 0 to 15 °, preferably 0 to 10. °, more preferably 0-5 °. By setting such an angle within the above range, the defect detection accuracy is further improved.

The positional relationship between the irradiation unit and the sensor unit is not particularly limited as long as defects in the film, especially cracks, can be detected.

The distance between the irradiation unit and the main surface of the resin film along the irradiation axis and the distance between the sensor unit and the main surface of the resin film along the irradiation axis are independent of each other, preferably 1 mm or more. It can be preferably 10 mm or more, still more preferably 20 mm or more, even more preferably 30 mm or more, preferably 250 mm or less, more preferably 150 mm or less, still more preferably 100 mm or less. By reducing the distance between the irradiation part and the resin film, the defect detection accuracy is improved.

This system can continuously detect defects while transporting a resin film. That is, this system can detect defects in the operating state without stopping the tenter type stretching device.

This system is used in a tenter type stretching device that grips, conveys, and stretches both ends of a resin film. Here, the tenter type stretching device is a tenter rail in which a plurality of gripping tools (hereinafter, also referred to as tenter clips) for gripping both ends of the resin film are continuously provided from the carry-in port of the stretching furnace to the carry-out port. It has a mechanism that moves on and continuously stretches the resin film uniaxially or biaxially.

When the resin film has a property of shrinking due to drying, heating, etc., the film width may be smaller after the resin film is carried out than before it is carried into the stretching furnace. That is, the resin film may shrink and the draw ratio may be less than 1. In this case as well, if the film width is wider, it can be said that the film is stretched when it is attached to the tenter-type stretching device than when it is dried or heated without being attached to the tenter-type stretching device. That is, in the present specification, pulling the resin film in order to suppress the degree of shrinkage is also included in stretching.

Here, the defect means that the film has a missing portion such as a crack, a tear, or a hole. Such a missing portion means a missing portion having a certain width, for example, a width of 0.1 mm or more when the film is viewed in a plan view, and a very small one such as a pinhole is not included in the missing portion.

The system of the present disclosure typically detects defects in the tenter clips of the tenter-type stretching apparatus, that is, at both ends of the resin film.

The system of the present disclosure can detect cracks in the portion where the film is gripped between the portion where the resin film is released from the gripper and the portion where the resin film is wound in the tenter type stretching apparatus. , Can be installed. It should be noted that both ends of the resin film, that is, the portions gripped by the gripping tool may be slit between the installation location of the system of the present disclosure and the location where the resin film is wound. By performing the slit, the edge portion of the film in which the crack has occurred can be removed, and the spread of the crack in the film and the breakage of the film can be suppressed.

In a preferred embodiment, the system of the present disclosure is preferably installed at a position where defects in the resin film can be detected as soon as possible after the resin film is released from the gripper. For example, in the system of the present disclosure, the transport distance after the resin film is released from the gripper is preferably within 3 m, more preferably within 2 m, still more preferably within 1.5 m, and even more preferably within 1.3 m. In particular, it is installed at a position within 1.2 m, and preferably at a position of 0.01 m or more. If the defects of the resin film are left unattended, the defects expand and the risk of the film breaking increases. By making it possible to detect defects at an early stage after being released from the gripper as described above, it is possible to take countermeasures and reduce the risk of film breakage. As the countermeasure, for example, a tape or the like is attached to the cracked portion to prevent the crack from spreading.

As described above, the system of the present disclosure can be incorporated into a tenter type stretching device and can detect defects satisfactorily. Therefore, the present disclosure provides a method for detecting defects in a resin film using the system of the present disclosure.

[Tenter type stretching device]
The present disclosure provides a tenter type stretching apparatus having the system of the present disclosure described above.

In the tenter type stretching apparatus of the present disclosure, a plurality of tenter clips for gripping both ends of the resin film are arranged at regular intervals, and tenter rails (or endless) are continuously provided from the carry-in port to the carry-out port of the stretching furnace. It has a mechanism that moves on a chain) and continuously stretches a resin film uniaxially or biaxially, and a mechanism that detects defects by the system of the present disclosure described above.

FIG. 3 is a diagram schematically showing a film stretching mechanism in a tenter type stretching device. As shown in FIG. 3, a device in which a plurality of gripping tools 6 grip the end portion of the film 3 and continuously move while grasping the end portion of the film 3 is a stretching mechanism 21 and is a film. The introduction unit 22 for introducing the film 3 grips the film 3, and the delivery unit 23 for delivering the film 3 releases the film 3. In the meantime, the gripping tools 6 are continuously arranged to grip and release the film 3. And repeat. As shown in FIG. 3, the grippers 6 are arranged in a loop at regular intervals, and the grippers released by the delivery unit 23 come around to the introduction unit 22 and grip again. There is.

