CN102218790A - Liquid crystal polyester film manufacturing method - Google Patents
Liquid crystal polyester film manufacturing method Download PDFInfo
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- CN102218790A CN102218790A CN2011100669498A CN201110066949A CN102218790A CN 102218790 A CN102218790 A CN 102218790A CN 2011100669498 A CN2011100669498 A CN 2011100669498A CN 201110066949 A CN201110066949 A CN 201110066949A CN 102218790 A CN102218790 A CN 102218790A
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- liquid crystal
- crystal polyester
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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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
- B29C41/02—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 definite length, i.e. discrete articles
- B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Laminated Bodies (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
A liquid crystal polyester film manufacturing method has the advantages of possibility decrease of flash generation in a liquid crystal polyester film or peeling difficulty of the liquid crystal polyester film, and easy manufacturing of the liquid crystal polyester film. A liquid composition 1 having liquid polyester and solvents is curtain coated on a base material 2. The liquid composition 1 curtain coated on the base material is dried to obtain a liquid crystal polyester precursor film 5 having a solvent state. The liquid crystal polyester precursor film 5 is peeled from the base material 2. The liquid crystal polyester precursor film 5 is then transfer printed on a metal base material 6 having a peeling layer at least on one main face. The liquid crystal polyester precursor film 5 is made to contact with the peeling layer so as to obtain a first laminated body L2 having the liquid crystal polyester precursor film 5 and the metal base material 6. The first laminated body L2 is performed heat treatment so as to obtain a second laminated body L3 having a liquid crystal polyester film 9 with basically no solvents and a metal base material 6. The liquid crystal polyester film 9 is peeled from the metal base material 6.
Description
Technical field
The present invention relates to the manufacture method of the improved liquid crystal polyester film of anisotropy (film that forms by liquid crystal polyester) of mechanical properties.
Background technology
Up to now, proposed by with of the liquid crystal polyester moulding of solvent cast method, improved because the anisotropy of the mechanical properties of the tearing strength that the molecularly oriented during moulding causes etc. or improve the manufacture method (referring to for example patent documentation 1～3) of the liquid crystal polyester film of dimensional stability thereby reach with solvent soluble.
Promptly, in patent documentation 1 (spy opens the 2004-203032 communique), disclose the fluid composition that will contain liquid crystal polyester and solvent and gone up curtain coating, drying, heat treatment at the substrate (not dilatable substrate in solvent) that constitutes by olefine kind resins such as polyethylene, polypropylene, polymethylpentenes, after the film forming, by this strippable substrate liquid crystal polyester film, thus the method (paragraph [0037]) of acquisition liquid crystal polyester film.
In addition, in patent documentation 2 (spy opens the 2006-88426 communique), fluid composition curtain coating, drying, heat treatment on base materials such as glass or metallic plate that will contain liquid crystal polyester and solvent are disclosed, after the film forming, peel off the liquid crystal polyester film by this base material, thereby obtain the method (paragraph [0026]) of liquid crystal polyester film.
In addition, in patent documentation 3 (spy opens the 2007-119610 communique), fluid composition curtain coating, drying, heat treatment on copper-coated laminated board that will contain liquid crystal polyester and solvent are disclosed, after the film forming, remove this copper-coated laminated board by etching, thereby obtain the method (paragraph [0046]) of liquid crystal polyester film.
Summary of the invention
Yet, in the technology that these patent documentations 1～3 propose, have following problem respectively.
At first, in the technology that patent documentation 1 proposes, glass transition temperature as the illustrated olefine kind resin of baseplate material of curtain coating fluid composition is identical or lower with the heat treatment temperature of fluid composition, and therefore when heat treatment, the elastic modelling quantity of substrate reduces.As a result, according to heat-treat condition, in gained liquid crystal polyester film, produce flash of light (ripple).
In addition, in the technology that in patent documentation 2, proposes, when fluid composition carries out curtain coating, drying, heat treatment, the small concavo-convex fusion of base materials such as liquid crystal polyester and glass or metallic plate, therefore when base material is peeled off polyester film, this liquid crystal polyester film is difficult to peel off from base material.
In addition, in the technology that in patent documentation 3, proposes,, must carry out soup and handle, when therefore having trouble, also produce the worry of handling the waste liquid that contains metal ion in a large number for the etching copper-coated laminated board.
Therefore, the present invention is in view of such problem, aims to provide a kind of situation that produces flash of light in the liquid crystal polyester film that is reduced in, and avoids the liquid crystal polyester film and be difficult to the situation about peeling off from base material and then the manufacture method of liquid crystal polyester film easy to manufacture.
In order to realize this purpose, the inventor is conceived to, heat-treating under the state of transfer printing liquid crystal polyester precursor film on the metal base that has peel ply on the interarea when making the liquid crystal polyester film for guaranteeing the fissility of liquid crystal polyester film, peel off the liquid crystal polyester film then, thereby finish the present invention.
