CN109366827A - The manufacturing method of the manufacturing method of transparent resin film and the laminated body with transparent resin film - Google Patents
The manufacturing method of the manufacturing method of transparent resin film and the laminated body with transparent resin film Download PDFInfo
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- CN109366827A CN109366827A CN201811055864.8A CN201811055864A CN109366827A CN 109366827 A CN109366827 A CN 109366827A CN 201811055864 A CN201811055864 A CN 201811055864A CN 109366827 A CN109366827 A CN 109366827A
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- resin film
- transparent resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/30—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length incorporating preformed parts or layers, e.g. moulding around inserts or for coating articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
- B05D7/26—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials synthetic lacquers or varnishes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/32—Making multilayered or multicoloured articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
- B29C43/28—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length incorporating preformed parts or layers, e.g. compression moulding around inserts or for coating articles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2505/00—Polyamides
- B05D2505/50—Polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
- B29K2079/08—PI, i.e. polyimides or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/008—Wide strips, e.g. films, webs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Problem of the present invention is that when manufacture has laminated body containing the high molecular transparent resin film such as polyimides, can on one side maintain transparent resin film it is transparent while more easily the laminated body that carries out laminated body coiling into web-like and will batch and roll out.A kind of method with supporter and the laminated body containing at least one kind of high molecular transparent resin film in polyimides, polyamidoimide and polyamide being formed on the supporter that the invention discloses manufactures.This method comprises the following steps: removing a part of solvent from the varnish being coated with, the transparent resin film containing remaining solvent is made to be formed on the supporter and obtain the process with the laminated body of supporter and transparent resin film；And laminated body is coiled into web-like and the process that obtains the volume of laminated body.By weight reduction rates L of the transparent resin film from 120 DEG C to 250 DEG C be greater than 7% and for 40% it is below in a manner of remove from varnish a part of solvent.
Description
It is on May 05th, 2017 that present patent application, which is for the applying date, application No. is 201710311907.3, hairs
What the application of bright entitled " manufacturing method of the manufacturing method of transparent resin film and the laminated body with transparent resin film " proposed
Divisional application.
Technical field
The present invention relates to the manufacturing method containing the high molecular transparent resin film for dissolving in polar solvent and have transparent
The manufacturing method of the laminated body of resin film.
Background technique
As the transparent component of equipment as liquid crystal display device and solar battery, transparent resin film is used sometimes.
As the transparent resin film, sometimes with the polyimide film (patent document 1) with high heat resistance.
Polyimide film usually manufactures by the following method: will contain polyimide precursor or polyamic acid and solvent
Varnish be coated on supporter, remove solvent from the varnish that is coated with, next, make imidizate terminate (patent document 2,
3)。
When obtaining transparent polyimide film, advantageously following method sometimes: using dissolving in the poly- of polar solvent
Acid imide is dried after being coated on supporter containing its varnish, does not form polyimide film via imidizate.
The manufacturing process of polyimide film generally includes following process as continuous process: by polyimide precursor or gathering
Imide solution be cast the heat resistance as example stainless steel band supporter on, 100~200 DEG C or so at a temperature of
It dries and forms the self-supported membrane of polyimides or its precursor and by the self-supported membrane removed from supporter at high temperature into one
Step heats and is dried or solidifies, or carries out stretching or rolling process as needed.It is known according to dry or solidification and
It stretches, the condition of rolling, is formed by the transparency of polyimide film, the physical property such as mechanical properties change (patent document 4
Deng).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 10-310639 bulletin
Patent document 2: International Publication No. 2009/107599
Patent document 3: Japanese Unexamined Patent Publication 2007-176055 bulletin
Patent document 4: No. 5589384 bulletins of Japanese Patent No.
Summary of the invention
In the manufacture of the transparent resin film as polyimide film, by not using commonly used stainless steel band
And using the supporter that can be batched as resin film, the transparent resin film and supporter that can will be formed as self-supported membrane
Laminated body temporarily coil into web-like.Expect by being dried, stretch, roll from the laminated body rolled out in various conditions
The transparent resin film of the different multi items of production physical property can be readily separated from Deng processing.Do not batch laminated body and continuously
When the processing such as being dried or stretch, in order to manufacture the transparent resin film of multi items simultaneously, need to prepare the painting of a large amount of high price
Cloth equipment, but by temporarily batching laminated body, a coating apparatus can be used only in the stage until forming laminated body, together
When the transparent resin films of multi items can be easily manufactured.
But it if is formed on the supporter that can be batched using macromolecules such as the polyimides for dissolving in polar solvent transparent
Resin film is then difficult to the laminated body being made of supporter and transparent resin film gallantly coiling into web-like sometimes.In addition, will
When coiling into the laminated body of web-like and rolling out, it is difficult to maintain the trend of the uniform transparency there are transparent resin film albefaction.Especially
It is to exist to be difficult to steadily manufacture demanding transparent, uniformity light via the process that laminated body is coiled into web-like
Learn the trend of the transparent resin film of purposes.
Therefore, it is an object of the present invention to have in manufacture containing macromolecules such as the polyimides for dissolving in polar solvent
Transparent resin film laminated body when, can on one side maintain transparent resin film it is transparent while more easily and carry out laminated body
It coils into web-like and rolls out the laminated body batched.
An aspect of of the present present invention, which relates to a kind of manufacture, to be had containing high molecular transparent resin film and supporters such as polyimides
Laminated body method.This method has following process: will contain the macromolecules such as solvent and the polyimides for being dissolved in the solvent
Varnish be coated on the process on supporter；A part that the solvent is removed from the varnish being coated with makes containing residual
The transparent resin film of the solvent be formed on the supporter and obtain that there is the supporter and the transparent resin film
Laminated body process；And the laminated body is coiled into web-like and the process of the volume that obtains the laminated body.To be formed
The transparent resin film pass through thermogravimetry-differential thermal analysis measurement (hereinafter sometimes referred to " TG-DTA measurement ")
The weight reduction rates from 120 DEG C to 250 DEG C found out are greater than 7% and remove for 40% mode below from the varnish of film forming
A part of the solvent.
By removing solvent from varnish under the conditions of weight reduction rates are such in above-mentioned specific range and making transparent
Resin film is formed on supporter, can on one side maintain transparent resin film it is transparent while be easy to carry out and batch laminated body
At rolling out for web-like and the laminated body batched.
Another aspect of the present invention relates to a kind of manufacturing methods of transparent resin film, have following process: by the stacking
The volume of body laminated body obtained from by the above-mentioned manufacture method rolls out, and removes the transparent resin from the laminated body rolled out
The process of film；And a part of the remaining solvent or complete is removed from the transparent resin film removed by the supporter
The process in portion.According to this method, fabrication can be readily separated from while maintaining the uniform transparency of transparent resin film
The transparent resin film of the different multi items of property.