[Manufacturing method of resin film]
A resin film can be produced by using a tenter type stretching apparatus equipped with the system of the present disclosure.

Hereinafter, a method for producing a resin film using the tenter type stretching apparatus of the present disclosure will be described.

The resin film processed by the tenter type stretching apparatus of the present disclosure is not particularly limited, but for example, the following steps:
(A) A step of preparing a liquid containing the resin (hereinafter, may be referred to as varnish) (varnish preparation step),
(B) A step of applying varnish to a base material to form a coating film (coating step), and (c) a step of drying the applied liquid (coating film) to form a resin film (resin film formation). Process)
It can be manufactured by a method including.

In the varnish preparation step, the resin is dissolved in a solvent, and if necessary, the filler and other additives are added and mixed by stirring to prepare the varnish. When silica is used as the filler, a silica sol obtained by substituting a dispersion liquid of silica sol containing silica with a solvent in which the resin can be dissolved, for example, a solvent used for preparing the following varnish may be added to the resin.

The solvent used for preparing the varnish is not particularly limited as long as the resin can be dissolved. Examples of such a solvent include amide solvents such as N, N-dimethylacetamide and N, N-dimethylformamide; lactone solvents such as γ-butyrolactone and γ-valerolactone; sulfur-containing solvents such as dimethyl sulfoxide, dimethyl sulfoxide and sulfolane. System solvents; carbonate-based solvents such as ethylene carbonate and propylene carbonate; and combinations thereof can be mentioned. Among these, an amide solvent or a lactone solvent is preferable. These solvents can be used alone or in combination of two or more. Further, the varnish may contain water, an alcohol solvent, a ketone solvent, an acyclic ester solvent, an ether solvent and the like. The solid content concentration of the varnish is preferably 1 to 25% by mass, more preferably 5 to 20% by mass. The solid content can be measured by a dry weight loss method.

In the coating step, a varnish is applied onto the substrate by a known coating method to form a coating film. Known coating methods include, for example, wire bar coating method, reverse coating, roll coating method such as gravure coating, die coating method, comma coating method, lip coating method, screen coating method, fountain coating method, spray method, salivation molding method and the like. Can be mentioned.

In the resin film forming step, a long strip-shaped resin film can be formed by drying the coating film and peeling it from the base material. After the peeling, a heat treatment step of further drying the resin film may be performed. The heat treatment of the coating film can usually be performed at a temperature of 50 to 350 ° C. If necessary, the coating film may be dried under an inert atmosphere or under reduced pressure conditions. Such heat treatment can be performed by the tenter type stretching apparatus of the present disclosure.

In the heat treatment, both ends of the long strip-shaped resin film are gripped by tenter clips, and while the gripped film is conveyed, the width of the gripped film is set to a predetermined distance, for example, in a stretching furnace of a dryer. Heat treatment is performed while transporting. At this time, the ratio of the width of the film after the heat treatment (however, the gripped portion is not included in the width) to the width of the film before the heat treatment (however, the gripped portion is not included in the width) is 1. The heat treatment of the resin film can be performed by setting the number to 2 or less and releasing the grip of the resin film from the dryer. The fact that the gripped portion is not included in the width does not include the distance from the contact portion between the resin film and the tenter clip to the end portion of the film at both ends of the film, in other words, the contact with the tenter clip. It means the width of the central portion of the film (indicated by X in FIG. 2).

The ratio of the width of the film after heat treatment (however, the gripped part is not included in the width) to the width of the film before heat treatment (however, the gripped part is not included in the width) (also called the draw ratio) , Usually 0.70 to 1.20, preferably 0.80 to 1.15, more preferably 0.9 to 1.10, still more preferably 0.90 to 1.10.

The film is gripped by using a plurality of tenter clips. Since the gripped portion is gripped by a clip or the like, it cannot have the width that can be stretched as described above. Therefore, when calculating the stretch ratio, it is calculated by excluding it from the film width.

The plurality of tenter clips can be fixed to an endless chain of a predetermined length, depending on the size of the transport device, the chain moves at the same speed as the film, and the tenter is in the appropriate position of the chain. A clip is installed to grip the film before entering the dryer, and when it leaves the dryer, the grip is released and the film is released. The tenter clip that has released the film moves to the carry-in inlet side of the dryer and grips the film again.

The plurality of tenter clips installed at one end of the film are installed at regular intervals so that the space between the adjacent tenter clips is, for example, 1 to 50 mm, preferably 3 to 25 mm, and more preferably 5 to 20 mm. Will be done.