Promptly, the invention provides a kind of manufacture method that comprises the liquid crystal polyester film of following operation: curtain coating contains the operation of the fluid composition of liquid crystal polyester and solvent on base material, will be on above-mentioned base material the fluid composition drying of curtain coating, thereby acquisition contains the operation of the liquid crystal polyester precursor film of above-mentioned solvent state, peel off the operation of above-mentioned liquid crystal polyester precursor film from above-mentioned base material, to the above-mentioned liquid crystal polyester precursor film of transfer printing on the metal base that has peel ply at least one interarea, above-mentioned liquid crystal polyester precursor film is contacted with above-mentioned peel ply, thereby acquisition comprises the operation of the 1st laminated body of this liquid crystal polyester precursor film and this metal base, above-mentioned the 1st laminated body is heat-treated, thereby obtain to comprise the operation of the 2nd laminated body of the liquid crystal polyester film that is substantially devoid of solvent and above-mentioned metal base, with the operation of peeling off above-mentioned liquid crystal polyester film from above-mentioned metal base.
In addition, the material of above-mentioned metal base is preferably aluminium, stainless steel, iron or copper.
In addition, above-mentioned peel ply is preferably the rubber-like elasticity layer.
In addition, the heat treatment of above-mentioned the 1st laminated body is preferably carried out under atmosphere of inert gases.
In addition, preferably also comprise operation and the above-mentioned operation that is wound into the 1st laminated body of web-like of debatching that above-mentioned the 1st laminated body is wound into web-like, the 1st laminated body of above-mentioned debatching is carried out the heat treatment of above-mentioned the 1st laminated body.
In addition, the preferred both ends that also are included in the width of above-mentioned the 1st laminated body are provided with the operation of sept and above-mentioned the 1st laminated body and above-mentioned sept are wound into the operation of web-like together, and above-mentioned the 1st laminated body that is wound into web-like is carried out the heat treatment of above-mentioned the 1st laminated body.
According to the present invention, when making the liquid crystal polyester film, to transfer printing liquid crystal polyester precursor film on the metal base that has peel ply on the interarea so that heat-treat under liquid crystal polyester precursor film and the peel ply state of contact, peel off gained liquid crystal polyester film then, therefore be reduced in the situation that produces flash of light in the liquid crystal polyester film, and avoid the liquid crystal polyester film and be difficult to situation about peeling off, and then make the liquid crystal polyester film easily from metal base.
Description of drawings
Fig. 1 is the process chart of the liquid crystal polyester film manufacturing method of embodiment of the present invention 1, (a) be to be illustrated in the operation that curtain coating on the base material contains the fluid composition of liquid crystal polyester and solvent, with the fluid composition drying, thereby obtain the figure of the operation of liquid crystal polyester precursor film, (b) be that expression is peeled off the operation of liquid crystal polyester precursor film and transfer printing liquid crystal polyester precursor film on metal base from base material, thereby obtain the figure of the operation of the 1st laminated body, (c) be that expression is heat-treated the 1st laminated body, thereby obtain the operation of the 2nd laminated body, and the figure that peels off the operation of liquid crystal polyester film from metal base.
Fig. 2 is illustrated in the manufacture method of liquid crystal polyester film of the present invention's the 2nd embodiment, and the 1st laminated body is wound into the figure of the operation of web-like with sept.
[symbol description]
1 ... fluid composition
2 ... base material
3 ... coating machine
5 ... the liquid crystal polyester precursor film
6 ... metal base
7 ... heating furnace
9 ... the liquid crystal polyester film
10 ... stripper roll
11 ... roller
12 ... sept
L1 ... the base material laminated body
L2 ... the 1st laminated body
L3 ... the 2nd laminated body
The specific embodiment
Below, embodiments of the present invention are described.
[working of an invention mode 1]
Embodiments of the present invention 1 shown in Figure 1.
The explanation of＜liquid crystal polyester film 〉
The liquid crystal polyester film of embodiment of the present invention 1 is the film of thickness 0.001～0.1mm of being formed by specific liquid crystal polyester, and moisture permeability is 0.5g/m
2Below the 24h.
This liquid crystal polyester is to have to demonstrate optical anisotropy when fusion, forms the polyester of the such characteristic of anisotropy molten mass under the temperature below 450 ℃.
As this liquid crystal polyester, preferably have following formula (1) expression construction unit (below, be called " formula (1) construction unit "), the construction unit that following formula (2) illustrates (below, be called " formula (2) construction unit "), and the construction unit that illustrates of following formula (3) (below, be called " formula (3) construction unit "), total content with respect to the entire infrastructure unit, the content of construction unit is 30～80mol% shown in the formula (1), the content of construction unit is 35～10mol% shown in the formula (2), and the content of construction unit is the liquid crystal polyester of 35～10mol% shown in the formula (3).