According to an aspect of the present invention, a kind of method is provided, is had in manufacture sub- containing the polyamides for dissolving in polar solvent
When the laminated body of resin film, can on one side maintain transparent resin film it is transparent while more easily and coil into laminated body
Web-like and the laminated body batched is rolled out.As to from the transparent resin film that the laminated body as obtained from this method is removed into
Row processing, can easily make the transparent resin film of the different multi items of physical property.In this way, for example, be capable of providing can
The transparent resin film compatibly used as the transparent component for constituting liquid crystal display device, solar battery etc..
Detailed description of the invention
Fig. 1 is the TG-DTA measurement result of polyimide film.
Symbol description
The weight of sample of the W0 ... at 120 DEG C of weight for keeping sample after five minutes, 250 DEG C of W1 ....
Specific embodiment
Hereinafter, being described in detail to several embodiments of the invention.But the present invention is not limited to realities below
Apply mode.
Manufacturing, there is an embodiment of the method for laminated body of transparent resin film and supporter to comprise the following steps: will contain
There is solvent and is dissolved in the process that the high molecular varnish such as polyimides of the solvent forms a film on supporter；From the varnish of film forming
Remove solvent a part, be formed in the transparent resin film containing remaining solvent on supporter and obtain with supporter with
The process of the laminated body of transparent resin film；And above-mentioned laminated body is coiled into web-like and the process of the volume that obtains laminated body.
Supporter is usually membranaceous substrate, such as can be resin film base material.
Method involved in present embodiment is particularly useful when supporter is resin film base material.As resin film base material,
Such as there is polyethylene terephthalate (PET) film.
The thickness of supporter is not particularly limited, preferably 50~250 μm, further preferably 100~200 μm, especially
Preferably 150~200 μm.It is more thin there are supporter more inhibit the trend of cost, it is more thick there are supporter more be able to suppress sometimes
The trend of the curling generated in the process for removing a part of solvent.
As long as transparent resin film has the high transparency to a certain degree, however it is not limited to it is colorless and transparent, it can also root
It is coloured according to needs in the range for not departing from purport of the invention.
The yellow chromaticity of transparent resin film is preferably 5 hereinafter, further preferably 3 or less.With such low yellow chromaticity
Film can aid in the high visuality of display device etc..
The film thickness of transparent resin film is preferably 10~120 μm, and more preferably 25~100 μm.If the film thickness of transparent resin film
In above-mentioned range, then exist be difficult to generate in coiling process curling, can more easily batch laminated body trend and
It is difficult to generate the trend of the crackle of end in the process for removing solvent.
As resin involved in present embodiment, for example, can enumerate polyimides system macromolecule (comprising polyimides and
Polyamidoimide), it is polyamide, polyester, poly- (methyl) acrylate, acetylcellulose, polyethylene terephthalate, poly-
(ethylene naphthalate), cyclic olefin polymer and their copolymer etc..It is excellent from the transparency, heat resistance, various mechanical properties
Different aspect is set out, and resin is preferably polyimides system macromolecule and polyamide, further preferably polyimides.Contained tree
Rouge can be a kind, be also possible to two or more.
In the present specification, polyimides refers to the constitutional repeating unit for containing imide as main repetition
The polymer of structural unit, polyamide refer to the constitutional repeating unit for containing amide groups as main constitutional repeating unit
Polymer.Polyimides system macromolecule is in addition to polyimides, also comprising having the repetition containing imide and amide groups
Polymer (polyamidoimide) of the structural unit as main constitutional repeating unit.In the present specification, main repetition
Structural unit refers to the constitutional repeating unit for constituting the 60 mass % or more in polymer entirety.Main constitutional repeating unit can
To be made of repetitive unit of more than two kinds.For example, polyimides is including the repetitive structure of more than two kinds containing imide
When unit, as long as total 60 mass % of ratio or more of these constitutional repeating units of more than two kinds.
Polyimides system macromolecule involved in present embodiment can be by aftermentioned tetracarboxylic compound and two amine compounds
Object is manufactured as main raw material, has constitutional repeating unit shown in following formula (10).Here, G is the organic group of 4 valences
Group, A are the organic group of divalent.Polyimides system macromolecule can also be different containing G and/or A formula of more than two kinds (10) institute
The constitutional repeating unit shown.In addition, polyimides system macromolecule involved in present embodiment can not also significantly damage
To the range of various physical property of polyimides system polymeric membrane (transparent resin film) contain formula (11), formula (12), formula (13) institute
The structure shown.
G and G1For the organic group of 4 valences, the organic group that can be preferably replaced by alkyl or fluorine-substituted alkyl.
As the example of G and G1, can illustrate formula below (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26),
The chain type alkyl below of carbon atom number 6 of group shown in formula (27), formula (28) or formula (29) and 4 valences.* in formula is indicated
Connecting key, Z indicate singly-bound ,-O- ,-CH2,-CH2- CH2,-CH (CH3)-,-C (CH3)2,-C
(CF3)2,-Ar- ,-SO2,-CO- ,-O-Ar-O- ,-Ar-O-Ar- ,-Ar-CH2- Ar- ,-
Ar-C (CH3)2- Ar- or-Ar-SO2- Ar-.Ar indicates the Asia virtue for the carbon atom number 6~20 that can be replaced by fluorine atoms
Base can enumerate phenylene as its concrete example.
G2For the organic group of trivalent, the organic group that can be preferably replaced by alkyl or fluorine-substituted alkyl, as
G2Example, can illustrate above-mentioned formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27),
Any of the connecting key of group shown in formula (28) or formula (29) is substituted by the group of hydrogen atom and the carbon atom number of trivalent
6 chain type alkyl below.
G3For the organic group of divalent, the organic group that can be preferably replaced by alkyl or fluorine-substituted alkyl, as
G3Example, can illustrate above-mentioned formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27),
In the connecting key of group shown in formula (28) or formula (29) 2 not adjacent groups for being substituted by hydrogen atom and carbon atom number 6 with
Under chain type alkyl.
A、A1、A2And A3It is the organic group of divalent, can be preferably had by what alkyl or fluorine-substituted alkyl replaced
Machine group, as A, A1、A2And A3Example, formula below (30), formula (31), formula (32), formula (33), formula (34), formula can be illustrated
(35), group shown in formula (36), formula (37) or formula (38)；They are replaced with methyl, fluorine-based, chloro or trifluoromethyl
Group and the chain type alkyl below of carbon atom number 6.* in formula indicates connecting key, Z1、Z2And Z3Each independently represent list
Key ,-O- ,-CH2,-CH2- CH2,-CH (CH3)-,-C (CH3)2,-C (CF3)2,-SO2Or-
CO-.1 example is Z1And Z3For-O- and Z2For-CH2,-C (CH3)2,-C (CF3)2Or-SO2?.Z1 and Z2
And Z2And Z3It is respectively meta or para position preferably with respect to each ring.