Further, when a straight line orthogonal to the film transport axis is aligned with the center of the grip portion of an arbitrary tenter clip at one end of the film, the intersection of the straight line and the other end of the film and the grip portion of the clip closest to the intersection. The distance from the center can be preferably 3 mm or less, more preferably 2 mm or less, still more preferably 1 mm or less. When the distance is in the above range, it is possible to homogenize the optical properties such as the phase difference between the left and right sides of the film.

When the ratio of the width of the film after the heat treatment to the width of the film before the heat treatment is in the above range, the appearance of the film tends to be good.

The amount of the solvent in the film after the heat treatment is preferably 0.0001% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.3% by mass or more, and preferably 0.3% by mass or more, based on the mass of the film. It is 2% by mass or less, more preferably 1.8% by mass or less, further preferably 1.7% by mass or less, and particularly preferably 1.2% by mass or less. When the amount of the solvent in the film after the heat treatment is in the above range, the appearance of the film tends to be good.

The total light transmittance of the resin film after the heat treatment is preferably 80% or more, more preferably 85% or more, still more preferably 88% or more, even more preferably 89% or more, particularly preferably 90% or more, and particularly more preferably. Is 91% or more, and usually 100% or less. When the total light transmittance is equal to or higher than the above lower limit, it is easy to improve the visibility when the resin film is incorporated into the image display device, particularly as a front plate. Since the resin film usually exhibits a high total light transmittance, it is possible to suppress the emission intensity of a display element or the like required to obtain a constant brightness as compared with the case of using a film having a low transmittance, for example. It will be possible. Therefore, power consumption can be reduced. For example, when the resin film is incorporated into an image display device, a bright display tends to be obtained even if the amount of light from the backlight is reduced, which can contribute to energy saving. The total light transmittance can be measured using a haze computer in accordance with, for example, JIS K 7105: 1981 or JIS K 7361-1: 1997. Further, the total light transmittance may be the total light transmittance in the range of the thickness of the resin film described later.

The haze of the transparent resin film after the heat treatment is usually 0.01% or more, preferably 3% or less, more preferably 2.5% or less, still more preferably 1.5% or less, still more preferably 1.0. % Or less, particularly preferably 0.5% or less, and particularly more preferably 0.3% or less. When the haze of the resin film is not more than the above upper limit, it is easy to improve the visibility when the resin film is incorporated into an image display device, particularly as a front plate. The haze can be measured using a haze computer in accordance with JIS K 7105: 1981 or JIS K 7136: 2000.

The YI value of the transparent resin film after the heat treatment is usually 0.1 or more, preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.2 or less. When the YI value of the resin film is not more than the above upper limit, the transparency becomes good, and it can contribute to high visibility when used for the front plate of the image display device. The YI value was measured by measuring the transmittance of light at 300 to 800 nm using an ultraviolet-visible near-infrared spectrophotometer, and the tristimulus values (X, Y, Z) were obtained, and YI = 100 × (1.2769X−). It can be calculated based on the formula of 1.0592Z) / Y.

The elastic modulus of the transparent resin film after the heat treatment is preferably 4.5 GPa or more, more preferably 5.0 GPa or more, still more preferably 5.5 GPa or more, still more preferably 6. It is 0 GPa or more, particularly preferably 6.2 GPa or more, particularly more preferably 6.4 GPa or more, and usually 100 GPa or less. The elastic modulus can be measured using a tensile tester (distance between chucks 50 mm, tensile speed 10 mm / min), for example, by the method described in Examples.

When the heat treatment is completed and the film is carried out from the dryer, the grip by the clip is released and the film is released.

After the film is released, defects are detected by the defect detection system described above. When a defect is detected, for example, a protective sheet can be attached to the cracked portion to prevent the film from breaking due to the expansion of the crack, and the device can be stopped due to the film breakage. It is possible to prevent deterioration of productivity.

The edges of the film are then slit. By performing slitting, cracks that are likely to occur between the gripped portion and the non-grasped portion at the edge of the film are removed from the film, so that the film is subsequently conveyed and its temperature is lowered. It is possible to prevent the film from spreading due to cracking in advance.

(Base material)
Examples of the base material include an endless belt made of SUS if it is metal-based, a long strip-shaped PET film or PEN film if it is resin-based, another polyimide-based resin or polyamide-based resin film, or a cycloolefin-based polymer (COP). ) Films, acrylic films, etc. can be mentioned. Among them, PET film, COP film and the like are preferable from the viewpoint of excellent smoothness and heat resistance, and PET film is more preferable from the viewpoint of adhesion to a transparent resin film and cost.