(1)-O-Ar
1-CO-
(2)-CO-Ar
2-CO-
(3)-X-Ar
3-Y-
(in the formula, Ar
1Expression phenylene or naphthylene, Ar
2The group of expression phenylene, naphthylene or following formula (4) expression, Ar
3The group of expression phenylene or following formula (4) expression, X and Y represent O or NH independently of one another.In addition, with Ar
1, Ar
2And Ar
3The aromatic rings bonded hydrogen atom can also be replaced by halogen atom, alkyl or aryl.)
(4)-Ar
11-Z-Ar
12-
(in the formula, Ar
11, Ar
12Represent phenylene or naphthylene independently of one another, Z represents O, CO or SO
2)
Formula (1) construction unit is the construction unit from aromatic hydroxy-carboxylic, as this aromatic hydroxy-carboxylic, can enumerate for example P-hydroxybenzoic acid, m-hydroxybenzoic acid, 6-hydroxyl-2-naphthoic acid, 3-hydroxyl-2-naphthoic acid, 4-hydroxyl-1-naphthoic acid etc.
Formula (2) construction unit is the construction unit from aromatic dicarboxylic acid, as this aromatic dicarboxylic acid, can enumerate for example terephthalic acid (TPA), M-phthalic acid, 2,6-naphthalene dicarboxylic acids, 1,5-naphthalene dicarboxylic acids, diphenyl ether-4,4 '-dicarboxylic acids, diphenyl sulphone (DPS)-4,4 '-dicarboxylic acids, benzophenone-4,4 '-dicarboxylic acids etc.
Formula (3) construction unit is from aromatic diol, has the aromatic amine of phenol hydroxyl or the construction unit of aromatic diamine.As this aromatic diol, can enumerate for example hydroquinones, resorcinol, 2,2-two (4-hydroxyl-3,5-3,5-dimethylphenyl) propane, two (4-hydroxy phenyl) ether, two-(4-hydroxy phenyl) ketone, two-(4-hydroxy phenyl) sulfone etc.
In addition, have the aromatic amine of phenol hydroxyl, can enumerate 4-amino-phenol (para-aminophenol), 3-amino-phenol (m-aminophenol) etc., as this aromatic diamine, can enumerate 1,4-phenylenediamine, 1,3-phenylenediamine etc. as this.
The liquid crystal polyester that uses among the present invention is solvent soluble, and so-called solvent soluble is meant and dissolves in solvent with the concentration more than the 1 quality % in the solvent of 50 ℃ of temperature.Solvent under this situation is any of the appropriate solvent that uses in the preparation of aftermentioned fluid composition 1, describes in detail in the back.
Have the liquid crystal polyester of solvent soluble as this,, comprise from the construction unit of aromatic amine and/or from the construction unit of aromatic diamine with phenol hydroxyl preferably as above-mentioned formula (3) construction unit.Promptly, as formula (3) construction unit, if at least one side who comprises X and Y is the construction unit of the NH (construction unit of formula (3 ') expression, below, be called " formula (3 ') construction unit "), then there is tendency to the solvent soluble excellence of appropriate solvent described later (non-proton property polar solvent), preferred.Especially preferably whole basically formula (3) construction units are formula (3 ') construction unit.In addition, this formula (3 ') construction unit except the solvent soluble that makes liquid crystal polyester fully, have at liquid crystal polyester on the point of low water absorbable more, also be preferred.
(3’)-X-Ar
3-NH-
(in the formula, Ar
3Identical with X with above-mentioned definition.)
Formula (1) construction unit is with respect to the total content of entire infrastructure unit, and preferably the scope at 30～80 moles of % contains, and more preferably the scope at 35～50 moles of % contains.The liquid crystal polyester that contains formula (1) construction unit with this mole fraction is fully kept liquid crystal liquid crystal property, also has the more excellent tendency of hear resistance.And then, if the aromatic hydroxy-carboxylic of formula (1) construction unit of also considering in the lump to derive is acquired, then as this aromatic hydroxy-carboxylic, preferred P-hydroxybenzoic acid and/or 6-hydroxyl-2-naphthoic acid.
Formula (2) construction unit is with respect to the total content of entire infrastructure unit, and preferably the scope at 35～10 moles of % contains, and more preferably the scope at 33～25 moles of % contains.The liquid crystal polyester that contains formula (2) construction unit with this mole fraction is fully kept liquid crystal liquid crystal property, also has the more excellent tendency of hear resistance.And then, if the aromatic dicarboxylic acid of formula (2) construction unit of also considering in the lump to derive is acquired,, be preferably selected from terephthalic acid (TPA), M-phthalic acid and 2, at least a kind of 6-naphthalenedicarboxylic acid then as this aromatic dicarboxylic acid.
Formula (3) construction unit is with respect to the total content of entire infrastructure unit, and more preferably the scope at 33～25 moles of % contains, and solvent soluble is better thus.
In addition, the gained liquid crystal polyester is embodied on the viewpoint of higher liquid crystal liquid crystal property, formula (2) construction unit and formula (3) are if the mole fraction of construction unit with [formula (2) construction unit]/[formula (3) construction unit] expression, is preferably 0.9/1～1/0.9 scope.
