JP2007197590A - Method for producing film, and film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a film which can be produced by the melt film-forming process being operated with advantageous productivity, and has heat-resistance whereby various functional layers are formable at a high temperature. <P>SOLUTION: The film having a glass transition temperature of ≥250°C, is formed by the followings. After forming a coating film by melt film-forming of a mixture of a polymer having a glass transition temperature of ≥250°C with a curable plasticizer, the coating film by the melt film-forming is cured. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a film having excellent heat resistance and a film produced by the production method.

  When a film made of an organic polymer is formed, the film is generally formed by giving a molten state by applying a temperature equal to or higher than the heat distortion temperature or the melting point, and discharging it from the die as a molten film. In contrast, a polymer having a heat distortion temperature or melting point close to the decomposition temperature, or a heat distortion temperature or melting point higher than the decomposition temperature, starts or advances simultaneously with melting, so the polymer is dissolved in an appropriate solvent, The obtained solution is cast on a support and then formed into a film by a solution casting method in which the solvent is removed. Examples of such a polymer include cellulose triacetate, aromatic polyamide, and aromatic polyimide. However, the film obtained by the solution casting method may be advantageous in terms of film properties such as surface smoothness as compared with the film obtained by melt casting, but it is disadvantageous in productivity because it takes time to remove the solvent. There are many cases.

  In recent years, in the field of flat panel displays such as liquid crystal display elements and organic electroluminescence elements (hereinafter referred to as “organic EL elements”), the substrate is replaced from glass to plastic in order to improve breakage resistance, reduce weight, and reduce thickness. Is being considered. In particular, there is a strong demand for a plastic substrate in a display device for mobile information communication equipment such as a portable information terminal such as a mobile phone, an electronic notebook, or a laptop personal computer.

  In order to impart conductivity to the plastic substrate, a semiconductor film such as an oxide of indium oxide, tin oxide or tin-indium alloy; a metal film such as an oxide film of gold, silver or palladium alloy; or the semiconductor film and the Studies have been made to form a transparent conductive layer combined with a metal film on a plastic substrate. In addition, various functionalizations such as liquid crystal alignment layers and TFTs are being studied. In either case, high heat resistance and transparency are required for plastic substrates.

  Patent Documents 1 and 2 describe a transparent conductive film using a polyimide having an alicyclic structure and a thin film transistor substrate. The polyimide is excellent in transparency and exhibits high heat resistance with a glass transition temperature of 250 ° C. or higher. Moreover, it is excellent in the solubility with respect to the organic solvent with respect to a general wholly aromatic polyimide, and is suitable for solution film forming.

  Patent Document 3 discloses 6,6′-dihydroxy-4,4,4 ′, 4 ′, 7,7′-hexamethyl-2,2′-spirobichroman (hereinafter also referred to as “spirobichromandiol”). And polyester films derived from isophthalic acid and terephthalic acid. The polyester is excellent in transparency and can form a film having excellent mechanical properties rich in flexibility, and the film exhibits a high heat resistance with a glass transition temperature of 250 ° C. or higher. Further, the film is excellent in solubility in a low boiling point solvent such as dichloromethane, and is suitable for solution film formation.

  Patent Document 4 describes a polyester film derived from 9,9-bis (4-hydroxyphenyl) fluorene (hereinafter also referred to as “bisphenolfluorene”), isophthalic acid and terephthalic acid. Patent Document 5 describes a polyester film derived from alkyl-substituted bisphenolfluorene, isophthalic acid and terephthalic acid. Furthermore, Patent Document 6 describes a polyester film derived from bisphenolfluorene in which the ortho position of phenol is substituted with halogen or the like. Polyesters derived from these substituted or unsubstituted bisphenolfluorenes and isophthalic acid and terephthalic acid all have a glass transition temperature (Tg) of around 300 ° C. or higher, and are flexible with excellent transparency and elongation at break. Film is produced. Moreover, it is excellent in solubility in low boiling point solvents such as dichloromethane, and is suitable for solution film formation.

Many studies have been made on the use of a film made of a polymer having excellent transparency and heat resistance as a plastic substrate as described above, all of which are formed by solution casting, and the melt casting method is known. Not.
JP 2003-141936 A (Claims) JP 2003-168800 A (Claims) Japanese Patent Laid-Open No. 11-302364 (Claims) JP-A-3-28222 (Claims) International Publication No. WO99 / 18141 (claim) JP 2002-145998 A (Claims)

  The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a heat-resistant film that can be produced by melt film formation with an advantage in productivity and can form various functional layers at high temperatures. It is in providing the manufacturing method and the film manufactured by this manufacturing method.

As a result of diligent studies to achieve the above object, the present inventors have found a production method capable of producing a heat-resistant film capable of forming various functional layers at high temperatures using a melt film-forming method with high productivity. The invention has been completed.
That is, the said subject of this invention is achieved by the following means.

(1) A glass transition temperature of 250 ° C. or higher is obtained by melt-forming a mixture of a polymer having a glass transition temperature of 250 ° C. or higher and a curable plasticizer to form a coating film, and curing the melt-formed coating film. The manufacturing method of the film characterized by including the process of manufacturing this film.

(2) A repeating unit containing a spiro structure represented by the following general formula (1) or a cardo structure represented by the following general formula (2), or a repeating unit represented by the following general formula (8) (1) The method for producing a film according to (1).

［一般式（１）中、環αは単環式または多環式の環を表し、２つの環αはそれぞれ同じであっても異なっていてもよい。２つの環αは、スピロ結合により連結されている。］

[In general formula (1), ring α represents a monocyclic or polycyclic ring, and the two rings α may be the same or different. The two rings α are connected by a spiro bond. ]

［一般式（２）中、環βおよび環γは、単環式または多環式の環を表し、２つの環γはそれぞれ同じであっても異なっていてもよい。２つの環γは、環β上の１つの４級炭素に連結されている。］

[In general formula (2), ring β and ring γ represent a monocyclic or polycyclic ring, and the two rings γ may be the same or different. Two rings γ are linked to one quaternary carbon on ring β. ]

［式中、Ｙは単環式もしくは縮合多環式の４価の脂肪族基を表し、Ｘは単環式もしくは縮合多環式の芳香族基、または、単環式もしくは縮合多環式の脂肪族基を含有し、構成する炭素原子数が４〜３０である２価の連結基を表す。］

[Wherein Y represents a monocyclic or condensed polycyclic tetravalent aliphatic group, X represents a monocyclic or condensed polycyclic aromatic group, or a monocyclic or condensed polycyclic aromatic group. A divalent linking group containing an aliphatic group and comprising 4 to 30 carbon atoms is represented. ]

(3) The curable plasticizer is a compound having two or more of a cyanate group, a maleimide group, and an acryloyl group represented by the following structure in the molecule. A method for producing a film.

(4) The method for producing a film according to any one of (1) to (3), wherein the total light transmittance of the film is 70% or more.

(5) A film produced by the production method according to any one of (1) to (4).

  According to the present invention, by using a mixture of a polymer having a glass transition temperature of 250 ° C. or higher and a curable plasticizer, a film having a glass transition temperature of 250 ° C. or higher can be produced by a melt film forming method with excellent productivity. A film production method and a film obtained by the production method can be provided.

  Hereinafter, the film manufacturing method and the film of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.

The method for producing a film of the present invention comprises forming a coating film by melting a mixture of a polymer having a glass transition temperature of 250 ° C. or higher and a curable plasticizer to form a coating film. It includes a step of producing a film having a transition temperature of 250 ° C. or higher.
The polymer having a glass transition temperature of 250 ° C. or higher that can be used in the present invention (hereinafter also referred to as “polymer in the present invention”) may be a thermoplastic resin or a curable resin, and if the glass transition temperature is 250 ° C. or higher. There is no particular limitation. On the other hand, as an aspect of the film of the present invention, the total light transmittance is preferably 70% or more. In this case, it is preferable that the polymer itself in the present invention is substantially colorless and transparent. Preferable examples of the polymer in the present invention include fluorine-containing polyimide, polyimide having an alicyclic structure, polyarylate and polyamide having a rigid linking group, and particularly preferably represented by the following general formula (1). Examples thereof include a polymer having a repeating unit containing a spiro structure or a cardo structure represented by the general formula (2) or a repeating unit represented by the following general formula (8).