(Protective film)
In the present invention, the transparent resin film may include a protective film bonded to the transparent resin film to form a laminate. The protective film is attached to the surface of the transparent resin film without a support. If there is a problem with winding performance such as blocking when winding the laminated body into a roll shape, in addition to the above, attach a protective film to the surface of the support opposite to the transparent resin film. May be good. The protective film attached to the transparent resin film is a film for temporarily protecting the surface of the transparent resin film, and is not particularly limited as long as it is a peelable film capable of protecting the surface of the transparent resin film. For example, polyester resin films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyolefin resin films such as polyethylene and polypropylene films, acrylic resin films and the like, and polyolefin resin films, polyethylene terephthalate resin films and the like. It is preferably selected from the group consisting of acrylic resin films. When the protective films are bonded to both sides of the laminate, the protective films on each side may be the same or different from each other.

The thickness of the protective film is not particularly limited, but is usually 10 to 100 μm, preferably 10 to 80 μm. When the protective films are bonded to both sides of the laminate, the thickness of the protective films on each side may be the same or different.

(Laminated film roll)
In the present invention, a laminate film roll in which the laminate (support, transparent resin film and, if necessary, a protective film) is wound around a winding core in a roll shape is called a laminate film roll. Laminated film rolls are often temporarily stored in the form of film rolls due to space and other restrictions in continuous production, and laminated film rolls are one of them.

Examples of the material constituting the core of the laminated film roll include polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyester resin, epoxy resin, phenol resin, melamine resin, silicon resin, polyurethane resin, polycarbonate resin, ABS resin and the like. Synthetic resin; metal such as aluminum; fiber-reinforced plastic (FRP: composite material in which fibers such as glass fiber are contained in plastic to improve strength) and the like. The winding core has a cylindrical or columnar shape, and its diameter is, for example, 80 to 170 mm. The diameter of the film roll after winding is not particularly limited, but is usually 200 to 800 mm.

Further, after the protective film is attached to the transparent resin film, it can be slit to a desired width.

[Bad clip detection method]
The system for detecting defects in the resin film of the present disclosure can continuously detect defects while transporting the resin film. On the other hand, the tenter clip is fixed to an endless chain that orbits at the same speed as the film is conveyed, and the resin film is periodically gripped and released. Therefore, in the presence of defective clips, defects are periodically detected at high frequency. By comparing the period of the tenter clip with the period in which the defect is detected, the defective clip that causes the defect can be identified. Thereby, for example, when the device is stopped, the defective clip can be replaced with a non-defective product to prevent cracking at that portion, and as a result, the yield of the film can be increased.

That is, the present disclosure discloses a resin film that is continuously conveyed and stretched in a tenter type stretching apparatus provided with a plurality of tenter clips that grips, conveys, and stretches both end portions of the resin film. Provided is a method for detecting a defective clip, which identifies a defective clip by continuously monitoring by the system of the above and comparing the period in which a defect of a resin film is detected with the period of a tenter clip.

^{The distance L 1} in which the clip goes around the tenter type stretching device is expressed as ^{L 1} = (L ² + L ^{3 ) × N from the clip length L 2} and the clip interval L ³ and the number of clips N. However, L ¹ , L ² and L ³ are all the same unit. A method for detecting defective clips will be described by taking such a tenter type stretching device as an example. Arbitrary clips are designated as the first clip, and the second, third, fourth, ... Nth clips are used in the order in which the film is gripped. In this case, since the moving speed of the clip is the same as the transport speed of the film and is constant, if the film transport speed is S, the next clip is obtained at each timing of ^{(L 2} + L ^{3) / S in the detection device.} If you set it to identify the fact and enter the clip number from which the detection is started in the detection device, it becomes clear which clip the defective clip hits.

Hereinafter, the present invention will be described in more detail with reference to Examples. Unless otherwise specified, "%" and "part" in the example mean mass% and parts by mass. First, a method for measuring physical property values will be described.

The abbreviations used in the following production examples and examples are as follows.
TFMB: 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl 6FDA: 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydride TPC: terephthaloyl chloride OBBC: 4,4 '-Oxybis (benzoyl chloride)
DMAc: N, N-dimethylacetamide GBL: γ-butyrolactone PET: polyethylene terephthalate DMF: N, N-dimethylformamide

<Weight average molecular weight (Mw)>
Gel permeation chromatography (GPC) measurement (1) Pretreatment method Dissolve the sample in GBL to make a 20% by mass solution, dilute it 100-fold with DMF eluate, and measure it by filtering it with a 0.45 μm membrane filter. It was made into a solution.
(2) Measurement condition column: TSKgel SuperAWM-H × 2 + SuperAW2500 × 1 (inner diameter 6.0 mm, length 150 mm, 3 connected)
Eluent: DMF (10 mmol / L lithium bromide added)
Flow rate: 0.6 mL / min Detector: RI detector Column temperature: 40 ° C
Injection volume: 20 μL
Molecular weight standard: Standard polystyrene