Below, the manufacture method of liquid crystal polyester is carried out simple declaration.
This liquid crystal polyester can be by various known method manufacturings.Making preferred liquid crystal polyester, promptly, under the situation of the liquid crystal polyester that constitutes by formula (1) construction unit, (2) construction unit and formula (3) construction unit, after the monomer of these construction units of will deriving is converted to ester and forms the property acid amides and form the property derivative, polymerization, thereby the method for making liquid crystal polyester is simple to operate, is preferred.
For above-mentioned ester formation property acid amides formation property derivative, explanation by way of example.
Form the property derivative as forming the property acid amides as this ester of aromatic hydroxy-carboxylic or aromatic dicarboxylic acid with monomer of carboxyl, can enumerate that this carboxyl becomes the high group of reactivities such as acyl chlorides, acid anhydrides for the reaction that promotes polyester or polyamide to generate or this carboxyl for generate by ester exchange acid amides exchange reaction polyester or polyamide and formation esters such as alcohols or ethylene glycol etc.
Form the property acid amides as the ester of the monomer that has the phenol hydroxyl as aromatic hydroxy-carboxylic or aromatic diol etc. and form the property derivative, can enumerate as for generate by ester exchange reaction polyester or polyamide make phenol hydroxyl and carboxylic acids formation ester etc.
In addition, as forming the property derivative as this acid amides of aromatic diamine with amino monomer, for example can enumerate for generate by the acid amides exchange reaction polyamide make amino and carboxylic acids form acid amides etc.
Wherein, in order to make liquid crystal polyester more easily; especially preferably with aromatic hydroxy-carboxylic; aromatic diol, aromatic amine, this monomer fatty acid anhydride acidylate of aromatic diamine with phenol hydroxyl and/or amino with phenol hydroxyl; form ester formation property acid amides formation property derivative (acylate); acyl group with this acylate carries out polymerization with the carboxyl with monomer of carboxyl then, to carry out the exchange of ester exchange acid amides, makes the method for liquid crystal polyester.
The manufacture method of this liquid crystal polyester is documented in that for example the spy opens the 2002-220444 communique or the spy opens in the 2002-146003 communique.
In acidylate, with respect to phenol hydroxyl and amino total amount, the addition of fatty acid anhydride is preferably 1～1.2 times of equivalent, more preferably 1.05～1.1 times of equivalents.When polymerization, there is the distillation of acylate or starting monomer in 1 times of equivalent of the addition deficiency of fatty acid anhydride and stops up the tendency of reaction system easily, in addition, is surpassing under the situation of 1.2 times of equivalents, has the painted significant tendency of gained liquid crystal polyester.
Acidylate was preferably reacted 5 minutes～10 hours down at 130～180 ℃, more preferably reacted 10 minutes～3 hours down at 140～160 ℃.
The fatty acid anhydride that uses in acidylate is from the viewpoint of price and operability, is preferably acetic anhydride, propionic andydride, butyric anhydride, isobutyric anhydride or is selected from wherein the mixture more than 2 kinds, is preferably acetic anhydride especially.
Polymerization after the acidylate heats up down with 0.1～50 ℃/minute ratio and to carry out preferably under 130～400 ℃, more preferably under 150～350 ℃, heats up down with 0.3～5 ℃/minute ratio and to carry out.
In addition, in polymerization, the acyl group of acylate is preferably 0.8～1.2 times of equivalent of carboxyl.
Therefore preferably when acidylate and/or polymerization, according to Le Xiateliai-Blang's law (principle that balance moves), balance can produce mobile, the aliphatic acid of by-product or unreacted fatty acid anhydride is distillated outside the system by evaporation etc.
In addition, acidylate or polymerization can also be carried out in the presence of catalyst.As this catalyst, can use known as the catalyst for polymerization of polyester in the past, can enumerate for example metal salt catalyst, N such as magnesium acetate, stannous acetate, butyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, organic compound catalyst such as N-dimethyl aminopyridine, N-methylimidazole.
In these catalyst, preferably use N, N-dimethyl aminopyridine, N-methylimidazole etc. contains the heterocyclic compound (opening the 2002-146003 communique referring to the spy) of 2 above nitrogen-atoms.
This catalyst adds fashionable input in the lump at monomer usually, need not must remove after acidylate.Under the situation of not removing this catalyst, can after acidylate, directly enter polymerization.
The liquid crystal polyester that obtains by this polymerization can be directly used in the present invention, but in order further to improve hear resistance or the such characteristic of liquid crystal liquid crystal property, preferably more macromolecule quantizes, and in this macromolecule quantizes, preferably carries out solid phase.Sequence of operations in this solid phase is described.The liquid crystal polyester of the lower molecular weight that taking-up obtains in above-mentioned polymerization is pulverized, and forms Powdered or sheet.Then, can with the liquid crystal polyester after should pulverizing in atmosphere of inert gases such as for example nitrogen, under 20～350 ℃, heat-treat such operation with solid state shape, thereby carry out solid phase with 1～30 hour.This solid phase can carry out while stirring, also can need not to stir, and carries out under the state that leaves standstill.In addition, the viewpoint from the liquid crystal polyester that obtains the suitable flow starting temperature of aftermentioned if the felicity condition of this solid phase is elaborated, then as reaction temperature, preferably surpasses 210 ℃, more preferably in 220 ℃～350 ℃ scope.Reaction time is preferably selected from 1～10 hour.