［一般式（１）中、環αは単環式または多環式の環を表し、２つの環αはそれぞれ同じであっても異なっていてもよい。２つの環αは、スピロ結合により連結されている。］

[In general formula (1), ring α represents a monocyclic or polycyclic ring, and the two rings α may be the same or different. The two rings α are connected by a spiro bond. ]

［一般式（２）中、環βおよび環γは、単環式または多環式の環を表し、２つの環γはそれぞれ同じであっても異なっていてもよい。２つの環γは、環β上の１つの４級炭素に連結されている。］

[In general formula (2), ring β and ring γ represent a monocyclic or polycyclic ring, and the two rings γ may be the same or different. Two rings γ are linked to one quaternary carbon on ring β. ]

The ring α in the general formula (1) represents a monocyclic or polycyclic ring, for example, an indane ring, a chroman ring, a 2,3-dihydrobenzofuran ring, an indoline ring, a tetrahydropyran ring, a tetrahydrofuran ring, or a dioxane ring. , Cyclohexane ring, cyclopentane ring and the like. The two rings α may be the same or different.
Further, the two rings α are connected by a spiro bond. Preferable examples of the polymer having a repeating unit containing a spiro structure represented by the general formula (1) include a polymer having a repeating unit containing a spirobichroman structure represented by the following general formula (3). it can.

The ring β in the general formula (2) represents a monocyclic or polycyclic ring. For example, a fluorene ring, a 1,4-bibenzocyclohexane ring, an indandione ring, an indanone ring, an indene ring, an indane ring. A ring, a tetralone ring, an anthrone ring, a cyclohexane ring, and a cyclopentane ring.
The ring γ in the general formula (2) represents a monocyclic or polycyclic ring. For example, a phenylene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a cyclohexane ring, a cyclopentane ring, a pyridine ring, a furan ring, a benzofuran Examples include a ring, a thiophene ring, a benzothiophene ring, a benzothiazole ring, an indane ring, a chroman ring, an indole ring, and an α-pyrone ring.
The ring β includes a quaternary carbon atom, and the ring β and the two rings γ are connected by the quaternary carbon atom. The two rings γ may be the same or different from each other. Moreover, as a preferable example of the polymer which has a repeating unit containing the cardo structure represented by General formula (2), the polymer which has a repeating unit containing the fluorene structure represented by following General formula (4) can be mentioned. .

In the general formula (3), R ⁴¹ represents a hydrogen atom or a substituent. R ⁴² represents a substituent. In addition, each may be linked to form a ring. m and n represent an integer of 1 to 3. Preferred examples of the substituent are a halogen atom, an alkyl group, and an aryl group. More preferred examples of R ⁴¹ are hydrogen atom, methyl group, and phenyl group, and more preferred examples of R ⁴² are hydrogen atom, chlorine atom, bromine atom, methyl group, isopropyl group, t-butyl group, and phenyl group. .

In the general formula (4), R ⁶¹ represents a hydrogen atom or a substituent. R ⁶² represents a substituent. In addition, each may be linked to form a ring. j and k represent an integer of 1 to 4. Examples of preferred substituents are a halogen atom, an alkyl group, and an aryl group. More preferred examples of R ⁶¹ and R ⁶² are a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an isopropyl group, a t-butyl group, and a phenyl group.

  The polymer containing the structure represented by the general formulas (1) to (4) in the repeating unit may be a polymer linked by various bonding methods such as polycarbonate, polyester, polyamide, polyimide, polyurethane, etc. Polyesters derived from bisphenol compounds having structures represented by formulas (1) to (4) are preferred from the viewpoints of heat resistance and transparency.

  Preferred examples of polyesters derived from bisphenol compounds having the structures represented by the general formulas (1) to (4) (hereinafter also referred to as “polyesters in the present invention”) include the following general formulas (5) or (6). The polyester which has a repeating unit represented by these can be mentioned.

In general formula (5), ring β represents a ring which may have a monocyclic or polycyclic substituent. Preferred ring β is a polycyclic ring containing at least one aromatic ring. Examples of the monocyclic or polycyclic ring include the rings exemplified as the ring β in the general formula (2). Preferred substituents on the ring β are an alkyl group, an aryl group, and a halogen atom, and more preferred examples include a chlorine atom, a bromine atom, a methyl group, an isopropyl group, a tert-butyl group, and a phenyl group.
In General Formula (5), L represents a divalent linking group composed of a hydrocarbon which may have a substituent. Preferred L is alkylene or arylene. Preferable examples of alkylene include alkylene having an alicyclic structure. Among these, as said L, an arylene connection is especially preferable. Examples of the arylene include phenylene, naphthalene, and biphenylene. Moreover, as a preferable substituent of the said arylene connection, an alkyl group, an aryl group, and a halogen atom are mentioned, More preferably, they are a methyl group, a chlorine atom, and a bromine atom.

Moreover, since the transparency improves by making it the copolymer of the 2 or more types of repeating unit from which L differs, the polyester which has a repeating unit represented by General formula (5) is especially preferable. A preferable combination of different L includes a combination of paraphenylene and metaphenylene; a combination of two or more selected from three types of paraphenylene, 2,6-naphthalene, and 4,4′-biphenylene.
In the general formula (5), R ¹ and R ² each represent a substituent, and preferred substituents include an alkyl group, an aryl group, and a halogen atom, and more preferably a chlorine atom, a bromine atom, and a methyl group. , An isopropyl group, a tert-butyl group, and a phenyl group. Moreover, in general formula (5), l and m represent the integer of 0-4.

  In general formula (6), ring α represents a ring which may have a monocyclic or polycyclic substituent, and the two rings are connected by a spiro bond. Examples of the monocyclic or polycyclic ring represented as the ring α include the rings exemplified as the ring α in the general formula (1). In General Formula (6), L represents a divalent linking group composed of a hydrocarbon which may have a substituent. Preferred L is alkylene or arylene. Preferable examples of alkylene include alkylene having an alicyclic structure. Among these, as said L, an arylene connection is especially preferable. Examples of the arylene include phenylene, naphthalene, and biphenylene. Moreover, as a preferable substituent of an arylene connection, an alkyl group, an aryl group, and a halogen atom are mentioned, More preferably, they are a methyl group, a chlorine atom, and a bromine atom.

Moreover, since the transparency improves by using as a copolymer of 2 or more types of repeating units from which L differs, the polyester which has a repeating unit represented by General formula (6) is especially preferable. As a preferred combination of different L, there can be mentioned a combination of paraphenylene and metaphenylene; a combination selected from two or more of three kinds of paraphenylene, 2,6-naphthalene and 4,4′-biphenylene.
In the general formula (6), R ¹ and R ² each represent a substituent, and preferred substituents include an alkyl group, an aryl group, and a halogen atom, and more preferably a chlorine atom, a bromine atom, a methyl group, Examples include isopropyl group, tert-butyl group, and phenyl group. Moreover, in General formula (6), l and m represent the integer of 0-3.

  Furthermore, a preferable example of the repeating unit represented by the general formula (5) includes a repeating unit represented by the following general formula (7).

In General Formula (7), R ³ and R ⁴ each represent a substituent, and preferred substituents include an alkyl group, an aryl group, and a halogen atom. More preferred examples of the substituent include a chlorine atom, a bromine atom, a methyl group, an isopropyl group, a tert-butyl group, and a phenyl group. In general formula (7), j and k represent the integer of 0-4.
Moreover, L in General formula (7) represents the bivalent coupling group which consists of the hydrocarbon which may have a substituent. Preferred L is alkylene or arylene. Preferable examples of alkylene include alkylene having an alicyclic structure. Among these, as said L, an arylene connection is especially preferable. Examples of the arylene include phenylene, naphthalene, and biphenylene. Moreover, as a preferable substituent of the said arylene connection, an alkyl group, an aryl group, and a halogen atom are mentioned, More preferably, they are a methyl group, a chlorine atom, and a bromine atom.

Moreover, since the transparency improves by making it the copolymer of the 2 or more types of repeating unit from which L differs, the polyester which has a repeating unit represented by General formula (7) is especially preferable. As a preferred combination of different L, there can be mentioned a combination of paraphenylene and metaphenylene; a combination selected from two or more of three kinds of paraphenylene, 2,6-naphthalene and 4,4′-biphenylene.
In the general formula (7), R ¹ and R ² each represent a substituent, and preferred substituents include an alkyl group, an aryl group, and a halogen atom, and more preferably a chlorine atom, a bromine atom, and a methyl group. , An isopropyl group, a tert-butyl group, and a phenyl group. Moreover, in General formula (7), l and m represent the integer of 0-4.