Polyamide involved in present embodiment is also possible to have constitutional repeating unit conduct shown in above-mentioned formula (13)
The polymer of main constitutional repeating unit.G in preferred example and concrete example and polyimides system macromolecule3And A3It is identical.
Polyamide can also contain G3And/or A3Constitutional repeating unit shown in different formulas of more than two kinds (13).
Polyimides system macromolecule can for example pass through the polycondensation of diamines and tetracarboxylic compound (tetracarboxylic dianhydride etc.)
It obtains, such as can be by recorded in Japanese Unexamined Patent Publication 2006-199945 bulletin or Japanese Unexamined Patent Publication 2008-163107 bulletin
Method and synthesize.As the commercially available product of polyimides, the Neoprim etc. of Mitsubishi Gas Chemical Co., Ltd can be enumerated.
Tetracarboxylic compound used in synthesis as polyimides can enumerate the fragrance such as aromatic tetracarboxylic dianhydride
The aliphatic tetracarboxylic compound such as race's tetracarboxylic compound and aliphatic tetracarboxylic dianhydride.Tetracarboxylic compound can individually make
With also two or more kinds may be used.Tetracarboxylic compound is also possible to the tetracarboxylic compounds such as chloride compounds in addition to dianhydride
Analog.
As the concrete example of aromatic tetracarboxylic dianhydride, 4,4 '-oxygen, two O-phthalic acid dianhydride, 3,3 ', 4 can be enumerated,
4 '-benzophenone tetracarboxylic dianhydrides, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-biphenyltetracarboxyacid acids two
Acid anhydride, 2,2 ', 3,3 '-biphenyltetracarboxylic dianhydrides, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydrides, bis- (the 3,4- dicarboxyls of 2,2-
Base phenyl) propane dianhydride, bis- (2,3- dicarboxyphenyi) propane dianhydrides of 2,2-, bis- (the 3,4- di carboxyl phenyloxy benzene of 2,2-
Base) propane dianhydride, 4,4 '-(hexafluoroisopropylidenyl) two O-phthalic acid dianhydrides, bis- (2,3- dicarboxyphenyi) ethane of 1,2-
Bis- (2,3- dicarboxyphenyi) the ethane dianhydrides of dianhydride, 1,1-, 1,2- bis- (3,4- dicarboxyphenyi) ethane dianhydrides, 1,1-
Bis- (3,4- dicarboxyphenyi) ethane dianhydrides, bis- (3,4- dicarboxyphenyi) methane dianhydrides, bis- (2,3- dicarboxyphenyi) first
Alkane dianhydride, 4,4 '-(to two oxygroup of phenylene) two O-phthalic acid dianhydrides, 4,4 '-(two oxygroup of metaphenylene) two adjacent benzene two
Formic acid dianhydride and 2,3,6,7- naphthalene tetracarboxylic acid dianhydride.They can be used alone or two or more is applied in combination.
As aliphatic tetracarboxylic dianhydride, the aliphatic tetracarboxylic dianhydride of ring type or non-ring type can be enumerated.Ring type aliphatic
Tetracarboxylic dianhydride is the tetracarboxylic dianhydride with ester ring type hydrocarbon structure, as its concrete example, can enumerate 1,2,4,5- hexamethylenes four
The cycloalkane tetrabasic carboxylic acids two such as carboxylic acid dianhydride, 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,3,4- pentamethylene tetracarboxylic dianhydride
Acid anhydride, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydride, dicyclohexyl 3,3 ' -4,4 '-tetracarboxylic dianhydride and
Their stereoisomer.They can be used alone or two or more is applied in combination.As non-ring type aliphatic tetracarboxylic dianhydride
Concrete example, 1,2,3,4- butane tetracarboxylic acid dianhydrides, 1,2,3,4- pentane tetracarboxylic dianhydrides etc. can be enumerated, they can be independent
Using or two or more is applied in combination.
In above-mentioned tetracarboxylic dianhydride, from the viewpoint of high transparency and less colored property, preferably 1,2,4,5- hexamethylenes four
Carboxylic acid dianhydride, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydride and 4,4 '-(hexafluoroisopropylidenyl) two are adjacent
Phthalic acid dianhydride.
Polyimides system macromolecule involved in present embodiment can be in the polyimides system that do not damage significantly
The range of the various physical property of polymeric membrane except above-mentioned polyimides synthesize used in tetrabasic carboxylic acid acid anhydride other than also make be selected from tetracarboxylic acid
Polyimides system high score made of acid, tricarboxylic acids and other acid anhydrides and diamine reactant in dicarboxylic acids and their acid anhydride and derivative
Son.
As tricarboxylic acid compound, the chloride similar with they of aromatic tricarboxylic acids, aliphatic tricarboxylic acids can be enumerated
Object, acid anhydrides etc. are closed, also two or more kinds may be used.As concrete example, the acid anhydride of 1,2,4- benzene tricarbonic acids can be enumerated；2,3,6- naphthalene
Tricarboxylic acids -2,3- acid anhydride；Phthalic anhydride and benzoic acid are with singly-bound ,-CH2,-C (CH3)2,-C (CF3)2,-
SO2Or the compound that phenylene links.
As dicarboxylic acid compound, the chloride similar with they of aromatic dicarboxylic acid, aliphatic dicarboxylic acid can be enumerated
Object, acid anhydrides etc. are closed, also two or more kinds may be used.As concrete example, can enumerate terephthalic acid (TPA)；M-phthalic acid；Naphthalene dicarboxyl
Acid；4,4 '-diphenyl dicarboxylic acids；3,3 '-diphenyl dicarboxylic acids；The dicarboxylic acid compound of the chain type hydrocarbon below of carbon atom number 8 and 2
Benzoic acid is with singly-bound ,-CH2,-C (CH3)2,-C (CF3)2,-SO2Or the conjunction object that phenylene links.
Diamines used in synthesis as polyimides, can for aliphatic diamine, aromatic diamine or they
Mixture." aromatic diamine " indicates that amino is bonded directly to the diamines of aromatic rings in present embodiment, can also be in its structure
A part include aliphatic group or other substituent groups.Aromatic rings can be monocycle, be also possible to condensed ring, can illustrate phenyl ring,
Naphthalene nucleus, anthracene nucleus and fluorenes ring etc., but it is not limited to these rings.In these aromatic rings, aromatic rings is preferably phenyl ring." aliphatic two
Amine " indicates that amino is bonded directly to the diamines of aliphatic group, in a part of its structure can also include aromatic rings and other
Substituent group.
