TWI791763B - film reel - Google Patents

Abstract

The present invention provides a film roll comprising a transparent resin film based on a polymer such as polyimide, which is less likely to cause uneven peeling when peeling off a protective film and achieves good appearance and visibility. The film roll of the present invention is wound with a film comprising: a transparent resin film comprising at least one material selected from the group consisting of polyimide, polyamide and polyamideimide A resin composition; and a protective film, which is bonded to the above-mentioned transparent resin film; The above-mentioned transparent resin film contains 0.1% by mass or more of a solvent relative to the total mass of the transparent resin film, At least one end in the width direction of the protective film is located on the inside of an end in the width direction of the transparent resin film.

Description

film reel

The present invention relates to a film reel comprising a transparent resin film and a protective film.

In recent years, with the thinning, lightening and softening of displays of various image display devices, transparent resin films based on polymers such as polyimide or polyamide have been widely used as a substitute for glass that has been used until now. Material. As one of methods for producing such a transparent resin film, a casting method (solution casting method) is known. In the casting method, a varnish containing a polymer such as polyimide dissolved in a solvent is usually coated on a support substrate to form a film, and after peeling off from the support substrate, the solvent is removed by drying, thereby The resin film is continuously formed. Appropriately layer a peelable protective film on the surface of the transparent resin film to protect the surface of the film (Patent Documents 1~3). [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-208312 [Patent Document 2] Japanese Patent Laid-Open No. 2015-214122 [Patent Document 3] Japanese Patent Laid-Open No. 2016-87799

[Problem to be solved by the invention]

When a solvent exists in a resin film, normally, the adhesiveness of a resin film and a protective film will become high. Therefore, it is difficult to peel the protective film uniformly from the resin film, and peeling unevenness remaining in the form of a pattern tends to occur on the surface of the resin film. In particular, transparent resin films produced by casting methods and using solvents are difficult to completely remove the solvent in the varnish during continuous production, and a certain amount of solvent remains in many cases, so that it is difficult to peel off the protective film. It is easy to produce uneven peeling tendency. Such peeling unevenness not only becomes a defect in appearance for a transparent resin film requiring high transparency, but also causes deterioration of visibility when used in displays such as various image display devices.

Therefore, an object of the present invention is to provide a film roll comprising a transparent resin film based on a polymer such as polyimide, which is less prone to uneven peeling when the protective film is peeled off and has good appearance and visibility. [Technical means to solve the problem]

The inventors of the present invention have diligently studied to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention provides the following suitable aspects. [1] A film roll wound with a film comprising: a transparent resin film comprising a material selected from the group consisting of polyimide, polyamide, and polyamideimide at least one resin composition; and a protective film, which is bonded to the above-mentioned transparent resin film; The above-mentioned transparent resin film contains 0.1% by mass or more of a solvent relative to the total mass of the transparent resin film, At least one end in the width direction of the protective film is located on the inside of an end in the width direction of the transparent resin film. [2] The film roll according to the above [1], wherein both ends of the protective film in the width direction are located on the inside of the ends of the transparent resin film in the width direction. [3] The film roll according to the above [1] or [2], wherein the length in the width direction of the protective film is 90 to 99% of the length in the width direction of the transparent resin film. [4] The film roll according to any one of [1] to [3] above, wherein the transparent resin film contains one or more solvents, and the solvent with the highest boiling point among the solvents has a boiling point of 120 to 300°C. [5] The film roll according to any one of the above [1] to [4], wherein the transparent resin film contains at least one kind selected from N,N-dimethylacetamide, γ-butyrolactone, N- Solvent in the group consisting of methylpyrrolidone, butyl acetate, cyclopentanone and amyl acetate. [6] The film roll according to any one of [1] to [5] above, wherein the protective film is a polyolefin-based resin film. [Effect of Invention]

According to the present invention, it is possible to provide a film roll comprising a transparent resin film based on a polymer such as polyimide, which is less likely to cause uneven peeling when peeling off a protective film and achieves good appearance and visibility.

Embodiments of the present invention will be described in detail below. In addition, the scope of the present invention is not limited to the embodiment described here, and various changes can be made in the range which does not impair the gist of the present invention.

The film reel of the present invention is formed by winding a laminated film comprising a transparent resin film and a protective film bonded to the above-mentioned transparent resin film. The transparent resin film constituting the film reel of the present invention contains a compound selected from , A resin composition of at least one kind selected from the group consisting of polyamide and polyamideimide.

In this specification, polyimide refers to a polymer containing a repeating structural unit containing an imide group, and polyamideimide refers to a repeating structural unit containing an imide group and a repeating structural unit containing an amide group A polymer of the two, polyamide means a polymer containing repeating structural units comprising amide groups. The polyimide-based polymer means a polymer containing any one or more selected from polyimide and polyimide-imide.

The polyimide-based polymer of this embodiment has a repeating structural unit represented by formula (10). Here, G represents a tetravalent organic group, and A represents a divalent organic group. G and/or A may contain two or more different repeating structural units represented by formula (10). Also, the polyimide-based macromolecule of the present embodiment may include any one of formula (11), formula (12), and formula (13) within the scope of not damaging the various physical properties of the obtained transparent resin film. Any one or more of the repeating structural units represented.

From the viewpoint of the strength and transparency of the transparent resin film, it is preferable that the main structural unit of the polyimide-based polymer is a repeating structural unit represented by formula (10). In the polyimide-based macromolecule of the present embodiment, the repeating structural unit represented by formula (10) is preferably more than 40 mol% with respect to the total repeating structural unit of the polyimide-based macromolecule, more preferably It is 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, especially preferably 98 mol% or more. The repeating structural unit represented by formula (10) may also be 100 mol%.

[chemical 1]

G and G ¹ each independently represent a tetravalent organic group, preferably a tetravalent organic group having 4 to 40 carbon atoms. The above-mentioned organic group may be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. In this case, the carbon number of the hydrocarbon group and the fluorine-substituted hydrocarbon group is preferably 1-8. As G and ^G1 , formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula ( 28) or a group represented by formula (29) and a tetravalent chain hydrocarbon group having 6 or less carbon atoms. In the formula, * means bond, Z means single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -Ar-, -SO ₂ -, -CO-, -O-Ar-O-, -Ar-O-Ar-, -Ar-CH ₂ -Ar-, -Ar-C( CH ₃ ) ₂ -Ar- or -Ar-SO ₂ -Ar-. Ar represents an arylylene group having 6 to 20 carbon atoms which may be substituted by a fluorine atom, and a specific example thereof includes a phenylene group. In terms of easily suppressing the yellowness of the obtained transparent resin film, as G and ^G1 , it is preferable to enumerate formula (20), formula (21), formula (22), formula (23), formula (24) ), the base represented by formula (25), formula (26) or formula (27).