  Preferred specific examples (PC-1) to (PS-8) of the polyester in the present invention are listed below, but the present invention is not limited thereto. In addition, the number of a repeating unit represents a copolymerization ratio (mol%), and a homopolymer is described as 100.

  Moreover, as a particularly preferable example of the polymer in the present invention, a polyimide containing an alicyclic structure having a repeating unit represented by the general formula (8) (hereinafter also referred to as “polyimide in the present invention”) can be given.

［式中、Ｙは単環式もしくは縮合多環式の４価の脂肪族基を表し、Ｘは単環式もしくは縮合多環式の芳香族基、または、単環式もしくは縮合多環式の脂肪族基を含有し、構成する炭素原子数が４〜３０である２価の連結基を表す。］

[Wherein Y represents a monocyclic or condensed polycyclic tetravalent aliphatic group, X represents a monocyclic or condensed polycyclic aromatic group, or a monocyclic or condensed polycyclic aromatic group. A divalent linking group containing an aliphatic group and comprising 4 to 30 carbon atoms is represented. ]

The Y is preferably a monocyclic or condensed polycyclic tetravalent aliphatic group having 4 to 30 carbon atoms, and more preferably a monocyclic having 6 to 20 carbon atoms. It is a cyclic or condensed polycyclic tetravalent aliphatic group.
X represents a divalent linking group containing 6 to 28 carbon atoms and containing an aromatic group, or a monocyclic or condensed polycyclic aliphatic group containing carbon atoms. Is preferably a divalent linking group of 4 to 20. More preferably, it is a divalent linking group containing 7 to 28 carbon atoms containing an aromatic group and a divalent linking group containing 4 to 12 carbon atoms containing a monocyclic aliphatic group. A linking group or a divalent linking group containing a condensed polycyclic aliphatic group and having 7 to 20 carbon atoms. Particularly preferred is a divalent linking group containing an aromatic group and having 12 to 28 carbon atoms.

  Examples of the ring structure of the monocyclic or condensed polycyclic aromatic group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyridine ring, pyrazine ring, benzofuran ring, carbazole ring, etc. A benzene ring and a naphthalene ring are preferable, and a benzene ring is particularly preferable. Examples of the ring structure of the monocyclic or condensed polycyclic aliphatic group include cyclobutane ring, cyclopentane ring, cyclohexane ring, bicycloheptane ring, bicyclooctane ring, tetracyclododecane ring, adamantane ring, diamantane A ring, a morpholine ring, and the like. Among them, a cyclopentane ring, a cyclohexane ring, a bicycloheptane ring, and a bicyclooctane ring are preferable.

  In general formula (8), Y and X may be composed of one ring structure described above, or may have a plurality of ring structures. In the case of having a plurality of ring structures, the plurality of ring structures may be linked by a single bond or may be linked by a group (carbonyl, methylene, ether, etc.) that links the rings. In order to obtain a polyimide having a high Tg and good film properties, biphenyl or terphenyl in which two or more benzene rings are directly bonded is particularly preferable.

Specific examples of Y are given as tetracarboxylic dianhydrides.
For example, (trifluoromethyl) pyromellitic acid, di (trifluoromethyl) pyromellitic acid, di (phenyl) pyromellitic acid, pentafluoroethyl pyromellitic acid, bis [3,5-di (trifluoromethyl) phenoxy] Pyromellitic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-tetracarboxydiphenyl ether, 2, 3 ', 3,4'-tetracarboxydiphenyl ether, 3,3', 4,4'-benzophenone tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetra Carboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 3,3 ′, 4,4′-tetracarboxydiphenylmethane, 3,3 ′, 4,4′- Tracarboxydiphenyl sulfone, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 5,5′-bis (trifluoromethyl) −3,3 ′, 4,4′-tetracarboxybiphenyl, 2,2 ′, 5,5′-tetrakis (trifluoromethyl) -3,3 ′, 4,4′-tetracarboxybiphenyl, 5,5 ′ -Bis (trifluoromethyl) -3,3 ', 4,4'-tetracarboxydiphenyl ether, 5,5'-bis (trifluoromethyl) -3,3', 4,4'-tetracarboxybenzophenone, bis ( 3,4-dicarboxyphenoxy) tetrakis (trifluoromethyl) benzene, 3,4,9,10-perylenetetracarboxylic acid, 2,2-bis [4- (3,4-di Ruboxyphenoxy) phenyl] propane, cyclobutanetetracarboxylic acid, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane, bis (3,4-dicarboxyphenyl) dimethylsilane, 1 , 3-bis (3,4-dicarboxyphenyl) tetramethyldisiloxane, difluoropyromellitic acid, 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene, 1,4-bis (3 , 4-dicarboxytrifluorophenoxy) octafluorobiphenyl, pyrazine-2,3,5,6-tetracarboxylic acid, pyrrolidine-2,3,4,5-tetracarboxylic acid, thiophene-2,3,4,5 -Tetracarboxylic acid, bicyclo [2.2.1] hepta-2,3,5,6-tetracarboxylic Acid, 1,2,3,4-cyclopentanetetracarboxylic acid, bicyclo [2.2.2] octa-2,3,5,6-tetracarboxylic acid, tetracyclo [6.2.1.1.1 ^3,6 such .0 ^2,7] dodecane -4,5,9,10- tetracarboxylic acid.

Specific examples of X are given as diamines.
Examples of aromatic diamines include p-phenylenediamine, benzidine, o-tolidine, m-tolidine, bis (trifluoromethyl) benzidine, octafluorobenzidine, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 3,3′- Difluoro-4,4′-diaminobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4, , 4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenyl) Noxy) phenyl] sulfone, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, 1 , 3-bis (4-aminophenoxy) benzene, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-diaminobenzophenone, m- Examples include phenylenediamine, o-phenylenediamine, 3,3′-diamino-diphenyl ether, 3,3′-diamino-biphenyl, 9,9-bis (4-aminophenyl) fluorene, and the like. Examples of the aliphatic diamine include 1,4-diaminocyclohexane, piperazine, methylene diamine, ethylene diamine, 2,2-dimethyl-propylene diamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, 3 ( 4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.0] decane and the like.

  From the viewpoint of improving the glass transition temperature (Tg) of the polyimide in the present invention, it is particularly preferable to use a rigid aromatic diamine as the diamine component.

  Here, the “rigid aromatic diamine” does not include a bending group such as an ether group, a methylene group, a 2,2-propylidene group, a hexafluoropropylidene group, a cyclohexylidene group, and a carbonyl group in the main chain, Since the bond angle of the main chain does not change, it means a diamine having low mobility. Examples of rigid aromatic diamines include p-phenylenediamine, benzidine, o-tolidine, m-tolidine, bis (trifluoromethyl) benzidine, octafluorobenzidine, 3,3′-dimethyl-4,4′-diamino. Biphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 3,3′-difluoro-4,4′-diaminobiphenyl, m-phenylene Examples thereof include diamine, o-phenylenediamine, and 3,3′-diamino-biphenyl. These can be used alone or in combination of two or more.

  On the other hand, flexible aromatic diamine is mentioned as diamine other than the said rigid aromatic diamine. “Flexible aromatic diamine” means an ether group, a methylene group, a 2,2-propylidene group, a hexafluoropropylidene group, a cyclohexylidene group, a carbonyl group, and the like in the main chain. It means a diamine containing. Examples of flexible aromatic diamines include 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4 , 4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-diaminodiphenyl ether, 3 , 4′-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2 -Bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-diamino Examples include benzophenone. If these flexible aromatic diamines are used, the Tg of the polyimide in the present invention tends to decrease, but it may be advantageous for transparency, and these may be used in combination in small amounts as necessary.

  Although the preferable specific example (P-01)-(P-15) of the polyimide in this invention is given to the following, this invention is not limited to this.

  The molecular weight of the polymer in the present invention is preferably 10,000 or more in terms of weight average molecular weight. More preferably, the weight average molecular weight is 20,000 to 300,000, and particularly preferably 30,000 to 150,000. When the molecular weight is 10,000 or more, the mechanical properties of the obtained molded product are advantageous when applied to a molded product such as a film. On the other hand, when the molecular weight is 300,000 or less, it is advantageous in terms of controlling the molecular weight in synthesis, and the viscosity of the solution is not too high, which is advantageous in handling. The viscosity corresponding to the molecular weight can be used as a guide.