上記式において、αはポリアミド酸（イミド化率０％）の場合におけるアミドプロトン１個に対するベンゼンプロトンＡの個数割合である。 <Imidization rate>
The imidization ratio was ^{determined by 1} H-NMR measurement as follows.
(1) Pretreatment method A sample _{was dissolved in deuterated dimethyl sulfoxide (DMSO-d 6} ) to prepare a 2% by mass solution, which was used as a measurement solution.
(2) Measurement conditions Measuring device: JEOL 400MHz NMR device JNM-ECZ400S / L1
Standard substance: DMSO-d ₆ (2.5 ppm)
Sample temperature: Room temperature Integral number: 256 times Relaxation time: 5 seconds (3) ^{Imidization rate analysis method In the obtained 1} H-NMR spectrum, benzene protons were observed at 7.0 to 9.0 ppm, of which imidization was performed. The integral ratio of benzene proton A derived from the structure that does not change before and after was defined as Int _A. Further, amide protons having an amic acid structure remaining in the polyimide were observed at 10.5 to 11.5 ppm, and this integration ratio was defined as Int _B. From these integration ratios, the imidization ratio was calculated by the following formula.

In the above formula, α is the number ratio of benzene protons A to one amide proton in the case of polyamic acid (imidization ratio 0%).

<Average primary particle size>
The specific surface area of the powder obtained by drying the silica sol at 300 ° C. was measured by measuring the specific surface area S (m ² / g) using the specific surface area measuring device Monosorb MS-16 manufactured by Yuasa Aiokunis Co., Ltd. The average primary particle diameter D was calculated from the value of D (nm) = 2720 / S.

<Varnish viscosity>
The measurement was performed using an E-type viscometer DV-II + Pro manufactured by Brookfield Co., Ltd. in accordance with JIS K 8803: 2011. The measurement temperature was 25 ° C.

<Thickness and thickness distribution of support>
Using ID-C112XBS manufactured by Mitutoyo Co., Ltd., the thickness of 20 points or more was measured in the width direction of the support, and the difference between the average value and each data was calculated to obtain a thickness distribution.

<Film thickness>
Using ID-C112XBS manufactured by Mitutoyo Co., Ltd., the film thickness at 10 points or more was measured, and the average value was calculated.

<Light transmittance of film at 365 nm and light transmittance at 450 nm>
The above optical characteristic values were measured using a spectrocolorimeter CM-3700A manufactured by Konica Minolta Co., Ltd.

<Amount of residual solvent>
Using TG-DTA (EXSTAR6000 TG / DTA6300 manufactured by SII Co., Ltd.), the transparent resin films obtained in Examples 1 and 2 and Comparative Examples and 2 were heated from 30 ° C. to 120 ° C. and 5 at 120 ° C. It was held for 1 minute, and then the temperature was raised to 400 ° C. at a heating rate of 5 ° C./min. The ratio of the mass loss of the film from 120 ° C. to 250 ° C. to the mass of the film at 120 ° C. was calculated as the solvent content (referred to as the residual solvent amount).

<Crack detection sensitivity>
Light of a specific wavelength was irradiated, the film was irradiated, and the transmitted light was imaged by a CCD camera as a sensor and processed by an image processing device. When the image was clearly captured, it was detected as a crack. When it was recognized as a crack in a separate visual inspection, the overlook rate was set to 0 when it was detected by the detector, and the detection rate was equivalent and there was no oversight. The equipment used is shown below.
UV bar lighting (peak wavelength 365 nm) (manufactured by U-Technology Co., Ltd.)
LED surface illumination (peak wavelength: 450 nm) (model number: OPF-150x150w-PS; manufactured by OPTEX FA Co., Ltd.)
CMOS camera: Area sensor camera (made by iDS)
Lens: Single focus lens (manufactured by Tamron Co., Ltd.)
Image processing software: Adaptive vision Studio (manufactured by Future Processing)

No defects are visually overlooked, and the number of crack defects visually recognized is the total number of crack defects, and the number of crack defects detected by this detector is subtracted from the total number of crack defects, and the number is the number of missed defects in the detector. The ratio of the number of overlooked defects in the detector to the total number of cracked defects was taken as the overlooked ratio, and evaluated according to the following criteria.
◎: Very good: Overlook rate 0%
〇: Good: Overlook rate exceeds 0% and 5% or less △; Slightly good: Overlook rate exceeds 5% and less than 10% ×: Defective: Overlook rate 10% or more