[Chem 2]

G ² represents a trivalent organic group, preferably a trivalent organic group having 4 to 40 carbon atoms. The above-mentioned organic group may be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. In this case, the carbon number of the hydrocarbon group and the fluorine-substituted hydrocarbon group is preferably 1-8. As ^G2 , formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28) or Any one of the bonds of the group represented by the formula (29) is replaced with a hydrogen atom group and a trivalent chain hydrocarbon group having 6 or less carbon atoms. The example of Z in the formula is the same as the example of Z in the description related to G.

G ³ represents a divalent organic group, preferably a divalent organic group having 4 to 40 carbon atoms. The above-mentioned organic group may be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. In this case, the carbon number of the hydrocarbon group and the fluorine-substituted hydrocarbon group is preferably 1-8. As ^G3 , formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28) can be illustrated Or two non-adjacent bonds of the group represented by formula (29) are substituted with hydrogen atoms and a divalent chain hydrocarbon group having 6 or less carbon atoms. The example of Z in the formula is the same as the example of Z in the description related to G.

A, A ¹ , A ² and A ³ all represent a divalent organic group, preferably a divalent organic group having 4 to 40 carbon atoms. The above-mentioned organic group may be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group having 1-8 carbon atoms. In this case, the hydrocarbon group and the fluorine-substituted hydrocarbon group preferably have 1-8 carbon atoms. Examples of A, A ¹ , A ² and A ³ include: formula (30), formula (31), formula (32), formula (33), formula (34), formula (35), formula (36) , a group represented by formula (37) or formula (38); these groups substituted with one or more of methyl, fluorine, chlorine or trifluoromethyl; and a chain hydrocarbon group having 6 or less carbon atoms.

The * in the formula represents a bond, and Z ¹ , Z ² and Z ³ independently represent a single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, - C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, -SO ₂ -, -CO- or -N(R ² )-. Here, R ² represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a halogen atom. Here, R ² represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a halogen atom. Preferably, Z ¹ and Z ² , and Z ² and Z ³ are respectively located in meta or para positions with respect to each ring.

[Chem 3]

In the present invention, the resin composition for forming the transparent resin film may contain polyamide. The polyamide of this embodiment is a polymer mainly composed of repeating structural units represented by formula (13). Preferred examples and specific examples of G ³ and A ³ in polyamide are the same as preferred examples and specific examples of G ³ and A ³ in polyimide-based polymers. The above-mentioned polyamide may contain two or more repeating structural units represented by formula (13) in which G ³ and/or A ³ are different.

Polyimide-based polymers can be obtained, for example, by polycondensation of diamines and tetracarboxylic acid compounds (tetracarboxylic dianhydrides, etc.), for example, according to Japanese Patent Laid-Open No. 2006-199945 or Japanese Patent Laid-Open No. 2008- 163107 bulletin of the method recorded in the synthesis. Examples of commercially available polyimides include Neopulim (registered trademark) manufactured by Mitsubishi Gas Chemical Co., Ltd., KPI-MX300F manufactured by Kawamura Sangyo Co., Ltd., and the like.

Examples of tetracarboxylic acid compounds used in the synthesis of polyimide-based polymers include aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic acids and their anhydrides, preferably dianhydrides, and aliphatic tetracarboxylic acids. Anhydrides thereof, preferably aliphatic tetracarboxylic acid compounds such as dianhydrides, and the like. The tetracarboxylic acid compound may be tetracarboxylic acid compound derivatives, such as a tetracarboxylic-acid acid chloride compound other than an anhydride, These may be used individually or in combination of 2 or more types.

Specific examples of aromatic tetracarboxylic dianhydrides include non-condensed polycyclic aromatic tetracarboxylic dianhydrides, monocyclic aromatic tetracarboxylic dianhydrides, and condensed polycyclic aromatic tetracarboxylic dianhydrides. . Examples of non-condensed polycyclic aromatic tetracarboxylic dianhydride include: 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride , 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-linked Benzene tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2- Bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenoxyphenyl)propane dianhydride, 4,4'-(hexafluoroisopropylidene) Diphthalic dianhydride (sometimes described as 6FDA), 1,2-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl) Ethane dianhydride, 1,2-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, bis(3,4 -dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 4,4'-(p-phenylenedioxy)diphthalic dianhydride, 4,4 '-(m-phenylenedioxy)diphthalic dianhydride. Moreover, examples of monocyclic aromatic tetracarboxylic dianhydrides include 1,2,4,5-benzenetetracarboxylic dianhydrides, and examples of condensed polycyclic aromatic tetracarboxylic dianhydrides include 2,3, 6,7-Naphthalene tetracarboxylic dianhydride.

Among these, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3, 3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3 ,3',4,4'-Diphenyl tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxy phenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenoxyphenyl)propane dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride ( 6FDA), 1,2-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,2-bis(3 ,4-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, bis(3,4-dicarboxyphenyl)methanedianhydride, bis( 2,3-dicarboxyphenyl)methane dianhydride, 4,4'-(p-phenylenedioxy)diphthalic dianhydride and 4,4'-(m-phenylenedioxy)di Phthalic dianhydride, more preferably 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3, 3'-Biphenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA), bis(3,4-dicarboxyphenyl)methane dianhydride and 4,4'-(p-phenylenedioxy)diphthalic dianhydride. These can be used individually or in combination of 2 or more types.

As aliphatic tetracarboxylic dianhydride, a cyclic or acyclic aliphatic tetracarboxylic dianhydride is mentioned. The so-called cycloaliphatic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride having an alicyclic hydrocarbon structure. Specific examples thereof include: 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, etc. cycloalkane tetracarboxylic dianhydride, bicyclo[2.2.2]-7 -octene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl-3,3',4,4'-tetracarboxylic dianhydride and their positional isomers. These can be used individually or in combination of 2 or more types. Specific examples of acyclic aliphatic tetracarboxylic dianhydride include 1,2,3,4-butane tetracarboxylic dianhydride, 1,2,3,4-pentane tetracarboxylic dianhydride, etc. ; These can be used alone or in combination of two or more. Moreover, a cycloaliphatic tetracarboxylic dianhydride and a noncyclic aliphatic tetracarboxylic dianhydride can also be used in combination.