  The polymer in the present invention may be a copolymer having a plurality of types of repeating units including the structures represented by the general formulas (1) to (8). Moreover, you may copolymerize well-known repeating units other than the repeating unit containing the structure represented by General formula (1)-(8) in the range which does not impair the effect of this invention.

  The total molar percentage of the repeating units including the structures represented by the general formulas (1) to (8) in the polymer in the present invention is preferably 40 to 100 mol%, and preferably 60 to 100 mol%. Is more preferable, and it is further more preferable that it is 80-100 mol%. When the polymer in this invention has multiple types of repeating units containing the structure represented by General formula (1)-(8), transparency may improve and it is preferable. In this case, the proportion of any one of them is preferably 5 to 95 mol%, more preferably 20 to 80 mol%, and particularly preferably 30 to 70 mol%. When the ratio of the repeating unit including the structures represented by the general formulas (1) to (8) in the polymer in the present invention is the above, it is advantageous from the viewpoints of heat resistance and solubility in addition to transparency.

The higher heat resistant temperature of the polymer in the present invention is preferably high, and the glass transition temperature by DSC measurement can be used as a guide. The glass transition temperature of the polymer in the present invention is 250 ° C or higher, more preferably 300 ° C or higher, particularly preferably 350 ° C or higher. Further, a case where a glass transition temperature is not substantially observed within a measurement range (for example, 420 ° C. or lower) is also preferable as the polymer in the present invention. The upper limit of the glass transition temperature of the polymer in the present invention is not particularly limited, but is the same as the measurement upper limit temperature when observable within the measurement range, and the measurement upper limit temperature is to avoid troubles on the apparatus such as deformation of the sample container. The temperature is preferably set to 500 ° C. or lower, and preferably 420 ° C. or lower.
Among the polymers having repeating units including the structures represented by the general formulas (1) to (8) contained in the polymer in the present invention, the structures represented by the general formulas (4), (7), and (8) are included. A polymer having at least one repeating unit is more preferable because of high heat resistance.

  In the present invention, a polymer having a glass transition temperature of 250 ° C. or higher is produced by mixing the polymer mentioned above with a curable plasticizer, forming a film by melting and forming a coating film, and then curing the coating film. Can do. Here, curing means that the crosslinking reaction of the crosslinkable functional group contained in the curable plasticizer is advanced.

  Here, the “curable plasticizer” is a compound having a crosslinkable functional group, and can be used without particular limitation as long as it has a plasticizing effect when mixed with the polymer in the present invention. Here, the “plasticizing effect” means that the glass transition temperature (Tg) of the polymer in the present invention is lowered by 10 ° C. or more. The kind of the curable plasticizer can be selected from general-purpose crosslinked resins, although the plasticizing effect varies depending on the kind of polymer used.

  As the kind of the cross-linked resin, various known ones can be used without particular limitation for both thermosetting resin and radiation curable resin.

  Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, silicone resin, diallyl phthalate resin, furan resin, bismaleimide resin, cyanate resin and the like. In addition, the thermosetting resin can be crosslinked without particular limitation as long as it is a reaction that forms a covalent bond. For example, a urethane bond is formed using a polyalcohol compound and a polyisocyanate compound. A system in which the reaction proceeds at room temperature can also be used without particular limitation. However, such a system often has a problem of pot life before film formation, and is usually preferably used as a two-component mixed type in which a polyisocyanate compound is added immediately before film formation.

  On the other hand, when a system in which the reaction proceeds at room temperature is used as a one-component type, it is effective to protect the functional group involved in the crosslinking reaction, and it is also commercially available as a block type curing agent. Commercially available block type curing agents include "B-882N" manufactured by Mitsui Takeda Chemical Co., Ltd., "Colonate 2513" manufactured by Nippon Polyarylate Kogyo Co., Ltd. (block polyisocyanate), Mitsui Cytec Co., Ltd. “Cymel 303” (methylated melamine resin) and the like are known. Further, a blocked carboxylic acid such as the following B-1 that protects a polycarboxylic acid that can be used as a curing agent for an epoxy resin is also known.

The radiation curable resins can be broadly classified into radical curable resins and cationic curable resins.
As the curable component of the radical curable resin, a compound having a plurality of radical polymerizable groups in the molecule is used. Typical examples include compounds called polyfunctional acrylate monomers having 2 to 6 acrylate groups in the molecule, and a plurality of acrylics in the molecule called urethane acrylate, polyester acrylate, and epoxy acrylate. A compound having an acid ester group is used.

  As a typical curing method of the radical curable resin, there are a method of irradiating an electron beam and a method of irradiating ultraviolet rays. Usually, in the method of irradiating with ultraviolet rays, a polymerization initiator that generates radicals upon irradiation with ultraviolet rays is added. In addition, if the polymerization initiator which generate | occur | produces a radical by heating is added, it can also be used as a thermosetting resin.

  As the curable component of the cationic curable resin, a compound having a plurality of cationic polymerizable groups in the molecule is used. As a typical curing method, a method of adding a photoacid generator that generates an acid upon irradiation with ultraviolet rays and irradiating with ultraviolet rays for curing can be mentioned. Examples of the cationic polymerizable compound include a compound containing a ring-opening polymerizable group such as an epoxy group and a compound containing a vinyl ether group. In addition, if an acid generator which generates an acid by heating is added, it can also be used as a thermosetting resin.

  In the film of the present invention, a plurality of each of the thermosetting resins and radiation curable resins mentioned above may be mixed and used, or a thermosetting resin and a radiation curable resin may be used in combination. In addition, when the film thickness of the film of this invention exceeds 40 micrometers, the effect by a radiation may become difficult to advance. In this case, a thermosetting resin can be preferably used rather than a radiation curable resin.

The curable plasticizer that can be used in the present invention is a compound having a crosslinkable functional group and is not particularly limited as long as it has a plasticizing effect when mixed with the polymer in the present invention. It is preferable that it is larger, 2) excellent in compatibility with the polymer in the present invention, and 3) high Tg after curing.
1) As a plasticizing effect, when the polymer in the present invention is mixed at a mixing ratio described later, it is sufficient that the Tg can be lowered by 10 ° C. or more with respect to the polymer in the present invention. Is preferably 100 ° C. or higher, particularly preferably 150 ° C. or higher.
2) As for the compatibility with the polymer in the present invention, it is preferable that when mixed with the polymer in the present invention, white turbidity or the like accompanying remarkable phase separation is not observed, and it becomes substantially transparent.
3) As Tg after hardening, 250 degreeC or more is preferable, More preferably, it is 300 degreeC or more, Most preferably, it is 350 degreeC or more. Moreover, it is also preferable that the glass transition temperature is not substantially observed within the measurement range (for example, 420 ° C. or lower).

  From the above viewpoint, the curable plasticizer used in the present invention is more preferably a compound having two or more cyanate groups, maleimide groups, and acryloyl groups represented by the following structures in the molecule. Moreover, it is more preferable to have one or more aromatic rings in the molecule. Among them, a compound having two or more acryloyl groups in the molecule can be radically polymerized, and a colorless and transparent cured product can be obtained by adding a radical generator as required and curing.

  Preferred specific examples (BA-1) to (LC-9) of the curable plasticizer of the present invention are listed below, but the present invention is not limited thereto.

  In the method for producing a film of the present invention, the above-mentioned polymer and curable plasticizer are mixed and melt-formed to form a coating film, and then the coating film is cured to have a glass transition temperature of 250 ° C. or higher. The film can be manufactured. The mixture of the polymer and the curable plasticizer in the present invention (hereinafter also referred to as “mixture in the present invention”) is various known additives for improving the film properties in addition to the polymer and the curable plasticizer in the present invention. Can be used in combination. For example, when a metal oxide and / or a metal complex oxide and a metal oxide obtained by a sol-gel reaction are included, the heat resistance, solvent resistance, and mechanical strength of the film mentioned above are improved. Can do. Furthermore, resin modifiers such as plasticizers, dyes / pigments, antistatic agents, ultraviolet absorbers, antioxidants, inorganic fine particles, peeling accelerators, leveling agents, and lubricants as long as the effects of the present invention are not impaired as necessary. May be added.