<Manufacturing example>
Production Example 1: Production of Polyamide-imide Resin 1 Under a nitrogen gas atmosphere, a reaction vessel equipped with a stirring blade in a separable flask and an oil bath were prepared. 45 parts of TFMB and 768.55 parts of DMAc were put into a reaction vessel installed in an oil bath. TFMB was dissolved in DMAc while stirring the contents in the reaction vessel at room temperature. Next, 19.01 parts of 6FDA was further charged into the reaction vessel, and the contents in the reaction vessel were stirred at room temperature for 3 hours. Then, 4.21 parts of OBBC and then 17.30 parts of TPC were put into the reaction vessel, and the contents in the reaction vessel were stirred at room temperature for 1 hour. Next, 4.63 parts of 4-methylpyridine and 13.04 parts of acetic anhydride were further added to the reaction vessel, and the contents in the reaction vessel were stirred at room temperature for 30 minutes. After stirring, the temperature inside the container was raised to 70 ° C. using an oil bath, maintained at 70 ° C., and stirred for another 3 hours to obtain a reaction solution.
The obtained reaction solution was cooled to room temperature and poured into a large amount of methanol in the form of filaments to precipitate a precipitate. The precipitated precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C. to obtain a polyamide-imide resin 1. The Mw of the obtained polyamide-imide resin 1 was 380,000, and the imidization rate was 99.0%.

Production Example 2: Production of Polyimide Resin 1 A reactor equipped with a silica gel tube, a stirrer and a thermometer in a separable flask, and an oil bath were prepared. 75.52 parts of 6FDA and 54.44 parts of TFMB were put into this flask. While stirring this at 400 rpm, 519.84 parts of DMAc was added, and stirring was continued until the contents of the flask became a uniform solution. Subsequently, stirring was continued for another 20 hours while adjusting the temperature inside the container to be in the range of 20 to 30 ° C. using an oil bath, and the reaction was carried out to generate a polyamic acid. After 30 minutes, the stirring speed was changed to 100 rpm. After stirring for 20 hours, the reaction system temperature was returned to room temperature, and 649.8 parts of DMAc was added to adjust the polymer concentration to 10% by mass. Further, 32.27 parts of pyridine and 41.65 parts of acetic anhydride were added, and the mixture was stirred at room temperature for 10 hours to obtain a reaction solution. The obtained resin solution was cooled to room temperature and poured into a large amount of methanol in the form of filaments to precipitate a precipitate. The precipitated precipitate was dried by heating to remove the solvent to obtain a polyimide resin 1. When GPC measurement was performed on the obtained polyimide resin 1, Mw was 325,000. The imidization ratio of the polyimide resin 1 was 98.8%.

Production Example 3: Preparation of Silica Sol 1 A GBL-substituted silica sol was prepared by solvent substitution using an amorphous silica sol having an average primary particle size of 27 nm measured by the BET method, which was produced by the sol-gel method. The obtained sol was filtered through a membrane filter having an opening of 10 μm to obtain GBL-substituted silica sol 1. The content of silica particles in the obtained GBL-substituted silica sol 1 was 30% by mass.

Production Example 4: Preparation of Varnish (1) The composition ratio of the polyamide-imide resin 1 obtained in Production Example 1 and the silica sol obtained in Production Example 3 to the polyamide-imide resin: silica particles in the GBL solvent is 60. It was mixed so as to be: 40. In the obtained mixed solution, an ultraviolet absorber "Sumisorb (registered trademark) 340" (manufactured by Sumika Chemtex Co., Ltd.) of 5.7 phr with respect to the total mass of the polyamide-imide resin and the silica particles and the polyamide-imide resin and the silica particles were added. 35 ppm of brewing agent "Sumiblast (registered trademark) Violet B" (manufactured by Sumika Chemtex Co., Ltd.) was added to the total mass of the particles, and the mixture was stirred until uniform to obtain a varnish (1). The solid content of the varnish (1) was 10.8% by mass, and the viscosity at 25 ° C. was 38,300 cps.

Production Example 5: Preparation of varnish (2) Polyimide resin 1 obtained in Production Example 2 and 5.0 phr UV absorber "Sumisolv 340" (manufactured by Sumika Chemtex Co., Ltd.) are applied to the polyimide resin. , GBL: DMAc = 1: 9 was dissolved in a mixed solvent at a concentration of 16.5% by mass to obtain a varnish (2). The solid content of the varnish (2) was 16.6% by mass, and the viscosity at 25 ° C. was 37,000 cps.