Among the tetracarboxylic acid compounds, from the viewpoint of easily improving the modulus of elasticity, bending resistance, and optical properties of the transparent resin film, the above-mentioned alicyclic tetracarboxylic dianhydrides or non-condensed polycyclic aromatic compounds are preferable. family of tetracarboxylic dianhydrides. As more specific examples, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA). These can be used individually or in combination of 2 or more types.

The polyimide-based macromolecule of this embodiment may also be made of tetracarboxylic acid in addition to the anhydride of tetracarboxylic acid used in the synthesis of polyimide as long as the various physical properties of the obtained transparent resin film are not impaired. Acids, tricarboxylic acid compounds, dicarboxylic acid compounds, their anhydrides and their derivatives are further reacted.

Examples of the tricarboxylic acid compound include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, and their analogous acid chloride compounds, acid anhydrides, and the like; two or more of these may be used in combination. Specific examples thereof include: 1,2,4-benzenetricarboxylic anhydride; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; phthalic anhydride and benzoic acid via a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ -, or phenylene-linked compounds.

Examples of the dicarboxylic acid compound include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and similar acyl chloride compounds, acid anhydrides, and the like, and two or more of these may be used in combination. Specific examples thereof include: terephthalic acid; isophthalic acid; naphthalene dicarboxylic acid; 4,4'-biphenyldicarboxylic acid; 3,3'-biphenyldicarboxylic acid; chains having 8 or less carbon atoms The dicarboxylic acid compound of the formula hydrocarbon and two benzoic acid skeletons through -CH ₂ -, -S-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -O-, -N(R ⁹ )-, -C(=O)-, -SO ₂ - or phenylene-linked compounds. These can be used individually or in combination of 2 or more types. Here, R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a halogen atom.

As the dicarboxylic acid compound, preferably: terephthalic acid; isophthalic acid; 4,4'-biphenyldicarboxylic acid; 3,3'-biphenyldicarboxylic acid; CH ₂ -, -C(=O)-, -O-, -N(R ⁹ )-, -SO ₂ - or phenylene-linked compounds; more preferably: terephthalic acid; 4,4'- Biphenyl dicarboxylic acid; and a compound in which two benzoic acid skeletons are linked by -O-, -N(R ⁹ )-, -C(=O)- or -SO ₂ -. These can be used individually or in combination of 2 or more types.

The ratio of the tetracarboxylic acid compound to the total of the tetracarboxylic acid compound, the tricarboxylic acid compound, and the dicarboxylic acid compound is preferably at least 40 mol %, more preferably at least 50 mol %, and still more preferably 70 mol % % or more, and more preferably more than 90 mol%, especially preferably more than 98 mol%.

Examples of diamines used in the synthesis of polyimide-based polymers include aliphatic diamines, aromatic diamines, and mixtures thereof. Furthermore, in this embodiment, the so-called "aromatic diamine" means a diamine whose amine group is directly bonded to an aromatic ring, and may contain an aliphatic group or other substituents in a part of its structure. The aromatic ring may be a single 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 used. Also, the term "aliphatic diamine" means a diamine in which an amine group is directly bonded to an aliphatic group, and part of its structure may contain an aromatic ring or other substituents.

Specific examples of aliphatic diamines include acyclic aliphatic diamines such as hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl) Cycloaliphatic diamines such as methyl)cyclohexane, northanediamine, and 4,4'-diaminodicyclohexylmethane; these may be used alone or in combination of two or more.

Specific examples of aromatic diamines include: p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene , 2,6-diaminonaphthalene and other aromatic diamines with one aromatic ring, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4 '-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3 ,4'-Diaminodiphenylphenylene, 3,3'-diaminodiphenylene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-amine phenyloxy)benzene, bis[4-(4-aminophenoxy)phenyl]pyridine, bis[4-(3-aminophenoxy)phenyl]pyridine, 2,2-bis[4 -(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2'-dimethylbenzidine, 2, 2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl (sometimes described as TFMB), 4,4'-bis(4-aminophenoxy)biphenyl, 9 ,9-bis(4-aminophenyl) fluorine, 9,9-bis(4-amino-3-methylphenyl) fluorine, 9,9-bis(4-amino-3-chlorophenyl) Aromatic diamines having two or more aromatic rings, such as ) fluorine, 9,9-bis(4-amino-3-fluorophenyl) fluorine, etc. These can be used individually or in combination of 2 or more types.

As the aromatic diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 3, 3'-diaminodiphenylether, 4,4'-diaminodiphenylene, 3,3'-diaminodiphenylene, 1,4-bis(4-aminophenoxy ) benzene, bis[4-(4-aminophenoxy)phenyl]pyridine, bis[4-(3-aminophenoxy)phenyl]pyridine, 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'-diaminobiphenyl (TFMB), 4,4'-bis(4-aminophenoxy)biphenyl, more preferably 4,4'-bis Aminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylene, 1,4- Bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]pyridine, 2,2-bis[4-(4-aminophenoxy)phenyl] Propane, 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 4,4'-bis(4- Aminophenoxy) biphenyl. These can be used individually or in combination of 2 or more types.

The above-mentioned diamine may have a fluorine-based substituent. Examples of the fluorine-based substituent include a perfluoroalkyl group having 1 to 5 carbon atoms such as a trifluoromethyl group, and a fluorine group.

Among the above-mentioned diamines, from the viewpoint of high transparency and low coloring property, it is preferable to use one or more kinds selected from the group consisting of aromatic diamines having a biphenyl structure. It is preferred to use a compound selected from 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB) and 4,4'-bis One or more species from the group consisting of (4-aminophenoxy)biphenyl groups. More preferably, it is a diamine having a biphenyl structure and a fluorine-based substituent. As a specific example, it is more preferable to use 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ( TFMB).