  The proportion of the polymer in the present invention contained in the mixture in the present invention is 30 to 99% by mass, preferably 50 to 97% by mass, more preferably 60 to 95% by mass, still more preferably 70 to 93% by mass, particularly Preferably it is 80-90 mass%. Moreover, the ratio of the curable plasticizer contained in the mixture in this invention is 1-70 mass%, Preferably it is 3-50 mass%, More preferably, it is 5-40 mass%, More preferably, it is 7-30 mass%. Especially preferably, it is 10-20 mass%. By setting the ratio, the film of the present invention having good mechanical properties that are not brittle can be obtained.

Next, the melt film-forming process of the present invention and its conditions will be described.
The melt film forming step is a pre-heating of the polymer and the curable plasticizer in the present invention to a predetermined temperature in advance, and a kneading / extruding step for mixing additives to be added if necessary, a casting step, a stripping step, a stretching step, The film of the present invention is obtained through a relaxation process, a curing process, a cooling process, a winding process, a processing process, and the like. In the following, the melt film-forming technique of the present invention will be described.

1) Preheating of polymer and curable plasticizer in the present invention The polymer in the present invention is sufficiently dried in advance, and then charged into a hopper of a melt extruder. As preferable drying conditions, the water content in the polymer in the present invention is 0.5% by mass or less, more preferably 0.2% by mass, and particularly 0.1% by mass or less. As a result, hydrolysis of the polymer in the present invention that occurs during melting can be suppressed, and generation of foreign substances associated therewith can be suppressed. Such drying can be achieved by drying the polymer in the present invention preferably at 80 ° C. to 180 ° C. and preferably for 0.1 hour to 100 hours. This drying process may be performed in an air atmosphere, an inert gas (for example, nitrogen) atmosphere, or in a vacuum.

Further, the curable plasticizer may be introduced into the hopper simultaneously with the polymer in the present invention, or may be introduced with a delay. Further, a mixture of the polymer and the curable plasticizer in the present invention may be prepared in advance, and the mixture may be put into a hopper.
As a method for separately preparing the mixture before introducing the hopper, a method of dissolving the polymer and the curable plasticizer in the present invention in a solvent and then removing the solvent can be used. Thereby, a mixture can be produced at low temperature, and it can avoid that a curable plasticizer hardens | cures before a hardening process, and it is advantageous in suppressing gelatinization generation | occurrence | production. There is also a method in which a mixture with a polymer in the present invention containing a curable plasticizer at a high concentration (hereinafter also referred to as “masterbatch”) is prepared in advance, and then the polymer and masterbatch in the present invention are charged into a hopper. It can be preferably used. In this case, a solvent may be used as a method for preparing the masterbatch, but since melt kneading is possible at a lower temperature than directly mixing the polymer and the curable plasticizer in the present invention, a melt kneader or a melt extrusion is possible. It can also be produced using a machine. The heating temperature of the hopper preferably used in the present invention can be based on the glass transition temperature (Tg) of the polymer and masterbatch in the present invention and the mixture in the present invention. Heating to (Tg-50 ° C) to (Tg + 30 ° C), more preferably (Tg-40 ° C) to (Tg + 10 ° C), more preferably (Tg-30 ° C) to Tg with respect to the Tg of the polymer used. It is recommended to keep it.

2) Kneading / extrusion process The polymer and masterbatch in the present invention, the mixture in the present invention, the curable plasticizer heated in the preheating process using the kneading screw having a compression ratio of 2 to 15 installed in the melt extruder Etc. are kneaded at a desired melting temperature. The melting temperature in the kneading step needs to be arbitrarily selected as long as the kneading temperature can be sufficiently kneaded. In the present invention, it is also recommended to use a screw with a high compression ratio for the purpose of improving kneadability. A preferable compression ratio is 3 to 15, more preferably 4 to 12, and more preferably 5 to 10. It is common to melt at a compression ratio of less than 3.

  The melting temperature in the kneading / extrusion step may be a constant temperature, or may be performed at a melting temperature obtained by being divided into several parts and controlled. More preferably, the temperature on the upstream side (hopper side) is higher by 1 ° C. to 50 ° C. than the temperature on the downstream side (T-die side), more preferably 2 ° C. to 30 ° C., and even more preferably 3 ° C. to 20 ° C. In the present invention, the decomposition of the polymer and the generation of the gelled product can be further suppressed, which is preferable. Preferably, in order to efficiently perform the melting, the temperature of the upstream portion of the liquid feeding is set to a higher temperature, and after the melting, the temperature is lowered to suppress the decomposition of the polymer in the present invention. The kneading time is preferably 2 minutes to 60 minutes, more preferably 3 minutes to 40 minutes, and further preferably 4 minutes to 30 minutes. Furthermore, it is also preferable to carry out the inside of the melt extruder in an inert (nitrogen or the like) stream.

3) Casting process The melted and kneaded mixture in the present invention is passed through a gear pump to remove the pulsation of the extruder. Subsequently, it is preferable to perform filtration with a metal mesh filter or the like. The mesh size is preferably 2 to 30 μm, more preferably 2 to 20 μm, and still more preferably 2 to 10 μm. At this time, it is preferable to pressurize and shorten the time required for filtration as much as possible. The filtration pressure is preferably 0.5 MPa to 15 MPa, more preferably 2 Pa to 15 MPa, and particularly preferably 10 Pa to 15 MPa. A higher filtration pressure is preferable because the filtration time can be shortened, but it is preferable to use a high pressure within a range in which the filter is not damaged. The time required for filtration is preferably as short as possible. Filtration rate of the filter 1 cm ² per minute, preferably 0.05～100Cm ^3, more preferably 0.1~100cm ^3, 0.5~100cm ³ is particularly preferred.

  Next, the sheet is extruded in a sheet form onto a cooling drum conveyed from a film forming die (T-type), but it is preferable to extrude from a T-die controlled to a temperature lower than the melting temperature as described above. It is possible to divide the melt temperature into a plurality of different temperatures in the melt extruder, and in this case, the melt temperature closest to the T-die is used as a reference. Thereafter, as described above, a constant distance (preferably 1 to 50 cm) is maintained between the T-die and the casting drum. At this time, it is preferable to put in the casing so that the temperature fluctuation during this period is small. Furthermore, in the present invention, it is preferable that the temperature of the T-die is lower by 5 ° C to 30 ° C than the melting temperature. This is to prevent the polymer in the present invention from decomposing and scorching on the T-die and causing die lines. In normal film formation, it is common to level the generated die line by reducing the melt viscosity to the same temperature or higher from the melt kneader to the T-die, but gelation due to thermosetting occurs. In the case where the mixture in the present invention which is easy to melt is melt-cast, it is effective to lower the temperature as described above.

  Moreover, in order to eliminate the horizontal dan (stepwise unevenness generated in the width direction) of the film of the present invention, it is preferable in the present invention that the distance between the T-die and the casting drum be 2 cm to 50 cm. More preferably, they are 5 cm-40 cm, More preferably, they are 7 cm-35 cm. On the other hand, in order to prevent neck-in, it is preferable that the T-die and the casting drum be as close as possible, and adjustment can be made as necessary. The temperature of the casting drum can be set based on the Tg of the mixture in the present invention. Specifically, (Tg-30 ° C) to Tg are preferable, more preferably (Tg-20 ° C) to (Tg-1 ° C), and further preferably (Tg-15 ° C) with respect to Tg of the mixture in the present invention. ) To (Tg-2 ° C.).

  Extrusion may be performed in a single layer, or multiple layers may be extruded using a multi-manifold die or a field block die. Thereafter, the resin is extruded onto a casting drum having an appropriately selected diameter (preferably 10 to 200 cm), number (preferably 2 to 20) and temperature (preferably Tg-30 ° C.). At this time, it is preferable to use a method such as an electrostatic application method, an air knife method, an air chamber method, a vacuum nozzle method, or a touch roll method to increase the adhesion between the casting drum and the melt-extruded sheet. Such a method for improving adhesion may be performed on the front surface of the melt-extruded sheet or may be partially performed.

  Next, the molten mixture (coating film) in the present invention extruded from the T-die is conveyed by a casting drum. The mixture (coating film) in the present invention is cured by heating and becomes a film of the present invention. When curing by heat proceeds, the temperature on the casting drum can be adjusted and cured by heating for a desired time. Further, when stretching before curing, it may be peeled off from the casting drum and fixed with a tenter, and after stretching, it may be cured using hot air or an infrared heater. In the case of curing by radiation, the radiation may be irradiated on the casting drum or may be irradiated after peeling off.