As the liquid crystal polyester that uses among the present invention, preferably its flow starting temperature is more than 250 ℃.If the flow starting temperature of this liquid crystal polyester in this scope, then forms under the situation of conductive layer (electrode) comprising on the layer of this liquid crystal polyester, between the layer that comprises this liquid crystal polyester and this conductive layer, there is the tendency of the higher tack of acquisition.Wherein so-called flow starting temperature refers in the melt viscosity of flowing test instrument is estimated, and under the pressure of 9.8MPa, the melt viscosity of liquid crystal polyester is the following temperature of 4800Pas.In addition, this flow starting temperature is as the index of liquid crystal polyester molecular weight, be known (going out the 95th page～105 pages of straight volumes " the synthetic one by one moulding of liquid crystal Port リ マ use-", シ one エ system シ one, distribution on June 5th, 1987) for those skilled in the art referring to for example for a short time.
The upper limit of the flow starting temperature of liquid crystal polyester is preferably below 350 ℃ by the soluble scope decision in solvent of this liquid crystal polyester.The upper limit of flow starting temperature is in this scope, and liquid crystal polyester is better to the dissolubility of solvent, and in addition, when obtaining aftermentioned fluid composition 1, its viscosity can obviously not increase, and therefore has the good tendency of operability of this fluid composition 1.In addition, for the flow starting temperature with liquid crystal polyester is controlled in this preferred range, the suitable optimization of polymerizing condition of above-mentioned solid phase polymerization is got final product.
The explanation of＜fluid composition 〉
Below, fluid composition 1 is described.
This fluid composition 1 comprises above-mentioned liquid crystal polyester and 2 kinds of compositions of solvent.
As this solvent, as long as dissolving liquid crystal polyester, just there is no particular limitation, can enumerate for example N, N-dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-, N-methyl caprolactam, N, dinethylformamide, N, N-DEF, N, N-diethyl acetyl are by halogeno-benzene phenols such as, N-methyl propanamide, methyl-sulfoxide, gamma-butyrolacton, methylimidazole alkane ketone, tetramethyl phosphoryl amine and ethyl cellosolve acetate and p-fluorophenol, parachlorophenol, perfluor phenol etc.These solvents may be used alone, or two or more kinds may be used in combination.
In these solvents, viewpoint from operability, be preferably selected from N, N-dimethylacetylamide, N-methyl-2-pyrrole be alkane ketone, N-methyl caprolactam, N slightly, dinethylformamide, N, N-DEF, N, the non-proton property polar solvent of N-diethyl acetamide, N-methyl propanamide, methyl-sulfoxide, gamma-butyrolacton, methylimidazole alkane ketone, tetramethyl phosphoryl amine and ethyl cellosolve acetate.
The use amount of this solvent is so long as can prepare the amount of the fluid composition 1 that contains the above liquid crystal polyester of 0.1 quality %, can suitably select according to the appropriate solvent kind, with respect to 100 mass parts solvents, be preferably 0.5～50 mass parts liquid crystal polyester, more preferably 5～30 mass parts.If liquid crystal polyester less than 0.5 mass parts, then the viscosity of fluid composition 1 is low excessively, and if surpass 50 mass parts, then there is the tendency of high viscosityization in the tendency that existence can't evenly be coated with.Inherent viscosity under when forming 0.5g/dl solution 25 ℃ of fluid composition 1 dilution that will obtain thus with above-mentioned organic solvent, this liquid crystal polyester is 0.1～10.
The manufacture method of＜liquid crystal polyester film 〉
And then the manufacture method of liquid crystal polyester film of the present invention is following order.
At first, shown in Fig. 1 (a), by coating machine 3 curtain coating aforesaid liquid composition 1 on base material 2, the dry stipulated time under the temperature of regulation.If so, then obtain to comprise the liquid crystal polyester precursor film 5 of the state of solvent.At this moment, liquid crystal polyester precursor film 5 obtains with the form at the base material laminated body L1 of its back laminate base material 2.Then, this base material laminated body L1 is wound into web-like.
Wherein, so-called liquid crystal polyester precursor film 5 is meant in the manufacture process of liquid crystal polyester film, in the stage before final goal thing liquid crystal polyester film, can change the film of liquid crystal polyester film by heat treatment into.
In addition,,, then have no particular limits preferred glass plate, stainless steel foil, PETG film, polyethylene film, polypropylene screen, polymethylpentene film, polytetrafluoroethylsheet sheet etc. as base material 2 as long as can peel off liquid crystal polyester precursor film 5.