Production example 6
The varnish (1) was applied onto a PET film (Toyobo Co., Ltd. "Cosmo Shine (registered trademark) A4100", thickness 188 μm, thickness distribution ± 2 μm) and salivated to form a varnish coating film. At this time, the linear velocity was 0.5 m / min. The varnish coating is dried at 80 ° C. for 10 minutes, then at 100 ° C. for 10 minutes, then at 90 ° C. for 10 minutes, and finally at 80 ° C. for 10 minutes. A film was formed. Then, the coating film was peeled off from the PET film to obtain a raw material film 1 having a thickness of 48 μm, a width of 700 mm, and a length of 1,200 m. The amount of residual solvent in the raw material film 1 was 9.7% by mass.

Production example 7
The varnish (2) was applied onto a PET film (Toyobo Co., Ltd. "Cosmo Shine (registered trademark) A4100", thickness 188 μm, thickness distribution ± 2 μm) and salivated to form a varnish coating film. At this time, the linear velocity was 0.4 m / min. The varnish coating is heated at 70 ° C. for 7.5 minutes, then at 120 ° C. for 7.5 minutes, then at 70 ° C. for 7.5 minutes, and finally at 75 ° C. for 7.5 minutes. It was dried under dry conditions to form a dry coating film. Then, the coating film was peeled off from the PET film to obtain a raw material film 2 having a thickness of 89 μm, a width of 700 mm, and a length of 1,200 m. The amount of residual solvent in the raw material film 2 was 9.6% by mass.

Example 1
The temperature inside the dryer using the clip using the raw material film 1 obtained in Production Example 6 as a gripping tool was set to 200 ° C., the clip gripping width was 25 mm, the film transport speed was 1.3 m / min, and the film width at the inlet of the dryer ( Adjust so that the ratio of the film width at the outlet of the dryer to the distance between the clips is 1.0, and adjust the wind speed in each chamber of the tenter dryer to 13.5 m / sec in one chamber and 13 m / sec in two chambers. The solvent was removed using a tenter type dryer (1 to 6 chamber configuration) adjusted to 11 m / sec in the 3 to 6 chambers to obtain a polyamide-imide film 1 having a thickness of 49 μm. After the film is separated from the clip, the film is passed through a system installed at a position advanced by 1,150 mm, that is, an ultraviolet irradiator with a peak wavelength of 365 nm and a sensor that receives the emitted light. It was. The irradiator and the sensor are installed so as to measure the part where the clip was holding the film on both sides of the film, the distance to the film is 40 mm and 75 mm, respectively, and the irradiation angle of light on the film is 55. The film was installed so that it was set to °, and crack defects were detected while visually checking by a person. Then, the clip portion was slit, a PET-based protective film was attached to the film, and the film was wound around an ABS 6-inch core to obtain a roll film having a length of 1,000 m. Table 2 summarizes the detection status of crack defects. The image detected by the system is shown in FIG.

Comparative Example 1
Defect detection was carried out in the same manner as in Example 1 except that the light irradiation device was changed to a visible light irradiation device having a peak wavelength of 450 nm.

Example 2
Defect detection was carried out in the same manner as in Example 1 except that the distance between the sensor and the film was changed to 150 mm.

Example 3
Defect detection was carried out in the same manner as in Example 1 except that the distances between the irradiator and the film and the sensor and the film were changed to 250 mm, respectively.

Example 4
Defect detection was carried out in the same manner as in Example 1 except that the angle between the irradiator and the sensor with respect to the film was 90 °.

Example 5
Defect detection was carried out in the same manner as in Example 1 except that the distance between the film and the irradiator was changed to 60 mm.

Example 6
Using the raw material film 2, a polyimide film 1 having a thickness of 79 μm was obtained in the same manner as in Example 1 except that the transport speed of the film was 0.9 m / min. Further, defect detection was carried out in the same manner as in Example 1.

Example 7
Defect detection was carried out in the same manner as in Example 6 except that the angle between the irradiator and the sensor with respect to the film was 5 °.

The system of the present disclosure can be used for detecting crack defects in a resin film in a tenter type stretching apparatus.

1 ... Irradiation part 2 ... Sensor part 3 ... Film 4 ... Ultraviolet light 5 ... Edge 6 ... Gripping tool (tenter clip)
7 ... Pedestal 8 ... Support 9 ... Grip 10 ... Support point 11 ... Front surface 12 ... Back side 21 ... Stretching mechanism 22 ... Introduction part 23 ... Sending part

Claims (23)