  In this invention, the number of the preferable casting drum is 2-10, More preferably, it is 2-6, More preferably, it is 3-5. The temperature of these casting drums may be the same or different. The diameter of these casting drums is usually 20 cm to 200 cm. Further, the film forming speed is preferably 15 m / min to 300 m / min, more preferably 20 m / min to 200 m / min, and further preferably 30 m / min to 100 m / min. is there.

After curing, the film of the present invention is peeled off from the casting drum, passed through a nip roll, cut with a nip roll, and then wound with a winding tension of 0.01 kg / cm ^{2 to} 10 kg / cm ^2. preferably, more preferably ^{0.10kg / cm 2 ~9kg / cm 2} , more preferably from ^{0.10kg / cm 2 ~9kg / cm 2} . The winding speed is preferably 10 m / min to 100 m / min, more preferably 15 m / min to 80 m / min, still more preferably 20 m / min to 70 m / min.

  The sheet thus obtained is preferably trimmed at both ends and wound up. The trimmed portion is re-processed as a raw material for the same type of film or as a raw material for a film of a different type after being pulverized or subjected to processing such as granulation or depolymerization / repolymerization as necessary. May be used. In addition, it is also preferable from the viewpoint of scratch prevention to attach a laminate film on at least one surface before winding.

4) Drawing process It is good to implement extending | stretching by (Tg-50 degreeC)-(Tg + 50 degreeC) with respect to Tg of the film of this invention. A preferable draw ratio is 1% to 500%, more preferably 3% to 400%, and still more preferably 5% to 300%. These stretching operations may be performed in one stage or in multiple stages. The draw ratio here is determined using the following equation.
Stretching ratio (%) = 100 × {(length after stretching) − (length before stretching)} / length before stretching Such stretching is performed by using two or more pairs of nip rolls with increased peripheral speed on the outlet side. The film may be stretched in the longitudinal direction (longitudinal stretching), or both ends of the film may be held by a chuck (tenter) and spread in the orthogonal direction (perpendicular to the longitudinal direction) (lateral stretching). Generally, in any case, when the draw ratio is increased, the optical anisotropy is increased and the linear thermal expansion coefficient is lowered. Therefore, the drawing is performed as necessary.

  As described above, the film of the present invention is preferably manufactured continuously while being conveyed because of high productivity. On the other hand, in order to obtain a small scale film, it is also possible to perform batch production. In the case of batch production, a method in which a pre-cured film is obtained by press molding a mixture prepared in advance and then cured is preferred because it is simple. In addition, press molding may be used in combination with the above-mentioned continuous film formation for the purpose of improving the flatness of the film of the present invention or for the purpose of stretching.

  The thickness of the film of the present invention is not particularly defined, but is preferably 30 to 700 μm, more preferably 40 to 200 μm, and further preferably 50 to 150 μm. In any case, the haze is preferably 3% or less, more preferably 2% or less, and even more preferably 1% or less. Further, the total light transmittance is preferably 70% or more, more preferably 80% or more, and further preferably 85% or more.

  The heat resistant temperature of the film of the present invention is preferably high, and Tg by DSC measurement can be used as a guide. The Tg of the film of the present invention is 250 ° C. or higher, and the preferable Tg is 300 ° C. or higher, more preferably 350 ° C. or higher, and particularly preferably 400 ° C. or higher. In addition, when it is difficult to detect Tg by DSC, the thermal deformation temperature using TMA can also be handled as the glass transition temperature.

  The surface of the film of the present invention may be subjected to treatments such as saponification, corona treatment, flame treatment, glow discharge treatment, etc. on the surface of the film substrate in order to enhance adhesion with other layers or components depending on the application. it can. Furthermore, an adhesive layer and an anchor layer may be provided on the film surface. Depending on the purpose, smoothing layer for surface smoothing, hard coat layer for imparting scratch resistance, ultraviolet absorbing layer for enhancing light resistance, surface roughening layer for improving film transportability, etc. Various known functional layers can be provided.

(Transparent conductive layer)
The film of the present invention can be provided with a transparent conductive layer. As the transparent conductive layer, known metal films, metal oxide films, and the like can be applied. Among these, metal oxide films are preferable from the viewpoint of transparency, conductivity, and mechanical properties. For example, metal oxide films such as indium oxide, cadmium oxide and tin oxide added with tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium, etc. as impurities, zinc oxide, titanium oxide, etc. added aluminum as impurities Can be mentioned. Among them, an indium oxide thin film mainly composed of tin oxide and containing 2 to 15% by mass of zinc oxide is excellent in transparency and conductivity, and is preferably used.

  These transparent conductive layers can be formed by any method as long as the target thin film can be formed. For example, a material from the gas phase such as sputtering, vacuum deposition, ion plating, or plasma CVD can be used. For example, a vapor deposition method in which a film is deposited to form a film is suitable, and a film can be formed by the methods described in Japanese Patent No. 3400324, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002-361774. Among these, the sputtering method is preferable from the viewpoint that particularly excellent conductivity and transparency can be obtained.

  A preferable degree of vacuum of the sputtering method, vacuum deposition method, ion plating method, and plasma CVD method is 0.133 mPa to 6.65 Pa, more preferably 0.665 mPa to 1.33 Pa. Before providing such a transparent conductive layer, it is preferable to subject the base film to a surface treatment such as plasma treatment (reverse sputtering) or corona treatment. Moreover, you may heat up to 50-200 degreeC during providing the transparent conductive layer.

  The thickness of the transparent conductive layer is preferably 20 to 500 nm, and more preferably 50 to 300 nm.

  Further, the surface electrical resistance measured at 25 ° C. and 60% relative humidity of the transparent conductive layer is preferably 0.1 to 200Ω / □, more preferably 0.1 to 100Ω / □, 0.5 More preferably, it is ˜60Ω / □. The light transmittance of the transparent conductive layer is 80% or more, more preferably 83% or more, and still more preferably 85% or more.

(Gas barrier layer)
The film of the present invention is preferably provided with a gas barrier layer in order to suppress gas permeability. Preferred gas barrier layers include, for example, metal oxides composed mainly of one or more metals selected from the group consisting of silicon, aluminum, magnesium, zinc, zirconium, titanium, yttrium, and tantalum, silicon, aluminum, boron Metal nitrides or mixtures thereof. Among these, the main component is silicon oxide having a ratio of the number of oxygen atoms to the number of silicon atoms of 1.5 to 2.0 in terms of gas barrier properties, transparency, surface smoothness, flexibility, film stress, cost, and the like. Metal oxide is good.

  These inorganic gas barrier layers can be produced, for example, by a vapor deposition method in which a material is deposited in a vapor phase such as sputtering, vacuum deposition, ion plating, or plasma CVD to form a film. Among these, the sputtering method is preferable from the viewpoint that particularly excellent gas barrier properties can be obtained. Moreover, you may heat up to 50-200 degreeC during providing the gas barrier layer.

  The film thickness of the gas barrier layer is preferably 10 to 300 nm, more preferably 30 to 200 nm.

  The gas barrier layer may be provided on the same side or the opposite side as the transparent conductive layer, but is preferably provided on the opposite side.

Gas barrier film having a gas barrier layer, 40 ° C., preferably water vapor permeability measured at 100% relative humidity is 0~5g / m ² · day, it is 0~1g / m ² · day Is more preferably 0 to 0.5 g / m ² · day. Further, 40 ° C., the oxygen permeability measured at 90% relative humidity is preferably from ^{0~1ml / m 2 · day · atm} (0~1 × 10 5 ml / m 2 · day · Pa), 0~ It is more preferably 0.7 ml / m ² · day · atm (0 to 0.7 × 10 ⁵ ml / m ² · day · Pa), and 0 to 0.5 ml / m ² · day · atm (0 to 0.5 × 10 ⁵ ml / m ² · day · Pa) is more preferable.

(Defect compensation layer)
In the film of the present invention, it is preferable to provide a defect compensation layer adjacent to the gas barrier layer for the purpose of improving the barrier property. The defect compensation layer is (1) a method using an inorganic oxide layer produced by using a sol-gel method as described in US Pat. No. 6,171,663 and JP-A-2003-94572, and (2) US Pat. No. 6413645. As described in US Pat. Nos. 6,163,645, the organic layer can be used. Further, as described in the above-mentioned document, the defect compensation layer is prepared by a method of curing under ultraviolet light or electron beam after vacuum deposition, or a method of curing with heating, electron beam, ultraviolet light or the like after coating. It is preferable to do. When the coating method is used, various conventionally used coating methods such as spray coating, spin coating, and bar coating can be used.