As aliphatic diamine, such as non-ring type aliphatic diamine and 1, the bis- (amino of 3- such as can enumerate hexamethylene diamine
Methyl) rings such as hexamethylene, bis- (amino methyl) hexamethylenes of 1,4-, norbornane diamines, 4,4 '-diamino-dicyclohexyl methanes
Formula aliphatic diamine etc., they can be used alone or two or more is applied in combination.
As aromatic diamine, such as p-phenylenediamine, m-phenylene diamine (MPD), 2,4- toluenediamine, xylylene can be enumerated
Diamines, to xylylene amine, 1,5- diaminonaphthalene, 2,6- diaminonaphthalene etc. have 1 aromatic rings aromatic diamine,
4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino-diphenyl propane, 4,4 '-diamino-diphenyl ethers, 3,4 '-diaminos
Base diphenyl ether, 3,3 '-diamino-diphenyl ethers, 4,4 '-diamino diphenyl sulfones, 3,4 '-diamino diphenyl sulfones, 3,
Bis- (4- amino-benzene oxygen) benzene of 3 '-diamino diphenyl sulfones, 1,4-, 1,3- bis- (4- amino-benzene oxygen) benzene, 4,4 '-two
Aminodiphenyl base sulfone, bis- (4- (4- amino-benzene oxygen) phenyl) sulfones, bis- (4- (3- amino-benzene oxygen) phenyl) sulfones, 2,2-
Bis- [4- (4- amino-benzene oxygen) phenyl] propane, 2,2- bis- [4- (3- amino-benzene oxygen) phenyl] propane, 2,2 '-diformazans
Base benzidine, 2,2 '-bis- (trifluoromethyl) benzidine, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, 4,4 '-diamino two
Phenyl ether, 3,4 '-diamino-diphenyl ethers, 4,4 '-diaminodiphenyl-methanes, 9,9- bis- (4- aminophenyl) fluorenes, 9,
Bis- (4- amino -3- aminomethyl phenyl) fluorenes of 9-, bis- (4- amino -3- chlorphenyl) fluorenes of 9,9-, bis- (the 4- amino-of 9,9-
3- fluorophenyl) aromatic diamine with 2 or more aromatic rings such as fluorenes, they can be used alone or be applied in combination 2 kinds with
On.
In above-mentioned diamines, from the viewpoint of high transparency and less colored property, it is preferable to use selected from having biphenyl structural
One or more of aromatic diamine.Further preferably using selected from 2,2 '-dimethylbenzidines, 2,2 '-bis- (trifluoromethyls)
Benzidine, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl and 4, one or more of 4 '-diamino-diphenyl ethers, further
It is preferable to use 2,2 '-bis- (trifluoromethyl) benzidine.
As the polymer comprising constitutional repeating unit shown at least one kind of formula (10), formula (11), formula (12) or formula (13)
Polyimides system macromolecule and polyamide be diamines with by the tetracarboxylic compound (tetracarboxylic acids such as chloride compounds, tetracarboxylic dianhydride
Acid compound analog), tricarboxylic acid compound (the tricarboxylic acids compound such as chloride compounds, tricarboxylic acid anhydride analog) and dicarboxylic acids
The polycondensation of at least one kind of compound contained in the group that compound (dicarboxylic acid compounds such as chloride compounds analog) is constituted generates
Object, that is, condensed type macromolecule.As starting material, aside from them, also further using dicarboxylic acid compound sometimes (includes
The analog of chloride compounds etc.).Constitutional repeating unit shown in formula (11) is usually derivative by Diamines and tetracarboxylic compound.
Constitutional repeating unit shown in formula (12) is usually derivative by diamines and tricarboxylic acid compound.Constitutional repeating unit shown in formula (13)
It is usually derivative by diamines and dicarboxylic acid compound.Diamines and the concrete example of tetracarboxylic compound are as described above.
The conversion of the standard polystyren of polyimides system macromolecule and polyamide involved in present embodiment is divided equally again
Son amount preferably 10000~500000, more preferably 50000~500000, further preferably 100000~400000.In the presence of
The weight average molecular weight of polyimides system macromolecule and polyamide is bigger, easier in membranization to show becoming for high resistance to bend(ing)
Gesture, if but the weight average molecular weight of polyimides system macromolecule and polyamide it is excessive, there are the viscosity of varnish to get higher, under processability
The trend of drop.
Polyimides system macromolecule and polyamide pass through containing fluoro substituents are contained, and there are elasticity modulus when membranization to improve,
And the trend that YI value reduces.If the elasticity modulus of film is high, there are the trend that the generation of scratch and fold etc. is inhibited.From
From the perspective of the transparency of film, polyimides system macromolecule and polyamide preferably have containing fluoro substituents.As fluorine-containing substitution
The concrete example of base can enumerate fluorine-based and trifluoromethyl.
The content of fluorine atom in polyimides system macromolecule and polyamide is with polyimides system macromolecule or polyamide
On the basis of quality, the preferably 1 mass % of mass %~40, further preferably 5 mass of mass %~40 %.
Transparent resin film involved in present embodiment in addition to above-mentioned polyimides system macromolecule and/or polyamide,
It can also be further containing inorganic material such as inorganic particulates.
As inorganic material, the seasons alkoxy silane such as silicon dioxide granule, tetraethyl orthosilicate (TEOS) can be preferably enumerated
Equal silicon compounds, from the viewpoint of varnish stability, preferred silicon dioxide granule.
The average primary particle diameter of silicon dioxide granule is preferably 10~100nm, further preferably 20~80nm.If dioxy
The average primary particle diameter of SiClx particle is 100nm hereinafter, then there is the trend that the transparency improves.If silicon dioxide granule is averaged
Primary particle size is 10nm or more, then exists since the cohesiveness of silicon dioxide granule weakens and easy-to-handle trend.
Silicon dioxide microparticle involved in present embodiment, which can be used, makes silicon dioxide granule be scattered in organic solvent etc.
Made of silicon dioxide gel, the silicon dioxide microparticle powder manufactured with vapor phase method also can be used, but from maneuverable side
Face is set out, preferably silicon dioxide gel.
(average) primary particle size of silicon dioxide granule in transparent resin film can be by micro- using transmission electron
The observation of mirror (TEM) and find out.The size distribution of silicon dioxide granule before forming transparent resin film can use commercially available
Laser diffraction formula particle size distribution meter and find out.
In the transparent resin film involved in present embodiment, the containing ratio of inorganic material is preferably 0 matter of mass %~90
Measure %, the more preferably 10 mass % of mass %~60, further preferably 20 mass of mass %~50 %.If polyimides system is high
The match ratio of molecule and polyamide and inorganic material (silicon materials) within the above range, then exists and is easy to have both transparent resin film
The trend of the transparency and mechanical strength.