Polyimide-based polymers are formed by polycondensation of diamines and tetracarboxylic acid compounds (including derivatives of tetracarboxylic acid compounds such as acyl chloride compounds and tetracarboxylic dianhydrides) and contain repeating structures represented by formula (10) Unit condensation polymer. As starting materials, in addition to these, tricarboxylic acid compounds (including derivatives of tricarboxylic acid compounds such as acyl chloride compounds and tricarboxylic anhydrides) and dicarboxylic acid compounds (including derivatives of acyl chloride compounds and the like) are sometimes used . Also, polyamide is a condensation-type macromolecule formed by polycondensation of diamine and dicarboxylic acid compound (including derivatives such as acyl chloride compound) and including a repeating structural unit represented by formula (13).

The repeating structural units represented by formula (10) and formula (11) are usually derived from diamines and tetracarboxylic acid compounds. The repeating structural unit represented by formula (12) is usually derived from diamine and tricarboxylic acid compounds. The repeating structural unit represented by formula (13) is usually derived from diamine and dicarboxylic acid compounds. Specific examples of diamine, tetracarboxylic acid compound, tricarboxylic acid compound, and dicarboxylic acid compound are as described above.

The molar ratio of diamine and carboxylic acid compounds such as tetracarboxylic acid compounds can be appropriately adjusted within the range of preferably 0.9 mol or more and 1.1 mol or less of tetracarboxylic acid with respect to 1.00 mol of diamine. In terms of the high molecular weight of the polyimide-based polymer obtained in order to exhibit higher folding resistance, the molar ratio of tetracarboxylic acid is more preferably 0.98 mol relative to 1.00 mol of diamine More than 1.02 mol, more preferably 0.99 mol% or more and 1.01 mol% or less.

Also, from the viewpoint of suppressing the yellowness of the obtained transparent resin film, the ratio of the amino group to the obtained polymer terminal is preferably low, and a tetracarboxylic acid compound, etc. is preferably used relative to 1.00 mol of diamine. The carboxylic acid compound is 1.00 mol or more.

The number of fluorine in the molecules of diamines and carboxylic acid compounds (such as tetracarboxylic acid compounds) can be adjusted. Based on the mass of polyimide-based polymers, the fluorine in the obtained polyimide-based polymers The amount of fluorine is 1% by mass or more, 5% by mass or more, 10% by mass or more, or 20% by mass or more. Since the raw material cost tends to increase as the ratio of fluorine increases, the upper limit of the amount of fluorine is preferably 40% by mass or less. A fluorine-type substituent may exist in any one of a diamine or a carboxylic acid compound, and may exist in both. In particular, the YI value may decrease by including a fluorine-based substituent.

The polyimide-based polymer of this embodiment may also be a copolymer including a plurality of different types of the above-mentioned repeating structural units. The standard polystyrene-equivalent weight-average molecular weight of the polyimide-based polymer is usually 100,000 to 800,000. From the viewpoint of improving the flexibility during film formation when the weight average molecular weight of the polyimide-based polymer is large, it is preferably at least 200,000, more preferably at least 300,000, and still more preferably at least 350,000. Moreover, it is preferably 750,000 or less, more preferably 600,000 or less, and still more preferably 500,000 or less, from the viewpoint of obtaining a varnish with a moderate concentration and viscosity that tends to improve film-forming properties.

Polyimide-based polymers and polyamides tend to increase the modulus of elasticity and decrease the YI value when formed into a film by containing a fluorine-containing substituent. When the elastic modulus of the film is high, there is a tendency that generation of scratches, wrinkles, and the like is suppressed. From the viewpoint of film transparency, polyimide-based polymers and polyamides preferably have fluorine-containing substituents. Specific examples of the fluorine-containing substituent include a fluorine group and a trifluoromethyl group.

The content of fluorine atoms in the polyimide-based macromolecule and the mixture of polyimide-based macromolecule and polyamide is determined by the mass of polyimide-based macromolecule or the mass of polyimide-based macromolecule and polyimide-based macromolecule. Based on the total mass of amide, it is preferably from 1% by mass to 40% by mass, more preferably from 5% by mass to 40% by mass. When the content of fluorine atoms is 1% by mass or more, the YI value at the time of film formation tends to be further lowered to further improve transparency. When the content of fluorine atoms is 40% by mass or less, the polyimide tends to be easily increased in molecular weight.

In the present invention, the content of the polyimide-based polymer and/or polyamide in the resin composition constituting the transparent resin film is preferably 40% by mass or more, more preferably It is 50 mass % or more, More preferably, it is 70 mass % or more, It may be 100 mass %. When the content of the polyimide-based polymer and/or polyamide is more than the above lower limit, the flexibility of the transparent resin film will be good. In addition, the term "solid content" refers to the total amount of components after removing the solvent from the resin composition.

In the present invention, the resin composition for forming the transparent resin film may further contain inorganic materials such as inorganic particles in addition to the above-mentioned polyimide-based polymer and/or polyamide. Examples of the inorganic material include inorganic particles such as silica particles, titanium particles, aluminum hydroxide, zirconia particles, and barium titanate particles; and silicon compounds such as quaternary alkoxysilanes such as tetraethylorthosilicate. From the standpoint of the stability of the varnish and the dispersibility of the inorganic material, silica particles, aluminum hydroxide, and zirconia particles are preferable, and silica particles are more preferable.

The average primary particle diameter of the particles of the inorganic material is preferably 10-100 nm, more preferably 10-50 nm, further preferably 10-40 nm, further preferably 10-30 nm. There exists a tendency for transparency to improve when the average primary particle diameter of a silica particle is 100 nm or less. When the average primary particle diameter of the silica particles is 10 nm or more, the cohesive force of the silica particles tends to be weakened, making it difficult to handle.

In the present invention, the silica particles may be silica sol obtained by dispersing silica particles in an organic solvent or the like, or silica microparticle powder produced by a vapor phase method, which is easy to handle. In terms of aspect, silica sol produced by liquid phase method is preferable.

The average primary particle size of the silica particles in the transparent resin film can be obtained by observation with a transmission electron microscope (TEM). The particle size distribution of the silica particles before forming the transparent resin film can be obtained by a commercially available laser diffraction particle size distribution meter.

In the present invention, when the resin composition contains an inorganic material, its content is preferably from 10% by mass to 90% by mass, more preferably from 10% by mass to 60% by mass, relative to the solid content of the resin composition. Mass % or less, More preferably, it is 20 mass % or more and 50 mass % or less. When content of the inorganic material in a resin composition exists in the said range, it exists in the tendency which simultaneously realizes transparency and mechanical strength of a transparent resin film easily. In addition, the term "solid content" refers to the total amount of components after removing the solvent from the resin composition.