[Image display element]
The film of the present invention can be used as a substrate for a thin film transistor (TFT) display element. Examples of the method for producing the TFT array include the method described in JP-T-10-512104. Further, these substrates may have a color filter for color display. The color filter may be produced by any method, but is preferably produced by a photolithography technique.

  The film of this invention can be used for an image display element, after providing various functional layers as needed. Here, it does not specifically limit as an image display element, A conventionally well-known thing can be used. Moreover, the flat panel display excellent in display quality can be produced using the film of this invention. Flat panel displays include liquid crystals, plasma displays, electroluminescence (EL), fluorescent display tubes, light-emitting diodes, etc. In addition to these, they are used as substrates that replace glass-type display substrates that have conventionally used glass substrates. be able to. Furthermore, the film of the present invention can be used for applications such as solar cells and touch panels. The solar cells are applied to those described in JP-A-9-148606, JP-A-11-288745, problems and countermeasures for the all-plasticization of new organic solar cells (2004, published by the Japan Society for Information Technology). it can. The touch panel can be applied to those described in JP-A-5-127822, JP-A-2002-48913, and the like.

  When the film of the present invention is used for liquid crystal display applications, it is preferably an amorphous polymer in order to achieve optical uniformity. The birefringence is preferably small, and the in-plane retardation (Re) is preferably 50 nm or less, more preferably 30 nm or less, and further preferably 15 nm or less. In order to obtain a film having a small birefringence, the cooling temperature during film formation can be adjusted as appropriate, or can be adjusted by stretching as necessary. Furthermore, for the purpose of controlling retardation (Re) and its wavelength dispersion, it is possible to combine resins and additives having different signs of intrinsic birefringence, or to combine resins and additives having large (or small) wavelength dispersion. . In addition, the film of the present invention can be suitably used for the purpose of controlling retardation (Re) and improving gas permeability and mechanical properties, such as lamination of different resins. Further, phase difference compensation can be performed by using a known retardation plate in combination.

  On the other hand, the film of the present invention can also be used as a retardation plate by controlling the optical anisotropy. In this case, the birefringence does not necessarily have to be small, and it is only necessary to have a desired birefringence. As a method for obtaining the desired birefringence, any known method such as stretching the film of the present invention, mixing a compound having birefringence, coating, or the like can be used.

  When used in a reflection type liquid crystal display device, it is composed of a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. Among these, the film of the present invention may be used as a λ / 4 plate, a protective film for a polarizing film, or other retardation plate (for example, a viewing angle compensation film) by adjusting optical characteristics. From the viewpoint of heat resistance, it is preferably used as a substrate, and from the viewpoint of transparency, it is preferably used as a transparent electrode and an upper substrate with an alignment film. Moreover, a gas barrier layer, TFT, etc. can also be provided as needed. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

  When used in a transmissive liquid crystal display device, the backlight, polarizing plate, λ / 4 plate, lower transparent electrode, lower alignment film, liquid crystal layer, upper alignment film, upper transparent electrode, upper substrate, λ / 4 are sequentially arranged from the bottom. It consists of a plate and a polarizing film. Of these, the film of the present invention may be used as a λ / 4 plate, a protective film for a polarizing film, or other retardation plate (for example, a viewing angle compensation film) by adjusting optical characteristics, but is a substrate from the viewpoint of heat resistance. And is preferably used as a transparent electrode and a substrate with an alignment film. Moreover, a gas barrier layer, TFT, etc. can also be provided as needed. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

  The liquid crystal cell is not particularly limited, but TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN (Supper Twisted Nematic) ), VA (Vertically Aligned) and HAN (Hybrid Aligned Nematic) have been proposed. In addition, a display mode in which the display mode is divided in orientation has been proposed. The film of the present invention is effective in any display mode liquid crystal display device. Further, it is effective in any of a transmissive type, a reflective type, and a transflective liquid crystal display device.

  These are JP-A-2-176625, JP-B-7-69536, MVA (SID97, Digest of tech. Papers (Preliminary Collection) 28 (1997) 845), SID99, Digest of tech. Papers (Preliminary Collection) 30. (1999) 206, JP-A-11-258605, SURVAIVAL (Monthly Display, Vol. 6, No. 3 (1999) 14), PVA (Asia Display 98, Proc. Of the-18th-Inter. Display res. Conf. (Preliminary Collection (1998) 383), Para-A (LCD / PDP Iternational`99), DDVA (SID98, Digest of tech. Papers (Preliminary Collection) 29 (1998) 838), EOC (SID98, Digest of tech Papers 29 (1998) 319), PSHA (SID98, Digest of tech. Papers 29 (1998) 1081), RFFMH (Asia Display 98, Proc. Of the-18th-Inter. Display res Conf. (Preliminary Collection) (1998) 375), HMD (SID98, Digest of tech. Papers (Preliminary Collection) 29 (1998) 702), JP-A-10-123478, International Publication W098 / 48320, Patent No. 3022477 And it is described in International Publication WO00 / 65,384 Patent Publication.

The film of the present invention is provided with a gas barrier layer and a TFT as necessary, and can be used for organic EL display applications as a substrate with a transparent electrode.
As a specific layer structure as the organic EL display element, anode / light emitting layer / transparent cathode, anode / light emitting layer / electron transport layer / transparent cathode, anode / hole transport layer / light emitting layer / electron transport layer / transparent cathode , Anode / hole transport layer / light emitting layer / transparent cathode, anode / light emitting layer / electron transport layer / electron injection layer / transparent cathode, anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron Examples include injection layer / transparent cathode.

  In the organic EL device in which the film of the present invention can be used, a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 40 volts) or a direct current is applied between the anode and the cathode. Thus, light emission can be obtained.

  Regarding driving of these organic EL elements, JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234665, and JP-A-8-241047. No. 5,828,429, US Pat. No. 6,023,308, Japanese Patent No. 2778415, etc. can be used.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Measurement method of characteristic values]
(1) Weight average molecular weight Using "HLC-8120GPC" manufactured by Tosoh Corporation, the weight average molecular weight was determined by polystyrene conversion GPC measurement using tetrahydrofuran as a solvent in comparison with a polystyrene molecular weight standard product.

(2) Glass transition temperature (Tg)
Using a “DSC6200” manufactured by Seiko Co., Ltd., the Tg of the polymer was measured by the DSC method (in nitrogen, at a heating temperature of 10 ° C./min) as follows.
First, a film sample (0.5 cm × 2.0 cm piece) was prepared, and the thermal deformation start temperature obtained by the tensile load method of TMA (manufactured by Rigaku Corporation, TMA8310) was measured under the condition of a tensile load of 100 mN. The glass transition temperature was measured.

(3) Film thickness Using “K402B” manufactured by Anritsu Corporation, the thickness of the film was measured with a dial-type thickness gauge.

(4) Total light transmittance of film The total light transmittance of the film was measured using the direct reading type | mold haze computer "HGM-2DP" by Suga Test Instruments.

[Comparative Example 1]
<BisA-I / T melt film formation>
The following “BisA-I / T” (weight average molecular weight: 73,000, Tg 206 ° C., white powder), which is a comparative polymer, is melted using a heating press machine (manufactured by Toyo Seiki Co., Ltd., Mini Test Press) according to the following procedure. Membrane was performed. The obtained film was a good film that had a thickness of 98 μm, Tg of 208 ° C., total light transmittance of 85%, colorless and transparent, and did not break even when wound around a cylinder having a diameter of 3 mm.

<Melt film-forming procedure using a heating press>
A commercially available polyimide film (trade name: Upilex 75S, manufactured by Ube Industries, Ltd.) on the substrate surface of a heating press machine (manufactured by Toyo Seiki Co., Ltd., mini test press) that has been heated to a film forming temperature (270 ° C.) in advance. And two copper plates with a thickness of 100 μm were installed with an interval of about 5 cm. About 1 g of “BisA-I / T” powder was piled in the center, and a commercially available polyimide film was placed thereon and pressed, and the state was maintained for 3 minutes. Thereafter, the pressure was increased to 30 MPa over 2 minutes, and the state was maintained for 3 minutes. Thereafter, the pressure was released and the “BisA-I / T” film sandwiched between the polyimide films was quenched with two copper plates. After standing for 30 minutes, the polyimide film was peeled off to obtain a BisA-I / T film.