In addition, as the method for curtain coating fluid composition 1 on base material 2, for example can enumerating, rolling method, gravure roll rubbing method, scraper plate rubbing method, scraper rubbing method, scraper rubbing method, dip coating, spraying process, curtain are coated with method, spray seam coating (slot coating) method, screen printing method etc.Wherein, calm easy to control and the more accurate more uniform viewpoint of thickness is set out, preferred scraper plate rubbing method or spray seam rubbing method.
Temperature and time during in addition, to dry liquid composition 1 has no particular limits.For example, the environment temperature during this fluid composition 1 of drying is preferably below 160 ℃, more preferably below 150 ℃, more preferably below 140 ℃.If this temperature is too high, then exist in the possibility that produces defective on the coated surface.On the other hand, if this temperature is low excessively, the time of then removing the cost of desolvating is elongated, and productivity probably can reduce.Therefore, the dry of this fluid composition 1 preferably carries out under the environment temperature more than 60 ℃ at least.
In addition, the residual solvent amount in the liquid crystal polyester precursor film 5 is preferably 18～2 quality %, more preferably 15～5 quality %.This residual solvent amount is that 18 quality % are following, and the surface that can be suppressed at liquid crystal polyester precursor film 5 produces the situation of viscosity, can prevent between the film adhering to each other.In addition, this residual solvent amount is that 2 quality % are above, then can keep the film-strength of liquid crystal polyester precursor film 5, as described below when base material 2 is peeled off liquid crystal polyester precursor film 5, perhaps when aftermentioned is heat-treated the 1st laminated body, can prevent the breakage of liquid crystal polyester film.
Prepare thus after the liquid crystal polyester precursor film 5, shown in Fig. 1 (b), the base material laminated body L1 of debatching web-like, peel off liquid crystal polyester precursor film 5 by base material 2, go up transfer printing liquid crystal polyester precursor film 5 to contact to the interarea (front) of the metal base 6 that on interarea (front), has the rubber-like elasticity layer then with the rubber-like elasticity layer.If so, the 1st laminated body L2 that obtains at the back side of liquid crystal polyester precursor film 5 superimposed layer metal base 6.Then, the 1st laminated body L2 is wound into web-like.
At this moment, at the back side of liquid crystal polyester precursor film 5 (that is, the face that contacts with base material 2) superimposed layer metal base 6, as long as the interarea (front) of base material 2 is level and smooth, the back side of liquid crystal polyester precursor film 5 also is level and smooth, can guarantee the tack of liquid crystal polyester precursor film 5 and metal base 6.
Wherein, as the material of metal base 6, can enumerate aluminium, stainless steel, iron, copper etc.Wherein, from the viewpoint of intensity and corrosion resistance, preferred especially stainless steel.
In addition, the thickness of metal base 6 is preferably in the scope of 20～200 μ m.As long as the thickness of metal base 6 is more than the 20 μ m, then the tolerance of metal base 6 impact vestiges improves, the reuse excellence.The thickness of metal base 6 is that 200 μ m are following, then easily is wound into web-like.
In addition, to the surface of metal base 6, as long as can guarantee the tack of metal base 6 and liquid crystal polyester precursor film 5, and aftermentioned liquid crystal polyester film 9 can carry out surface treatment arbitrarily from the fissility of metal base 6.For example, be difficult to peel off, can also carry out embossing processing on the surface of metal base 6 from metal base 6 in order to make the rubber-like elasticity layer.
In addition, as the rubber-like elasticity layer, can enumerate the polysiloxane series rubber elastic layer, fluorine is rubber elastic layer, acrylic rubber elastic layer etc.Wherein, preferred especially polysiloxane series rubber elastic layer.So long as the polysiloxane series rubber elastic layer, then with the tack of metal base 6 good the time, liquid crystal polyester film 9 described later is also good from the fissility of metal base 6.
The thickness of this rubber-like elasticity layer is preferably in the scope of 5～100 μ m.The thickness of rubber-like elasticity layer is that 5 μ m are above, then can fully relax the elastic modulus difference of metal base 6.The thickness of rubber-like elasticity layer is that 100 μ m are following, then when operation metal base 6, can prevent the fragmentation of rubber-like elasticity layer.
In addition, as the printing transferring method of liquid crystal polyester precursor film 5, there is no particular limitation, and shown in Fig. 1 (b), liquid crystal polyester precursor film 5 is clipped by pair of rolls 11,11 with metal base 6 and exerts pressure, and from improving productive viewpoint, is preferred.
In addition, as the transfer printing temperature of liquid crystal polyester precursor film 5, that is, the temperature of liquid crystal polyester precursor film 5 and metal base 6 during transfer printing, there is no particular limitation, preferably in 10～200 ℃ scope.This transfer printing temperature is more than 10 ℃, and is then good with the tack of metal base 6.This transfer printing temperature is below 200 ℃, and aftermentioned liquid crystal polyester film 9 is good from the fissility of metal base 6.