The resin composition constituting the transparent resin film may further contain other components in addition to the components described above. Examples of other components include antioxidants, mold release agents, light stabilizers, bluing agents, flame retardants, lubricants, and leveling agents.

In the present invention, when the resin composition contains resin components such as polyimide-based polymers and other components other than inorganic materials, the content of other components is preferably 0.001% by mass relative to the total mass of the transparent resin film. It is more than 20 mass %, More preferably, it is 0.002 mass % or more and 10 mass % or less.

In the present invention, the transparent resin film can be produced, for example, from a resin varnish made of a polyimide-based polyimide obtained by selecting and reacting the above-mentioned tetracarboxylic acid compound, the above-mentioned diamine, and the above-mentioned other raw materials. It is prepared by adding a solvent to a resin composition of a polymer and/or polyamide reaction solution, an optional inorganic material, and other components, followed by mixing and stirring. In the above-mentioned resin composition or resin varnish, a solution of purchased polyimide-based polymer, etc., or a solution of purchased solid polyimide-based polymer, etc. can also be used instead of polyimide-based polymer, etc. of the reaction solution.

As the solvent used for the preparation of the resin varnish, those capable of dissolving or dispersing resin components such as polyimide-based polymers can be appropriately selected. From the viewpoints of solubility, applicability, and drying properties of the resin component, it is preferably an organic solvent with a boiling point of 120-300°C, more preferably an organic solvent with a boiling point of 120-270°C, and more preferably an organic solvent with a boiling point of An organic solvent with a temperature of 120~250℃, especially an organic solvent with a boiling point of 120~230℃. Specific examples of such organic solvents include amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; -Lactone-based solvents such as butyrolactone and γ-valerolactone; ketone-based solvents such as cyclohexanone, cyclopentanone, and methyl ethyl ketone; acetate-based solvents such as butyl acetate and amyl acetate; Sulfur-containing solvents such as dimethicone, dimethylsulfene, and cyclobutylene, and carbonate-based solvents such as ethylene carbonate and propylene carbonate. Among them, in terms of excellent solubility in polyimide-based polymers and polyamides, N,N-dimethylacetamide (boiling point: 165°C), γ-butyrol Esters (boiling point: 204°C), N-methylpyrrolidone (boiling point: 202°C), butyl acetate (boiling point: 126°C), cyclopentanone (boiling point: 131°C) and amyl acetate (boiling point: 149°C ) in the group consisting of solvents. As the solvent, one type may be used alone, or two or more types may be used in combination. Furthermore, when using two or more kinds of solvents, it is preferable to select the kind of solvent so that the boiling point of the solvent with the highest boiling point among the solvents used falls within the said range.

The amount of the solvent is not particularly limited as long as it is selected so that the viscosity of the resin varnish can be processed. For example, it is preferably 50-95% by mass, more preferably 70-95% by mass relative to the total amount of the resin varnish. , and more preferably 80 to 95% by mass.

Moreover, content of the solvent in the transparent resin film which comprises the film roll of this invention is 0.1 mass % or more with respect to the gross mass of a transparent resin film. The film roll of the present invention suppresses peeling unevenness that occurs when the transparent resin film contains a solvent due to improved adhesion with the protective film, making it difficult to peel the protective film uniformly. The total mass of the transparent resin film relative to the film For example, when it is at least 0.5% by mass, preferably at least 1% by mass, more preferably at least 5% by mass, a higher effect of suppressing uneven peeling can be obtained. Although the upper limit of the solvent content in a transparent resin film is not specifically limited, Usually, it is 20 mass % or less with respect to the total mass of a transparent resin film. Furthermore, in the present invention, the solvent content in the transparent resin film, for example, can be measured using a thermogravimetric-differential thermal (TG-DTA) measuring device as described in the following examples, and the mass loss rate from 120°C to 250°C can be calculated ( quality%).

The thickness of the transparent resin film may be appropriately determined according to the application of the transparent resin film, etc., and is usually 10-500 μm, preferably 15-200 μm, and more preferably 20-100 μm. When the thickness of the transparent resin film is within the above range, the flexibility of the transparent resin film is favorable.

The total light transmittance of the transparent resin film in the present invention with a thickness of 50 μm is preferably at least 80%, more preferably at least 85%, further preferably at least 88%, even more preferably at least 89%, especially preferably at least 80%. More than 90. The total light transmittance can be measured using a haze meter according to JIS K 7361-1:1997.

The yellowness at a thickness of 50 μm of the transparent resin film in the present invention is preferably 3.5 or less, more preferably 3.0 or less, further preferably 2.5 or less, still more preferably 2.2 or less. If the yellowness of the transparent resin film is within the above range, it is suitable for optical applications requiring higher transparency. Yellowness (YI value) can be measured with a UV-Vis-near-infrared spectrophotometer for the light transmittance of 300~800 nm, and the three stimulus values (X, Y, Z) can be obtained, and based on YI=100×(1.2769X- 1.0592Z)/Y formula and calculated.

The haze of the transparent resin film in the present invention at a thickness of 50 μm is preferably 5% or less, more preferably 4% or less, further preferably 3% or less, further preferably 2.5% or less, and still more preferably 2% or less. % or less, preferably less than 1%. When the haze of an optical film is below the said upper limit, especially when an optical film is incorporated in an image display apparatus as a front panel, it becomes easy to improve visibility. In addition, the lower limit of haze is usually 0.01% or more. In addition, haze can be measured using the haze meter based on JISK7136:2000.

The film roll of the present invention includes a protective film bonded to the above-mentioned transparent resin film. The protective film may be attached to only one side of the transparent resin film, or may be attached to both sides. The protective film attached to the transparent resin film is a film used to temporarily protect the surface of the transparent resin film. As long as it is a peelable film that can protect the surface of the transparent resin film, it is not particularly limited, preferably selected from polyethylene , Polypropylene film and other polyolefin-based resin films in the group. When the protective film is bonded to both sides of the transparent resin film, the protective films on each side may be the same or different.