A system for detecting defects in a resin film in a tenter-type stretching device that grips, conveys, and stretches both ends of the resin film.
It has an irradiation unit that irradiates ultraviolet light and a sensor unit that detects the ultraviolet light.
A system for detecting defects in a resin film by irradiating the resin film with the ultraviolet light and detecting the ultraviolet light transmitted through the resin film with the sensor unit. A system that detects defects in the resin film in a tenter-type stretching device that grips, conveys, and stretches both ends of the resin film between the pedestal of the gripper and the grip.
It has an irradiation unit that irradiates light and a sensor unit that detects the light.
The irradiation unit and the sensor unit are arranged so as to face each other with the resin film interposed therebetween.
The irradiation portion is located on the surface side where the resin film is in contact with the pedestal, and the sensor portion is located on the surface side where the resin film is in contact with the grip portion.
A system for detecting defects in a resin film by irradiating the resin film with the light and detecting the light transmitted through the resin film with the sensor unit. The system according to claim 2, wherein the light is ultraviolet light. The system according to claim 1 or 3, wherein the wavelength of the maximum intensity of the ultraviolet light is in the range of 200 to 380 nm. The system according to any one of claims 1 to 4, wherein the resin film is installed between a portion where the resin film is released from the gripper after stretching and a portion where the resin film is wound up. The system according to any one of claims 1 to 5, wherein the angle formed by the irradiation axis connecting the irradiation unit and the sensor unit and the main surface of the resin film is 10 to 80 °. The angle formed by the irradiation axis connecting the irradiation unit and the sensor unit and a surface parallel to the transport direction of the resin film and perpendicular to the main surface of the resin film is 0 to 15 °, according to claims 1 to 6. The system according to any one item. The system according to any one of claims 1 to 7, wherein the distance between the irradiation unit and the main surface of the resin film along the irradiation axis is 1 to 250 mm. The system according to any one of claims 1 to 8, wherein the distance between the sensor unit and the main surface of the resin film along the irradiation axis is 1 to 250 mm. The system according to any one of claims 1 to 9, wherein the gripped resin film is irradiated with ultraviolet light at a portion released from the gripper. The system according to any one of claims 1 to 10, wherein the resin film is a resin film selected from the group consisting of a polyimide resin and a polyamide resin. The system according to any one of claims 1 to 11, wherein the resin film contains an ultraviolet absorber. A tenter type stretching apparatus having the system according to any one of claims 1 to 12. A method for producing a resin film using the tenter type stretching apparatus according to claim 13. A method for detecting defects in a resin film, which uses the system according to any one of claims 1 to 12. A method for producing a resin film in which a resin film is heat-treated using a tenter type stretching device.
The process of gripping both ends of the resin film,
The process of transporting the resin film tenter type stretching device into the furnace,
The process of releasing the resin film from the device from the gripper,
A sensor unit that detects ultraviolet light is provided with a detection unit that receives light emitted from an irradiation unit that irradiates ultraviolet light, which is provided in a tenter type stretching device, and a resin film passes between the detection units. Process,
A method for producing a resin film, which comprises a step of passing ultraviolet light through the defective portion and receiving the ultraviolet light by the light receiving portion when the resin film has a defect. A method for producing a resin film in which a resin film is dried by using a tenter type stretching device provided with a gripping tool for gripping the resin film between a pedestal and a gripping portion.
The process of gripping both ends of the resin film,
The process of transporting the resin film tenter type stretching device into the furnace,
The process of releasing the resin film from the device from the gripper,
The light emitted from the irradiation portion installed on the back surface side of the resin film that was in contact with the pedestal of the gripper provided in the tenter type stretching device is the surface of the resin film that was in contact with the grip portion of the gripper. A step in which a sensor unit for detecting light provided on the side is provided with a detection unit that receives light, and a resin film passes between the detection units.
A method for producing a resin film, which comprises a step of passing light through the defective portion and receiving the light by the light receiving portion when the resin film has a defect. The production method according to claim 17, wherein the light is ultraviolet light. The manufacturing method according to any one of claims 16 to 18, wherein the angle formed by the irradiation shaft connecting the irradiation unit and the sensor unit and the main surface of the resin film is 10 to 80 °. 16 to 19 of claims 16 to 19, wherein the angle formed by the irradiation axis connecting the irradiation unit and the sensor unit with a surface parallel to the transport direction of the resin film and perpendicular to the main surface of the resin film is 0 to 15 °. The production method according to any one of the following items. The manufacturing method according to any one of claims 16 to 20, wherein the distance between the irradiation portion and the main surface of the resin film along the irradiation axis is 1 to 250 mm. The manufacturing method according to any one of claims 16 to 21, wherein the distance between the sensor unit and the main surface of the resin film along the irradiation axis is 1 to 250 mm. In a tenter type stretching apparatus provided with a plurality of tenter clips, which grips, conveys, and stretches both ends of the resin film, the resin film continuously conveyed and stretched is subjected to any one of claims 1 to 12. A defective clip detection method for identifying defective clips by continuously monitoring by the system described in the section and comparing the period in which defects in the resin film are detected with the period in which the tenter clip is detected.

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