[Example 1]
<PF-7 / BA-1 melt film formation>
Specific example (PF-7) (weight average molecular weight 55000, Tg 350 ° C., white powder) as a polymer in the present invention and the following “BA-1” as a curable plasticizer in a mass ratio of 75/25 Dissolved in 4 times the mass of dichloromethane of Example (PF-7). The solution was cast on a glass substrate and the solvent was removed by drying to obtain a PF-7 / BA-1 mixture in film form.
The Tg of the resulting mixture film measured using TMA was 220 ° C. The white powder obtained by pulverizing the mixture film was used in place of “BisA-I / T” in Comparative Example 1 and the film forming temperature was changed to 220 ° C. Carried out. The obtained mixture film was heated at 300 ° C. for 1 h under a nitrogen stream to obtain a PF-7 / BA-1 melt-cured film of the present invention. The obtained film was 99 μm thick, Tg 342 ° C., total light transmittance 78%, light yellow transparent, and was a good film that did not break even when wound around a cylinder with a diameter of 3 mm.

[Example 2]
<PF-7 / BM-1 melt film formation>
The above-described specific example (PF-7) (weight average molecular weight 55000, Tg 350 ° C., white powder) which is a polymer in the present invention and the following “BM-1” as a curable plasticizer in a mass ratio of 80/20 It was dissolved in N, N-dimethylacetamide having a mass 7 times that of “PF-7”. The solution was cast on a glass substrate and the solvent was removed by drying to obtain a PF-7 / BM-1 mixture in film form. The Tg of the PF-7 / BM-1 mixture film measured using TMA was 208 ° C.
The light yellow powder obtained by pulverizing the mixture film obtained as described above was used in place of “BisA-I / T” in Comparative Example 1, and the film forming temperature was changed to 200 ° C. Melt film formation was carried out according to the procedure. The obtained mixture film was heated at 250 ° C. for 1 h under a nitrogen stream to obtain a PF-7 / BM-1 melt-cured film of the present invention. The obtained film was a good film that had a thickness of 98 μm, Tg of 347 ° C., a total light transmittance of 74%, light yellow and transparent, and did not break even when wound around a cylinder with a diameter of 3 mm.

[Example 3]
<P-01 / BM-1 melt film formation>
Specific example (P-01) (weight average molecular weight 64000, Tg 390 ° C., white powder), which is a polymer in the present invention, and the above-mentioned “BM-1” as a curable plasticizer in a mass ratio of 80/20 It was dissolved in N, N-dimethylacetamide having a mass 7 times that of Example (P-01). The solution was cast on a glass substrate and the solvent was removed by drying to obtain a P-01 / BM-1 mixture in film form.
The T-01 of the P-01 / BM-1 mixture film measured using TMA was 201 ° C. A light yellow powder obtained by pulverizing the mixture film was used in place of “BisA-I / T” in Comparative Example 1, and the melt was made by the same procedure as Comparative Example 1 except that the film forming temperature was changed to 200 ° C. Membrane was performed. The obtained mixture film was heated at 250 ° C. for 1 h under a nitrogen stream to obtain a PF-7 / BM-1 melt-cured film of the present invention. The obtained film was 99 μm thick, Tg 372 ° C., total light transmittance 72%, light yellow transparent, and was a good film that did not break even when wound on a cylinder with a diameter of 3 mm.

[Example 4]
<PF-7 / LC-1 melt film formation>
The above-mentioned specific example (PF-7) (weight average molecular weight 55000, Tg 350 ° C., white powder) which is a polymer in the present invention and the following “LC-1” as a curable plasticizer at a mass ratio of 80/20 It was dissolved in 3 mass% of the following initiator NBC of (PF-7) in 4 times mass of dichloromethane of the specific example (PF-7). The solution was cast on a glass substrate and the solvent was removed by drying to obtain a PF-7 / LC-1 mixture in film form.
The Tg of the PF-7 / LC-1 mixture film measured using TMA was 180 ° C. The white powder obtained by pulverizing the mixture film was used in place of “BisA-I / T” in Comparative Example 1 and the film forming temperature was changed to 190 ° C. Carried out. The obtained mixture film was heated at 240 ° C. for 3 hours under a nitrogen stream to obtain a PF-7 / LC-1 melt-cured film of the present invention. The obtained film was 97 μm in thickness, Tg 338 ° C., total light transmittance 84%, colorless and transparent, and was a good film that did not break even when wound around a cylinder having a diameter of 3 mm.

[Example 5]
<P-01 / LC-1 melt film formation>
Specific example (P-01) (weight average molecular weight 64000, Tg 390 ° C., white powder) as a polymer in the present invention and the above-mentioned “LC-1” as a curable plasticizer in a mass ratio of 80/20 Along with 3% by mass of the initiator NBC of (P-01), it was dissolved in 2-butanone having a mass four times that of the specific example (P-01). The solution was cast on a glass substrate, and the solvent was removed by drying to obtain a P-01 / LC-1 mixture in the form of a film.
The Tg of the P-01 / LC-1 mixture film measured using TMA was 180 ° C. The white powder obtained by pulverizing the mixture film was used in place of “BisA-I / T” in Comparative Example 1 and the film forming temperature was changed to 190 ° C. Carried out. The obtained mixture film was heated at 240 ° C. for 3 hours under a nitrogen stream to obtain a P-01 / LC-1 melt-cured film of the present invention. The obtained film was a good film having a thickness of 99 μm, Tg of 360 ° C., a total light transmittance of 80%, light yellow and transparent, and did not break even when wound around a cylinder having a diameter of 3 mm.

[Comparative Example 2]
<PF-7 single melt film formation>
As the polymer in the present invention, the above-mentioned specific example (PF-7) (weight average molecular weight 55000, Tg 350 ° C., white powder) was used instead of “BisA-I / T” in Comparative Example 1, and the film forming temperature was 390 ° C. The melt film was formed in the same procedure as in Comparative Example 1 except that the pressure holding time was extended to 30 minutes. Although the obtained PF-7 film had a transparent part in some places, it became a state where the cloudy part and the brown part were mixed, and a good film was not obtained. The film was not evaluated because the film thickness unevenness was large, fragile and difficult to cut.

[Comparative Example 3]
<P-01 single melt film formation>
As the polymer in the present invention, the above-mentioned specific example (P-01) (weight average molecular weight 64000, Tg 390 ° C., white powder) was used instead of “BisA-I / T” in Comparative Example 1, and the film forming temperature was 390 ° C. The melt film was formed in the same procedure as in Comparative Example 1 except that the pressure holding time was extended to 30 minutes. The obtained P-01 film was in a state where a cloudy part having no transparent part and a brown part were mixed, and a good film could not be obtained. The film was not evaluated because the film thickness unevenness was large, fragile and difficult to cut.

  From the above results, the film production method of the present invention using the mixture of the polymer and the curable plasticizer in the present invention can produce a film having a high glass transition temperature by a melt film formation method. Furthermore, by carrying out continuous melt film formation, it is possible to produce a transparent film having heat resistance capable of installing various functional layers such as a display substrate with good productivity.

Claims (5)

  A mixture of a polymer having a glass transition temperature of 250 ° C. or higher and a curable plasticizer is melt-formed to form a coating film, and the melt-formed coating film is cured to form a film having a glass transition temperature of 250 ° C. or higher. The manufacturing method of the film characterized by including the process to manufacture. The polymer has a repeating unit including a spiro structure represented by the following general formula (1) or a cardo structure represented by the following general formula (2), or a repeating unit represented by the following general formula (8). The method for producing a film according to claim 1.

[In general formula (1), ring α represents a monocyclic or polycyclic ring, and the two rings α may be the same or different. The two rings α are connected by a spiro bond. ]

[In general formula (2), ring β and ring γ represent a monocyclic or polycyclic ring, and the two rings γ may be the same or different. Two rings γ are linked to one quaternary carbon on ring β. ]

[Wherein Y represents a monocyclic or condensed polycyclic tetravalent aliphatic group, X represents a monocyclic or condensed polycyclic aromatic group, or a monocyclic or condensed polycyclic aromatic group. A divalent linking group containing an aliphatic group and comprising 4 to 30 carbon atoms is represented. ] 3. The film production according to claim 1, wherein the curable plasticizer is a compound having two or more of a cyanate group, a maleimide group, and an acryloyl group represented by the following structure in the molecule. Method.

  The total light transmittance of the said film is 70% or more, The manufacturing method of the film of any one of Claims 1-3 characterized by the above-mentioned.   The film manufactured by the manufacturing method of any one of Claims 1-4.