In the film roll of the present invention, the protective film can be formed of a base film and laminated thereon, for example, an acrylic adhesive, an epoxy adhesive, a urethane adhesive, a polysiloxane adhesive, etc. The composition of the adhesive layer is preferably a self-adhesive resin film such as polyolefin-based resin from the viewpoint of the cost of the protective film. Also, if the tension and the peeling angle during peeling of the protective film are not strictly controlled, components derived from additives and the like contained in the polyolefin-based resin film tend to remain on the transparent resin film as peeling unevenness, but Since the film roll of the present invention has a high effect of suppressing uneven peeling, when a polyolefin-based resin film is included as a protective film, an especially advantageous effect can be obtained. Therefore, in a suitable embodiment of the present invention, the protective film-based polyolefin-based resin film constituting the film roll of the present invention is preferably a polypropylene-based resin film or The polyethylene-based resin film is more preferably a polyethylene-based resin film. Examples of polyethylene-based resins include high-pressure low-density polyethylene (LDPE), linear short-chain branched polyethylene (LLDPE), medium-low pressure high-density polyethylene (HDPE), and ultra-low-density polyethylene (VLDPE). etc. As the resin on the surface adjacent to the transparent resin film, LLDPE is preferable from the viewpoint of adhesiveness with the transparent resin film and workability.

The thickness of the protective film is not particularly limited, and is usually 10-100 μm, preferably 10-80 μm, more preferably 10-50 μm. When the protective film is attached to both sides of the transparent resin film, the thickness of the protective film on each side may be the same or different.

In the film roll of the present invention, at least one end in the width direction of the protective film bonded to the transparent resin film is located on the inner side than the end in the width direction of the transparent resin film. Here, an example of the layer configuration in the film roll of the present invention will be described based on FIG. The reel 1 winds a laminated film (4) having a transparent resin film 2 and a protective film 3 attached to one side of the transparent resin film 2 on a core (5), and overlaps each other to form a multilayer structure. Moreover, at least one end (3a) in the width direction of the protective film 3 is located on the inner side (the center side in the width direction of the film) than the end (2a) in the width direction of the transparent resin film 2 . When the protective film is attached to only one side of the transparent resin film, the laminated film can be wound with the protective film on the core side as shown in Figure 1, or the transparent resin film can be wound on the core side laminated film.

In the case where the width of the protective film is longer than that of the transparent resin film or the same case, the remaining part of the end of the protective film is caught by the interference of the end of the transparent resin film or the protective film and the ends of the transparent resin film interfere with each other , so it is difficult to peel the protective film uniformly and easy to generate uneven peeling. In the film roll of the present invention, at least one end in the width direction of the protective film is located on the inner side than the end in the width direction of the transparent resin film, so that jamming is less likely to occur when the protective film is peeled off from the transparent resin film. If jamming occurs during peeling, peeling unevenness will occur at the place where the jamming occurs. However, by uniformly peeling the protective film, the occurrence of peeling unevenness can be suppressed, and a transparent resin film with a good appearance can be obtained. In order to peel the protective film more uniformly from the transparent resin film, it is preferable that the both ends of the width direction of the protective film are positioned on the inner side than the ends of the width direction of the transparent resin film.

In the film roll of the present invention, the length of the protective film in the width direction is preferably 90-99%, more preferably 93-99%, and still more preferably 95-99% of the length of the transparent resin film in the width direction. . Also, in a suitable embodiment of the present invention, the length in the width direction of the protective film is preferably 5-40 mm shorter than the length in the width direction of the transparent resin film, more preferably 5-30 mm shorter, and then shorter than the length in the width direction of the transparent resin film. The best is 5~20 mm shorter. When the length in the width direction of the protective film and the transparent resin film is in the relationship of the above-mentioned ratio or range, the jamming during peeling can be reduced without damaging the function of the protective film protecting the surface of the transparent resin film, thereby preventing peeling failure. all. Furthermore, when the two ends of the width direction of the protective film are located on the inner side of the two ends of the transparent resin film, the lengths of the non-bonded parts of the transparent resin film and the protective film can be different from each other, so that more uniform peeling can be achieved. From this point of view, it is preferable to bond the protective film so that both ends of the transparent resin film remain at the same length. In addition, the length of the width direction of a film roll is not specifically limited, Usually, it is 500-1,500 mm.

In the present invention, the film roll is usually formed by winding a laminated film including a transparent resin film and a protective film on a core in a roll shape. Examples of materials constituting the core include: polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyester resin, epoxy resin, phenolic resin, melamine resin, silicone resin, polyurethane resin, Polycarbonate resin, ABS (Acrylonitrile-Butadiene-Styrene, acrylonitrile-butadiene-styrene) resin and other synthetic resins; metals such as aluminum; fiber reinforced plastics (FRP: plastics containing fibers such as glass fibers to increase strength composite materials), etc. The winding core is formed into a cylindrical shape or a cylindrical shape, and its diameter is, for example, 80 to 170 mm. Moreover, the diameter (diameter after winding) of a film roll is not specifically limited, Usually, it is 200-800 mm.

The film roll of the present invention can be manufactured by laminating a transparent resin film and a protective film using a known method and device/equipment, and then winding it on a core. Specifically, for example, it can be produced by a method including: a) coating a resin varnish obtained by mixing and stirring a resin composition for forming a transparent resin film and a solvent on a support substrate; b) The solvent is removed by drying the applied resin varnish to form a transparent resin film layer on the support substrate; c) attaching a protective film to the surface of the transparent resin film formed on the support substrate opposite to the support substrate; d) a step of peeling the support substrate from the layer of the transparent resin film formed on the support substrate to obtain a laminated film with a protective film bonded to the transparent resin film; and e) A step of winding the obtained laminated film.

The effect of the present invention of suppressing peeling unevenness when the protective film is peeled from the transparent resin film is particularly advantageously obtained when the transparent resin film contains a certain amount of solvent. For example, in the case of continuously producing a transparent resin film by a method including a step of coating a resin varnish containing a solvent to form a film and then removing the solvent by drying as represented by the casting method, it is difficult to completely remove the solvent by drying. Removal, in many cases, the solvent remains in the transparent resin film and is wound up directly. Therefore, the film roll of this invention which has the structure in which the end part of the width direction of a protective film is located inside rather than the end part of the width direction of a transparent resin film is especially advantageous as a structure of the film roll manufactured by the said method. In addition, after the above-mentioned step e) for removing the solvent in the transparent resin film, the film roll can be rolled out and then subjected to a drying step. The film is usually peeled from the surface of the transparent resin film. In such a case, the film roll of the present invention is particularly advantageous because it can effectively suppress peeling unevenness.