Transparent resin film can also further contain other ingredients in addition to ingredient described above.As other ingredients,
Such as antioxidant, release agent, stabilizer, blueing agent, fire retardant, lubricant and levelling agent can be enumerated.
Quality of the containing ratio of ingredient other than resin component and inorganic material relative to transparent resin film, preferably greater than
0% and be 20 mass % hereinafter, further preferably greater than 0% and be 10 mass % or less.
The thickness of transparent resin film can have a various equipment of transparent resin film and appropriate adjustment according to application, but preferably 10
~500 μm, more preferably 15~200 μm, further preferably 20~100 μm.The transparent resin film of such composition can have
There is especially excellent bendability.
Then, the manufacture in case where transparent resin is polyimides system macromolecule to the optical film of present embodiment
One example of method is illustrated.
Varnish used in the production of the high molecular film of polyimides system involved in present embodiment can for example pass through
Polyimides system obtained from selecting from above-mentioned tetracarboxylic compound, above-mentioned diamines and above-mentioned other raw materials and reacting it is high
The reaction solution of molecule and/or polyamide, above-mentioned solvent and above-mentioned other ingredients that are as needed and using are mixed, are stirred
And it prepares.Also the polyimides system macromolecule of solid that the solution of polyimides system macromolecule bought etc. can be used or buy
Deng solution replace the reaction solution of polyimides system macromolecule etc..
When manufacture contains the transparent resin film of organic and/or inorganic materials (silicon materials), inorganic material is added, is stirred and mixes,
Preparation is uniformly dispersed the varnish (dispersion liquid) of organic and/or inorganic materials.
Next, varnish is coated on supporter, the one of solvent is removed from the varnish (film) being coated with by dry
Partially form transparent resin film.In other words, varnish (film) is dried in a manner of a part of residual solvent.?
This, be to be formed by the weight reduction rates L from 120 DEG C to 250 DEG C of transparent resin film found out by TG-DTA measurement
The mode of prescribed limit removes a part of solvent from the varnish of film forming.These processes can for example pass through roll-to-roll or interval side
Formula carries out.The detailed content for finding out the method for the weight reduction rates L of transparent resin film is illustrated in the later-described embodiments.
If remove (drying) solvent after transparent resin film weight reduction rates L it is somewhat big, laminated body it is curved
The deformations such as folding are inhibited, and the batching property of laminated body improves.From this viewpoint, the weight of the transparent resin film after preferably drying
Slip L is greater than 7%, more preferably 8% or more, further preferably 9% or more.
If the weight reduction rates L for removing the transparent resin film after (drying) solvent is somewhat small, transparent resin film
It is difficult to be attached at supporter, therefore, can easily while maintaining the uniform transparency of transparent resin film by laminated body
It is rolled out from volume.From this viewpoint, the weight reduction rates L after dry is preferably 40% hereinafter, more preferably 35% hereinafter, into one
Step preferably 30% or less.
Especially in transparent resin film when containing organic and/or inorganic materials, if removing the weight reduction rates of the transparent resin film after solvent
L is preferably 7~40%, more preferably 10~38%, then can further play significantly for improving the treatability of laminated body
Effect.
In order to remove solvent from film, film can also be heated.The condition heated by appropriate adjustment, can
Solvent is removed in the way of prescribed limit by weight reduction rates L.For example, can by heating temperature 40~140 DEG C range into
Row adjustment, the range by heating time 10~180 minutes, preferably 10~120 minutes are adjusted.In the drying using hot wind
In the case where (removing of solvent), the wind speed of hot wind can be adjusted in 0~15m/ seconds ranges.When removing solvent,
Film can be heated under conditions of inert atmosphere, decompression.
With supporter and the laminated body for being formed by transparent resin film web-like can be coiled by usual way.Example
Such as, laminated body can be batched around the winding tube (plastic core, metallic roll etc.) of 50~200mm of outer diameter, obtains laminated body
Volume.As winding tube, commercially available 3 inches, the plastic core of 6 inch diameters etc. can be used.Thereby, it is possible to by laminated body to roll up
State saved and carried.
It can suitably while rolling out laminated body from the volume of laminated body and remove supporter and be used for transparent resin film
The manufacture of various components.Transparent resin film obtained from the method as involved in present embodiment is from the good transparency
And aspect also excellent is set out in terms of heat resistance and bendability, as the various flexibilities such as display device, solar battery
The transparent component of equipment is useful.
Method by comprising the following steps can obtain transparent resin film: laminated body rolled out from the volume of laminated body, from
The process of the laminated body removing transparent resin film rolled out；And remaining solvent is removed from the transparent resin film removed by supporter
Some or all of process.I.e., it is possible to the transparent tree that transparent resin film is fully dried via following process
Adipose membrane: first drying process of a part of solvent is removed from the varnish being coated on supporter；And batching in laminated body
After rolling out, from the transparent resin film removed by supporter remove after the first drying process a part of remaining solvent or
The second whole drying processes.By temporarily batching laminated body after the first drying process, the film thickness of transparent resin film can be improved
Uniformity.
Transparent resin film after second drying process can contain micro solvent, but usually be removed by the second drying process
Solvent is removed until the weight reduction rates L from 120 DEG C to 250 DEG C found out by thermogravimetry-differential thermal analysis measurement is small
In 2% or less than 1% until.Transparent resin film after second drying process passes through thermogravimetry-differential thermal analysis measurement
And the lower limit of the weight reduction rates L from 120 DEG C to 250 DEG C found out is not particularly limited, such as can be 0.1%.Transparent tree
Second drying process of adipose membrane can be carried out and heating to transparent resin film.The condition of the heating of second drying process
It is not particularly limited, such as can be adjusted in the range of 150~300 DEG C of heating temperature, 10~180 minutes heating times.
Transparent resin film after second drying process or before the second drying process can also be stretched.Stretching can be
It is uniaxially stretched, is also possible to multi-shaft stretching.Stretching ratio is not particularly limited, such as can be 1.01 times~2.0 times.Second is dry
Transparent resin film can also be stretched in drying process.By suitably setting stretching ratio, elasticity modulus can be obtained not
Same transparent resin film.
Transparent resin film can be rolled to replace stretching.Rolling for example can be transparent by passing through between multiple rollers
Resin film is simultaneously applied stressed processing and is carried out.Line pressure when rolling can be 1000~100000N/m, can add in rolling
Heat is to 50~200 DEG C.By making the residual solvent amount in the transparent resin film for rolling corresponding to above-mentioned weight reduction rates L
Range, exist be easy to get the effect for improving scratch hardness trend and being difficult in transparent resin film generate because of albefaction or
The trend of the coarse caused mist degree on surface.By suitably setting rolling condition, the different transparent tree of scratch hardness can be obtained
Adipose membrane.