Prepare thus after the 1st laminated body, shown in Fig. 1 (c), the 1st laminated body L2 of debatching web-like under nitrogen atmosphere, with the temperature of regulation, heat-treats official hour to the 1st laminated body L2 continuously in heating furnace 7.If so, obtain to comprise the liquid crystal polyester film 9 that is substantially devoid of solvent and the 2nd laminated body L3 of metal base 6.
At this moment, because the heat treatment of the 1st laminated body L2 is carried out under nitrogen atmosphere, therefore can prevent in advance because the deterioration of the liquid crystal polyester film 9 that the oxidation of liquid crystal polyester causes.
Wherein, the heat treatment temperature of the 1st laminated body L2 is preferably in 200～350 ℃ scope.This heat treatment temperature is more than 200 ℃, increases the molecular weight of liquid crystal polyester by heat treatment, can manifest characteristic as liquid crystal polyester film 9 from liquid crystal polyester precursor film 5.This heat treatment temperature is below 350 ℃, can suppress the thermal decomposition of liquid crystal polyester film 9.
On the other hand, there is no particular limitation for the heat treatment time of the 1st laminated body L2, usually, with after programming rate is warming up to above-mentioned heat treatment temperature below 10 ℃/minute, kept under this temperature 0～10 hour.
In addition, there is no particular limitation to the heat treated mode of the 1st laminated body L2, except continuously by beyond the mode of heating furnace 7, adopting for example special mode of putting down in writing in the 2008-207537 communique of opening by volume to volume (roll form is supplied with raw material, and roll form is reeled and finished the mode of goods).
Prepare thus after the 2nd laminated body L3, shown in Fig. 1 (c), peel off liquid crystal polyester film 9 from metal base 6.At this moment, the interarea (front) at metal base 6 promptly is provided with the rubber-like elasticity layer on the face of liquid crystal polyester film 9 one sides, therefore can easily peel off liquid crystal polyester film 9 from metal base 6.
Wherein, as the stripping means of liquid crystal polyester film 9, there is no particular limitation, shown in Fig. 1 (c), uses a pair of stripper roll 10,10, and stripping metal base material 6 is preferred with the method for liquid crystal polyester film continuously.
In addition, thus after metal base 6 is peeled off liquid crystal polyester film 9, can also by methods such as solvent wash, UV processing, sided corona treatment, plasma treatment, flame treatment, remove polluter (polysiloxanes, fluorine-containing material etc.) as required from liquid crystal polyester film 9.
After metal base 6 is peeled off liquid crystal polyester film 9, finish the manufacturing process of liquid crystal polyester film 9 thus.
Thus, according to this manufacture method, in transfer printing on the metal base 6 that has the rubber-like elasticity layer on the interarea heat-treat under the state of liquid crystal polyester precursor film 5, peel off liquid crystal polyester film 9 from metal base 6 then.
Therefore, the technology that proposes with patent documentation 1 is different, can be reduced in the situation that produces flash of light on the liquid crystal polyester film 9.In addition, the technology that proposes with patent documentation 2 is different, can avoid liquid crystal polyester film 9 and be difficult to situation about peeling off from base material.In addition, compare with the technology that patent documentation 3 proposes, easy to manufacture.
In addition, adopt the manufacture method of volume to volume can make liquid crystal polyester film 9 continuously, therefore can improve the productivity of liquid crystal polyester film 9.
Mechanical properties excellence when the liquid crystal polyester film of making thus in addition, 9 heats.
[invention embodiment 2]
Embodiments of the present invention 2 shown in Figure 2.
In this embodiment 2, except when making liquid crystal polyester film 9, as shown in Figure 2, the sept 12 of the honeycomb shape (waveform cross sectional shape) of aluminum is set respectively in two ends of the width (arrow A, B direction) of the 1st laminated body L2, the 1st laminated body L2 is wound into web-like with sept 12, beyond the 1st laminated body L2 that is wound into web-like directly heat-treated with web-like, adopt same order with above-mentioned embodiment 1.
Therefore, in this embodiment 2, have the action effect same with above-mentioned embodiment 1.In addition,, therefore compare, can significantly save the room and time of the heat treatment needs of the 1st laminated body L2 with the situation that the 1st laminated body L2 of debatching web-like heat-treats because the heat treatment of the 1st laminated body L2 is directly carried out with web-like.In addition, owing to have sept,, also can easily remove and desolvate even therefore the 1st laminated body L2 directly is a web-like.
[other embodiments of invention]
In addition, at above-mentioned embodiment 1, in 2, to peel ply is that the situation of rubber-like elasticity layer describes, can also replace using or coupling rubber-like elasticity layer beyond peel ply (for example, the vacuum evaporation layer of chrome plating, nickel-coating such as phosphorus coating, chromium nitride, titanium nitride chromium, titanium carbide molybdenum, titanium nitride molybdenum, titanium nitride, titanium carbonitride, titanium carbide, TiAlN, zirconium nitride, carbon, triazine thiol, fluororesin etc. or deposited metal or by metallic substrate surface being carried out nitride layer that direct nitrogen treatment forms etc.).