In the case of manufacturing the film roll of the present invention by the method comprising the above-mentioned a) to e), the supporting substrate used in the step of a) is a film-shaped substrate, such as a resin film substrate, a steel wire Substrate (such as SUS tape). As a resin film base material, there exists a polyethylene terephthalate (PET) film, for example. The thickness of the supporting substrate is not particularly limited, for example, it is 10-500 μm, preferably 100-200 μm.

In the drying step of b), it is preferable to remove at least a part of the solvent in the resin varnish by drying. In the film reel of the present invention, the solvent content of the transparent resin film is not less than 0.1% by mass of the total mass of the transparent resin film. In terms of preventing uneven peeling, preventing damage, production efficiency and safety, etc., Drying is preferably performed so that the amount of the solvent is preferably 0.1% by mass to 20% by mass, more preferably 2% by mass to 15% by mass.

Drying for removing the solvent can be performed by natural drying, ventilation drying, heat drying, or reduced pressure drying, and combinations thereof. From the viewpoints of production efficiency and the like, heat drying is preferable. Drying conditions can be appropriately determined according to the type of solvent used and the content in the transparent resin film within the range that does not damage the optical properties of the film. For example, it can be heated at a temperature of 50 to 230° C., preferably 100 to 210° C., for about 5 to 60 minutes.

Then, in the step of c), the protective film is bonded to the transparent resin film and the supporting substrate in such a manner that at least one end in the width direction of the protective film is located on the inside of at least one end in the width direction of the transparent resin film On the opposite side, a layered film in which a transparent resin film is formed on a support base and a protective film is further laminated on the transparent resin film is obtained. Thereafter, the support substrate is peeled off from the layer of the transparent resin film to obtain a laminated film in which a protective film is bonded to the transparent resin film. The film roll of the present invention can be obtained by winding this laminated film around a core in the form of a roll. It is also possible to carry out a further drying step (baking step) for removing the solvent or to improve the smoothness of the transparent resin film after the film roll of the present invention obtained by the above method is unwound. The step of surface modification (tentering step).

The polyimide or polyamide-based transparent resin film obtained by unwinding the laminated film from the film roll of the present invention and peeling the protective film from the transparent resin film suppresses uneven peeling when the protective film is peeled off, and has High transparency and good appearance, so it can be used especially for optical purposes. [Example]

Hereinafter, the present invention will be further described in detail with examples. Unless otherwise specified, "%" and "parts" in examples are mass % and mass parts.

Example 1 (1) Preparation of film roll Polyimide ("KPI-MX300F" manufactured by Kawamura Sangyo Co., Ltd.) was prepared. This polyimide was dissolved in a mixed solvent of N,N-dimethylacetamide (DMAc) and γ-butyrolactone (GBL) at a mass ratio of 9:1 to prepare a resin varnish (concentration: 20% by mass) . The obtained resin varnish was coated with a width of 870 mm on a strip-shaped polyethylene terephthalate (PET) film substrate with a thickness of 188 μm and a width of 900 mm by a casting method to form a film. The resin varnish to be filmed is passed through a furnace with a length of 12 m at a linear speed of 0.4 m/min, and the temperature is set from 70°C to 120°C in stages, thereby removing the solvent from the resin varnish and forming Transparent resin film (thickness 80 μm). Thereafter, align the center of the width direction of the transparent resin film with the center of the width direction of the protective film, and place the protective film ("N711" manufactured by Toray Film Processing Co., Ltd., a polyethylene protective film with weak adhesive force, the width : 830 mm) is attached to the surface of the transparent resin film and the PET film base material in such a way that the two ends of the protective film in the width direction are respectively located 20 mm inside from the ends of the width direction of the transparent resin film. Opposite side. The film-shaped laminate composed of the obtained protective film, transparent resin film, and PET film substrate was wound up on a roll core to form a roll. Thereafter, the PET film substrate was peeled off while unwinding the roll-shaped laminate, and the laminate composed of a transparent resin film and a protective film was wound up to obtain a film roll.

(2) Evaluation of uneven peeling After peeling off the protective film from the film roll obtained in said (1), and drying (baking) at 200 degreeC for 15 minutes, peeling unevenness was evaluated by the following method. Irradiate POLARION LIGHT ["PS-X1" manufactured by POLARION] (3,400 lumens) from the direction of travel (that is, vertical direction). At this time, irradiate the film surface at a tilting angle of about 20-70°. The viewing direction is approximately directly above the surface of the resin film to be evaluated (at an angle of 90° from the surface of the resin film), and the evaluation is performed with the naked eye.

＜Evaluation criteria for uneven peeling＞ ◯: Peeling unevenness was not confirmed. ×: Peeling unevenness was confirmed.

<Amount of solvent in transparent resin film> Peel off the protective film from the film roll obtained in (1) above, measure the total mass of the transparent resin film immediately, then measure the amount of solvent contained in the transparent resin film, and obtain the solvent relative to the total mass of the transparent resin film The content (mass%). In addition, content (mass %) of the solvent with respect to the gross mass of a transparent resin film was calculated|required as mass change rate L (%) by the following method.

TG/DTA6300 manufactured by Hitachi-hitec-science Co., Ltd. was used as a thermogravimetry-differential calorimetry (TG-DTA) measurement device. A sample of about 20 mg was obtained from the prepared transparent resin film. The sample is heated from room temperature to 120°C at a heating rate of 10°C/min, and kept at 120°C for 5 minutes, then heated to 400°C at a heating rate of 10°C/min while measuring The mass change of the sample.

Based on the measurement results of the mass change of the sample measured by TG-DTA, the mass loss rate L (%) from 120°C to 250°C was calculated by the following formula. L(%)=100-(W ₁ /W ₀ )×100 Here, W ₀ represents the mass of the sample kept at 120°C for 5 minutes, and W ₁ represents the mass of the sample at 250°C.