Embodiment
The present invention is further concretely demonstrated hereinafter, enumerating embodiment.But the present invention is not limited to these
Embodiment.
1. evaluation method
Thermogravimetry-differential thermal analysis (TG-DTA) measurement
The TG/DTA6300 of Hitachi High-Tech Science corporation is used to fill as the measurement of TG-DTA
It sets.The sample of about 20mg is obtained from the transparent resin film (polyimide film) of production.By sample with 10 DEG C/min of heating rate
From room temperature to 120 DEG C, keep after five minutes, being warming up to 400 DEG C on one side with 10 DEG C/min of heating rate at 120 DEG C
Under the conditions of heat on one side measure sample weight change.Fig. 1 shows the TG- of the polyimide film made in aftermentioned embodiment 1
DTA measurement result.
According to TG-DTA measurement result, the weight reduction rates L (%) that is calculated from 120 DEG C to 250 DEG C by following formula.
L (%)=100- (W1/W0) × 100
Here, W0 indicates the weight for keeping sample after five minutes at 120 DEG C, W1 indicates the weight of the sample at 250 DEG C.
Yellow chromaticity (YI)
The UV, visible light near infrared spectrometer V-670 of Japan's light splitting corporation is utilized according to JIS K 7373:2006
Measure the yellow chromaticity (Yellow Index:YI) of transparent resin film (polyimide film).It is carried on the back in the state of no sample
After scape measurement, film is set to specimen holder and is carried out to the measurement of the transmissivity of the light of 300~800nm, find out 3 values (X, Y,
Z).YI is calculated based on following formula.
YI=100 × (1.2769X-1.0592Z)/Y
Mist degree
The full-automatic direct-reading haze computer HGM-2DP of Suga testing machine corporation is utilized according to JIS K7105:1981
Measure the mist degree of transparent resin film (polyimide film).
Total light transmittance
It is measured according to JIS K7105:1981 using the full-automatic direct-reading haze computer HGM-2DP of testing machine corporation
The total light transmittance of transparent resin film (polyimide film).
Elasticity modulus
Use the springform of Autograph AG-IS measurement transparent resin film (polyimide film) of Shimadzu Seisakusho Ltd.
Amount.The test film for making 10mm width measures S-S song between chuck under conditions of distance 500mm, tensile speed 20mm/min
Line calculates elasticity modulus by its gradient.
Scratch hardness
Transparent resin film (polyimide film) is evaluated using the pencil-type scratch hardness tester 318S of Erichsen corporation
Scratch hardness.By the surface of transparent resin film standard needle while periodically increasing load with 0.1N scale
(Standard pin) (0.75mm) scrapes 5cm, and record does not generate the maximum value conduct of the scratch of 1cm or more or the load of recess
Scratch hardness.
2. the production of laminated body
Embodiment 1
Prepare polyimides (Mitsubishi Gas Chemical Co., Ltd's system " Neoprim ", 390 DEG C of glass transition temperature).It will
The polyimides is dissolved in the in the mixed solvent of the 9:1 of n,N-dimethylacetamide and gamma-butyrolacton, prepares varnish (concentration
20 mass %).By casting by the varnish in 188 μm of thickness, the polyethylene terephthalate (PET) of width 750mm
It forms a film on film.Make the varnish of film forming by linear speed 0.2m/ minutes by by periodically from 50 DEG C to 75 DEG C in a manner of set temperature
Length 12m furnace in, thus from varnish remove solvent and form transparent resin film (polyimide film, 80 μm of thickness) (first
Drying process).Then, by by being formed transparent resin film and the membranaceous laminated body that constitutes of PET film coil into web-like.Laminated body
Web-like can easily be coiled into.It can not to generate while maintaining the uniform transparency of transparent resin film and fracture and crackle
Ground rolls out laminated body from the volume of the laminated body batched.
It will be removed from the transparent resin film of the laminated body rolled out from PET film.The transparent resin film of removing passes through TG-
The weight reduction rates L from 120 DEG C to 250 DEG C that DTA is measured and found out is 9%.
By the transparent resin film removed from the laminated body rolled out by volume under nitrogen atmosphere under conditions of 210 DEG C, 60 minutes
Further heating, to make it dry (the second drying process).Total light of transparent resin film after second drying process transmits
Rate is 90%, YI 1.4, mist degree 0.2.
Comparative example 1
By periodically from 60 DEG C to 140 DEG C in a manner of set the first drying process furnace in temperature so that from laminated body
The weight reduction rates L of transparent resin film before second drying process of removing found out by TG-DTA measurement is 5%, will
Linear speed is adjusted to 0.3m/ minutes, in addition to this, makes the laminated body of transparent resin film and PET film similarly to Example 1.By
In the contraction of transparent resin film, laminated body is substantially crimped along the direction TD (direction vertical with the moving direction of laminated body).Cause
This, laminated body fractures together with PET film, laminated body can not be coiled into web-like.
Comparative example 2
By periodically from 40 DEG C to 70 DEG C in a manner of set the first drying process furnace in temperature so that from laminated body
The weight reduction rates L of transparent resin film before second drying process of removing found out by TG-DTA measurement is 45%, will
Linear speed is adjusted to 2m/ minutes, in addition to this, makes the laminated body of transparent resin film and PET film similarly to Example 1.It can
The laminated body of production is coiled into web-like.But transparent resin film is attached at the PET film on the outside of it in volume, from the layer batched
When the volume of stack rolls out laminated body, transparent resin film extends and albefaction.Therefore, it is impossible to maintain the uniform of transparent resin film on one side
The transparency rolls out laminated body on one side.
Embodiment 2
Prepare polyimides (" Neoprim " of Mitsubishi Gas Chemical Co., Ltd, vitrifying similarly to Example 1
390 DEG C of transition temperature).It disperses gamma-butyrolacton solution (20 mass % of concentration), the silicon dioxide granule of the polyimides in
The two of dispersion liquid made of gamma-butyrolacton (30 mass % of silicon dioxide granule concentration) and the alkoxy silane with amino
The mixing of methyl vinyl amine aqueous solution, stirs 30 minutes, obtains the varnish containing polyimides and silicon dioxide granule.Titanium dioxide silicon grain
The mass ratio of son and polyimides is 30:70, and the amount of the alkoxy silane with amino is relative to silicon dioxide granule and polyamides
Total 100 mass parts of imines are 1.67 mass parts.
By casting by the varnish in 188 μm of thickness, polyethylene terephthalate (PET) film of width 750mm
Upper film forming.Make the varnish of film forming by linear speed 0.8m/ minutes by by periodically from 50 DEG C to 70 DEG C in a manner of the length that sets
In the furnace of 12m, to remove solvent from varnish and form transparent resin film (polyimide film, 50 μm of thickness) (first back tender
Sequence).Then, by by being formed transparent resin film and the membranaceous laminated body that constitutes of PET film coil into web-like and obtain laminated body
Volume.Laminated body can easily coil into web-like.It can not while maintaining the uniform transparency of transparent resin film and produce
Raw fracture with crackle rolls out laminated body from the volume of the laminated body batched.
Transparent resin film is removed from the laminated body rolled out by volume.The transparent resin film of removing is measured by TG-DTA
The weight reduction rates L from 120 DEG C to 250 DEG C found out is 18%.
By the transparent resin film removed from the laminated body rolled out by volume under nitrogen atmosphere under conditions of 210 DEG C, 60 minutes
Further heating, to make it dry (the second drying process).Total light of transparent resin film after second drying process transmits
Rate is 91%, YI 1.3, mist degree 0.1.The elasticity modulus of obtained polyimide film is 5.0GPa.In addition, pencil-type scratch
Scleroscopic evaluation result is 0.1N or less.
Embodiment 3
By periodically from 45 DEG C to 70 DEG C in a manner of set the first drying process furnace in temperature so that from laminated body
The weight reduction rates L of transparent resin film before second drying process of removing found out by TG-DTA measurement is 35%, will
Linear speed is adjusted to 1m/ minutes, in addition to this, makes the layer of transparent resin film (50 μm of thickness) and PET film similarly to Example 2
Stack.Laminated body can easily coil into web-like.It can not while maintaining the uniform transparency of transparent resin film and produce
Raw fracture with crackle rolls out laminated body from the volume of the laminated body batched.
By the transparent resin film removed from the PET film of the laminated body rolled out by volume under nitrogen atmosphere at 210 DEG C, 60 minutes
Under the conditions of further heating make it dry (the second drying process).Total light of transparent resin film after second drying process transmits
Rate is 91%, YI 1.3, mist degree 0.1.
Embodiment 4
The volume of laminated body is obtained similarly to Example 2.Transparent resin film is removed from the laminated body rolled out by volume.To removing
Transparent resin film exist while fixing its end 150 DEG C at a temperature of be stretched to 1.2 times.The transparent resin film of stretching is existed
It is further heated under conditions of 210 DEG C, 60 minutes under nitrogen atmosphere, to make it dry (the second drying process).Second is dry
The elasticity modulus of the draw direction of transparent resin film after process is 5.9GPa.Laminated body same as Example 2 is used on one side
Volume condition of the change for dry heating on one side, so as to make the different optical film of elasticity modulus.
Embodiment 5
The volume of laminated body is obtained similarly to Example 2.Transparent resin is removed from the PET film of the laminated body rolled out by volume
Film.It is rolled by transparent resin film of the rolling process to removing.Rolling is carried out at room temperature with line pressure 10000N/m.It will be through
The transparent resin film of rolling heats under conditions of 210 DEG C, 60 minutes under nitrogen atmosphere, to make it dry (the second back tender
Sequence).The scratch hardness of transparent resin film after second drying process is 1.4N.Laminated body same as Example 2 is used on one side
Volume change on one side the second drying process heating condition, so as to make the different optical film of scratch hardness.
Comparative example 3
By periodically from 60 DEG C to 140 DEG C in a manner of set the first drying process furnace in temperature so that from laminated body
The weight reduction rates L of transparent resin film before second drying process of removing found out by TG-DTA measurement is 7%, will
Linear speed is adjusted to 0.8m/ minutes, in addition to this, makes transparent resin film (50 μm of thickness) and PET film similarly to Example 2
Laminated body.In furnace, due to the contraction of transparent resin film, laminated body substantially crimps in the direction TD.Therefore, laminated body is together with PET
Film fractures, if laminated body is coiled into web-like.Then cracked in the end of transparent resin film.
Comparative example 4
By periodically from 40 DEG C to 70 DEG C in a manner of set the first drying process furnace in temperature so that from laminated body
The weight reduction rates L of transparent resin film before second drying process of removing found out by TG-DTA measurement is 50%, will
Linear speed is adjusted to 2m/ minutes, in addition to this, makes the layer of transparent resin film (50 μm of thickness) and PET film similarly to Example 2
Stack.Laminated body is coiled into web-like.But transparent resin film is attached at the PET film on the outside of it in volume, the stacking that will be batched
When body rolls out, transparent resin film extends and albefaction.Therefore, it is impossible to be followed while maintaining the uniform transparency of transparent resin film
Roll out laminated body.
Embodiment 6
Prepare polyimides (KPI-300MXF (100) of industry companies of river village).The polyimides is dissolved in N,
The in the mixed solvent of the 9:1 of N- dimethyl acetamide and gamma-butyrolacton, further addition is relative to 100 mass of polyimides
Part is the Sumisorb350 of the Sumika Chemtex corporation of 0.8 mass parts as UV absorbent, and preparing varnish, (polyamides is sub-
The 17 mass % of concentration of amine).By casting by the varnish in 188 μm of thickness, the polyethylene terephthalate of width 750mm
It forms a film on ester (PET) film.Make the varnish of film forming by linear speed 0.2m/ minutes by by periodically from 50 DEG C to 80 DEG C in a manner of set
Determine in the furnace of length 12m of temperature, to remove solvent from varnish and form transparent resin film (polyimide film, average thickness
82 μm) (the first drying process).Then, by by being formed transparent resin film and the membranaceous laminated body that constitutes of PET film coil into
Web-like and the volume for obtaining laminated body.Laminated body can easily coil into web-like.The uniform of transparent resin film can be maintained on one side
The transparency do not generate to fracture and with crackle roll out laminated body from the volume of the laminated body batched on one side.
Transparent resin film is removed from the laminated body rolled out by volume.The transparent resin film of removing is measured by TG-DTA
The weight reduction rates L from 120 DEG C to 250 DEG C found out is 8%.
By the transparent resin film removed from the laminated body rolled out by volume in the state of securing the end of volume width direction
It is heated under conditions of 210 DEG C, 60 minutes under nitrogen atmosphere, to make it dry (the second drying process).Second drying process
The total light transmittance of transparent resin film afterwards is 92%, YI 2.1, mist degree 0.3.Average thickness is 79 μm.
Embodiment 7
The volume of laminated body is obtained similarly to Example 6.The transparent resin film removed from the laminated body rolled out by volume is existed
It is not fixed in the state of the end of volume width direction and is heated 24 minutes with 200 DEG C under nitrogen atmosphere, (second is dry to make it dry
Drying process).The total light transmittance of transparent resin film after drying is 93%, YI 2.0, mist degree 0.3.Transparent resin film
Average thickness is 86 μm.The heating of the second drying process is changed while using the volume of laminated body same as Example 6
Condition, so as to make the different optical film of film thickness.