Embodiment 2～6 and comparative example 1～6 As the thickness and width of the transparent resin film, the thickness, width and type of the protective film, and the solvent, those shown in Table 1 were used respectively, and the protective film and the transparent resin film were not overlapped at the length of the end shown in Table 1. A film roll was produced in the same manner as in Example 1 except that the film was bonded together in the same manner as in Example 1. The protective film was peeled off from the obtained film roll, and the peeling nonuniformity at the time of drying (baking) based on the conditions described in Table 1 was evaluated. Furthermore, the lamination of the transparent resin film and the protective film is to align the center of the width direction of the transparent resin film with the center of the width direction of the protective film, and make the two ends of the width direction of the protective film be located at a distance from the transparent resin film. The ends in the width direction of the film are bonded to the inside of the same length. The results are shown in Table 1. In addition, the protective film "25-MK01" used in Example 4 and Example 6 is a polypropylene (PP) film "trade name Torayfan (registered trademark)" manufactured by Toray Co., Ltd., and the protective film used in Example 5 The protective film "ForceField" is a polyethylene film "ForceField 1035" manufactured by Tredegar Film Products, and "7832C" used in Comparative Examples 1 to 4 is a polyethylene (PE) film manufactured by Toray Film Processing Co., Ltd. "Product name Tretec (registered trademark)".

Example 7 (1) Preparation of silica sol Amorphous silica sol with a BET (Brunauer-Emmett-Teller, Buert) diameter (average primary particle diameter measured by the BET method) of 27 nm produced by the sol-gel method was used as a raw material. A γ-butyrolactone (hereinafter, sometimes referred to as GBL) substituted silica sol was prepared by solvent substitution. The obtained sol was filtered through a membrane filter with a mesh size of 10 μm to obtain a GBL-substituted silica sol. The silica particles of the obtained GBL-substituted silica sol were all 30 to 32% by mass.

(2) Preparation of resin varnish Mix the same polyimide (KPI-MX300F) as the user in Example 1 and the GBL-substituted silica sol obtained above with γ-butyrolactone (GBL) to prepare a resin varnish (polyimide and the total concentration of silica particles is 10% by mass). The amount of GBL-substituted silica sol used was adjusted so that the mass ratio of polyimide to silica particles in the GBL-substituted silica sol was 60:40.

(3) Preparation of film roll Use the resin varnish obtained above to replace the resin varnish used in Example 1, the thickness and width of the transparent resin film, and the thickness, width and type of the protective film are set as recorded in Table 1, so that the protective film and the transparent resin film A film roll was produced in the same manner as in Example 1 except that the lengths of the ends shown in Table 1 were not overlapped. Furthermore, the lamination of the transparent resin film and the protective film is to align the center of the width direction of the transparent resin film with the center of the width direction of the protective film and make the two ends of the width direction of the protective film be located at a distance from the transparent resin film. The ends in the width direction are attached to the inner side of the same length. The results are shown in Table 1. Then, the protective film was peeled off from the obtained film roll, and the edge part of the film roll was held by the clip in the tenter process, and it dried at 200 degreeC for 9 minutes (drying). Thereafter, peeling unevenness was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 8 (1) Preparation of polyamideimide Add 25.000 kg of 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl (TFMB) and 321.035 kg of DMAc to the reactor equipped with stirring blades under nitrogen atmosphere While stirring at room temperature, TFMB was dissolved in DMAc. Next, 10.420 kg of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added to the flask, and it stirred at room temperature for 3 hours. Thereafter, 4,4'-oxybis(benzoyl chloride) (OBBC) 4.615 kg, followed by terephthaloyl chloride (TPC) 7.785 kg were added to the flask, and stirred at room temperature for 1 hour . Next, 4.945 kg of 4-picoline and 7.185 kg of acetic anhydride were added to the flask, and after stirring at room temperature for 30 minutes, the temperature was raised to 70° C. and further stirred for 3 hours to obtain a reaction liquid. The obtained reaction solution was cooled to room temperature, and was poured into a large amount of methanol in a linear form, and the precipitated precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Then, the precipitate was dried under reduced pressure at 100° C. to obtain transparent polyamideimide (molecular weight Mw in terms of polystyrene: 420,000).

(2) Preparation of film roll Use the polyamide imide obtained above to replace the polyimide (KPI-MX300F) used in Example 1, and set the thickness and width of the transparent resin film, and the thickness, width and type of the protective film as follows Except for the description in Table 1, a film roll was produced in the same manner as in Example 7. Then, the protective film was peeled off from the obtained film roll, and the edge part of the film roll was held by the clip in the tenter process, and it dried (baked) at 200 degreeC for 12 minutes. Thereafter, peeling unevenness was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 9 Use the polyamide imide obtained in Example 8 to replace the polyimide (KPI-MX300F) used in Example 7, and set the thickness and width of the transparent resin film, and the thickness, width and type of the protective film. A film roll was produced in the same manner as in Example 7 except that it was as described in Table 1. Then, the protective film was peeled off from the obtained film roll, and the end part of the film roll was held by clips in the tenter process, and it dried (baked) at 200 degreeC for 13 minutes. Thereafter, peeling unevenness was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Table 1]

1‧‧‧Film reel 2‧‧‧Transparent resin film 2a‧‧‧Transparent resin film end 3‧‧‧Protective film 3a‧‧‧Protective film end 4‧‧‧Laminated film 5‧‧‧Reel

Fig. 1 is a schematic diagram of a section cut from the outside of the film roll toward the core in the width direction of the film roll in the film roll of the present invention.

Claims (6)

A film roll, which is wound with a film comprising the following: a transparent resin film comprising at least 1 selected from the group consisting of polyimide, polyamide and polyamideimide A resin composition; and a protective film, which is attached to the above-mentioned transparent resin film; the above-mentioned transparent resin film contains a solvent of 0.1% by mass or more relative to the total mass of the transparent resin film, and at least One end portion is located on the inner side than the end portion in the width direction of the above-mentioned transparent resin film. The film roll according to claim 1, wherein both ends of the protective film in the width direction are located on the inner side than the ends of the transparent resin film in the width direction. The film roll according to claim 1 or 2, wherein the length of the protective film in the width direction is 90-99% of the length of the transparent resin film in the width direction. The film roll according to claim 1 or 2, wherein the transparent resin film contains more than one solvent, and the solvent with the highest boiling point among the solvents has a boiling point of 120-300°C. The film reel according to claim 1 or 2, wherein the transparent resin film contains at least one kind selected from N,N-dimethylacetamide, γ-butyrolactone, N-methylpyrrolidone, butyl acetate, Solvent in the group consisting of cyclopentanone and amyl acetate. The film roll according to claim 1 or 2, wherein the protective film is a polyolefin-based resin film.

Images