Embodiment 8
Using varnish same as Example 6, by periodically from 50 DEG C to 80 DEG C in a manner of set the first drying process
Furnace in temperature so that from laminated body remove the second drying process before transparent resin film by TG-DTA measurement asking
Weight reduction rates L out is 9%, and linear speed is adjusted to 0.3m/ minutes, in addition to this, makes transparent tree similarly to Example 6
The laminated body of adipose membrane (polyimide film, 70 μm of average thickness) and PET film, is coiled into web-like and obtains the volume of laminated body.
The width of transparent resin film is 70cm.
Comparative example 5
The laminated body formed similarly to Example 8 is not coiled into web-like and directly removes transparent resin film from laminated body
(70 μm of average thickness).
For the transparent resin film after the first drying process of embodiment 8 and comparative example 5, with 5cm measuring space film width
The film thickness of the center portion 40cm in direction, calculates its standard deviation.The standard deviation of embodiment 8 is 0.2, the standard of comparative example 5
Deviation is 0.4.Confirmed by the result, by the way that laminated body is temporarily coiled into web-like, the uniformity of film thickness is improved.
Claims (4)
1. a kind of manufacturing method of laminated body, comprises the following steps:
Containing solvent and at least one kind of in polyimides, polyamidoimide and polyamide of the solvent will be dissolved in
High molecular varnish is coated on the process on supporter；
It is greater than 7% with the weight reduction rates from 120 DEG C to 250 DEG C found out by thermogravimetry-differential thermal analysis measurement
And a part of the solvent is removed from the varnish being coated with by 40% mode below, make containing the remaining solvent
Transparent resin film be formed on the supporter and obtain the laminated body with the supporter and the transparent resin film
Process；And
The laminated body is coiled into web-like and the process of the volume that obtains the laminated body.
2. manufacturing method as described in claim 1, wherein the supporter is resin film base material.
3. manufacturing method as claimed in claim 1 or 2, wherein the varnish further contains organic and/or inorganic materials.
4. a kind of manufacturing method of transparent resin film, has following process:
The laminated body is rolled out from the volume of the laminated body as obtained from manufacturing method according to any one of claims 1 to 3,
The process for removing the transparent resin film from the laminated body rolled out；And
The some or all of process of the remaining solvent is removed from the transparent resin film removed by the supporter.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-094530 | 2016-05-10 | ||
| JP2016094530 | 2016-05-10 | ||
| JP2016-199059 | 2016-10-07 | ||
| JP2016199059A JP6170224B1 (en) | 2016-05-10 | 2016-10-07 | Method for producing transparent resin film, and method for producing laminate having transparent resin film |
| CN201710311907.3A CN107443645B (en) | 2016-05-10 | 2017-05-05 | The manufacturing method of the manufacturing method of transparent resin film and laminated body with transparent resin film |
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| CN201710311907.3A Division CN107443645B (en) | 2016-05-10 | 2017-05-05 | The manufacturing method of the manufacturing method of transparent resin film and laminated body with transparent resin film |
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| CN109366827A true CN109366827A (en) | 2019-02-22 |
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| CN201811055864.8A Pending CN109366827A (en) | 2016-05-10 | 2017-05-05 | The manufacturing method of the manufacturing method of transparent resin film and the laminated body with transparent resin film |
| CN201710311907.3A Active CN107443645B (en) | 2016-05-10 | 2017-05-05 | The manufacturing method of the manufacturing method of transparent resin film and laminated body with transparent resin film |
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| CN201710311907.3A Active CN107443645B (en) | 2016-05-10 | 2017-05-05 | The manufacturing method of the manufacturing method of transparent resin film and laminated body with transparent resin film |
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| Country | Link |
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| JP (1) | JP6170224B1 (en) |
| KR (2) | KR101907787B1 (en) |
| CN (2) | CN109366827A (en) |
| TW (1) | TWI603845B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6494845B1 (en) | 2017-10-31 | 2019-04-03 | 住友化学株式会社 | Manufacturing method of resin film |
| JP6494844B1 (en) * | 2017-10-31 | 2019-04-03 | 住友化学株式会社 | Manufacturing method of resin film and resin film with few micro scratches |
| WO2019135366A1 (en) * | 2018-01-04 | 2019-07-11 | 東洋紡株式会社 | Film laminate manufacturing method and film laminate manufacturing device |
| JP6450048B1 (en) * | 2018-02-14 | 2019-01-09 | 住友化学株式会社 | Laminate |
| JP2019137555A (en) * | 2018-02-14 | 2019-08-22 | 住友化学株式会社 | Film roll |
| JP2019195997A (en) * | 2018-05-08 | 2019-11-14 | 住友化学株式会社 | Laminate and method for producing the same |
| JP6434186B1 (en) * | 2018-05-08 | 2018-12-05 | 住友化学株式会社 | Laminated body and method for producing the same |
| KR101920631B1 (en) * | 2018-08-22 | 2019-02-13 | 국도화학 주식회사 | A low gloss black polyimide film comprising a stress canceling resin layer and a method for producing the same |
| JP2020095079A (en) * | 2018-12-10 | 2020-06-18 | 住友化学株式会社 | Laminate and image display device using the same |
| KR102283535B1 (en) * | 2019-09-30 | 2021-07-29 | 에스케이이노베이션 주식회사 | Polyaimde based film and display device comprising the same |
| JP7356895B2 (en) | 2019-12-24 | 2023-10-05 | 株式会社カネカ | Optical film containing transparent polyimide resin and its manufacturing method |
| JP2021115861A (en) * | 2020-01-29 | 2021-08-10 | 住友化学株式会社 | Film roll |
| TW202138198A (en) * | 2020-01-29 | 2021-10-16 | 日商住友化學股份有限公司 | Film roll wound with an optical film, a cured resin layer, and a protective film sequentially from the core side of the film roll |
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2016
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- 2017-05-05 CN CN201811055864.8A patent/CN109366827A/en active Pending
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| JP2009233944A (en) * | 2008-03-26 | 2009-10-15 | Unitika Ltd | Method for manufacturing polymide film |
| CN101392059A (en) * | 2008-11-05 | 2009-03-25 | 东华大学 | Colorless transparent aromatic polyimide film and preparation method thereof |
| CN102869632A (en) * | 2010-04-30 | 2013-01-09 | 日东电工株式会社 | Method for producing transparent substrate |
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| Publication number | Publication date |
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| CN107443645A (en) | 2017-12-08 |
| KR20180111745A (en) | 2018-10-11 |
| TW201739621A (en) | 2017-11-16 |
| JP6170224B1 (en) | 2017-07-26 |
| CN107443645B (en) | 2018-10-16 |
| KR101907787B1 (en) | 2018-10-12 |
| JP2017203146A (en) | 2017-11-16 |
| KR20170126799A (en) | 2017-11-20 |
| TWI603845B (en) | 2017-11-01 |
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