In addition, in above-mentioned embodiment 1,2, the situation of under nitrogen atmosphere the 1st laminated body L2 being heat-treated is described, can also under the atmosphere of nitrogen inert gas (for example helium, argon gas etc.) in addition, carry out this heat treatment.In addition, in above-mentioned, use specific liquid crystal polyester, can also use liquid crystal polyester in addition.
[embodiment]
Below, embodiments of the invention are described.In addition, the present invention is not subjected to the qualification of embodiment.
＜contain the Production Example of the fluid composition of liquid crystal polyester and solvent 〉
In reactor, add 941g (5mol) 6-hydroxyl-2-naphthoic acid, 273g (2.5 moles) 4-amino-phenol, 415.3g (2.5 moles) M-phthalic acid and 1123g (11 moles) acetic anhydride with agitating device, torquemeter, nitrogen ingress pipe, thermometer and reflux cooler.After in reactor, fully replacing, under stream of nitrogen gas, be warming up to 150 ℃ with 15 minutes, keep this temperature (150 ℃) to reflux 3 hours with nitrogen.
Then, on one side distillation remove by-product acetic acid and the unreacted acetic anhydride that distillates, be warming up to 320 ℃ with 170 minutes on one side, will confirm that time point that moment of torsion raises is considered as reaction and finishes the taking-up content.The solid constituent that obtains thus is cooled to room temperature, pulverizes, under nitrogen atmosphere, kept 3 hours then, in solid phase, carry out polymerisation at 250 ℃ with Roughpulverizer.The powder that obtains thus arrives the distinctive striped style of liquid crystalline phase with polarized light microscope observing under 350 ℃.In addition,, be heated to 120 ℃, then can obtain consoluet clear solution if in the 92gN-N-methyl-2-2-pyrrolidone N-, add this powder of 8g.
＜on interarea, have a Production Example 1 of the metal base of rubber-like elasticity layer 〉
15kg polysiloxane series stripping treatment agent [SD7226 デ イ ス パ one ジ ヨ Application], 15kg toluene, 150g catalyst " SRX212 " are mixed, stir, thus preparation stripping treatment agent S1.Use has the coating mouth mould of width 1200mm, the coating machine of continuous stove, go up this stripping treatment agent of coating S1 at the soft aluminium foil (サ Application ア Le ミ ニ ウ system industry (strain) manufacturing) of thickness 100 μ m, drying oven with 110 ℃～130 ℃ of temperature is handled, thereby obtains to have on the front aluminium base of 10 μ m rubber-like elasticity layers.In addition, on the back side of this aluminium base, by with above-mentioned same method, form the rubber-like elasticity layer of 1 μ m, obtain to have positive 10 μ m, the aluminium base (M1) of the rubber-like elasticity layer of the back side 1 μ m.
＜on interarea, have a Production Example 2 of the metal base of rubber-like elasticity layer 〉
Except the stainless steel foil (Japanese metal (strain) manufacturing) of the soft aluminium foil of thickness 100 μ m being changed into thickness 50 μ m, with above-mentioned＜on interarea, have a Production Example 1 of the metal base of rubber-like elasticity layer same, obtain to have the stainless steel substrate (M2) of the rubber-like elasticity layer of positive 10 μ m, the back side 1 μ m.
＜embodiment 1 〉
Use has the coating mouth mould of width 1500mm, the coating machine of continuous stove, OPP film (stretched polypropylene films) go up coating according to＜contain the Production Example of the fluid composition of liquid crystal polyester and solvent the fluid composition that obtains, in the drying oven of 100 ℃～110 ℃ of temperature, handle, thereby obtain the laminated body that liquid crystal polyester precursor film and OPP film by thickness 50 μ m constitute.Peel off liquid crystal polyester precursor film from the OPP film, transfer printing liquid crystal polyester precursor film and the contact-making surface OPP film contacting with the rubber-like elasticity layer of 10 μ m of the aluminium base with rubber-like elasticity layer (M1), thereby obtain laminated body (1).The thermogravimetric amount determining device " TGA50 " that uses (strain) Shimadzu Seisakusho Ltd. to make with 10 ℃/minute of programming rates, is warming up to 250 ℃ from 66 ℃ with laminated body (1), by weight reduce calculate the residual solvent amount after, this residual solvent amount is 10%.
Then, the honeycomb sept of aluminum is set in two ends of laminated body (1), the honeycomb sept is wound into web-like with laminated body (1), pass through heat-treatment furnace, under nitrogen atmosphere, with 13 hours laminated body (1) is warming up to 270 ℃ by normal temperature, cooling then obtains the laminated body (2) that is made of liquid crystal polyester film and aluminium base.
Then, peel off the liquid crystal polyester film, thereby obtain the liquid crystal polyester film of thickness 42 μ m by laminated body (2).Gained liquid crystal polyester film is not adhere to each other with aluminium base, does not have the film of flash of light.The characteristic of gained liquid crystal polyester film is shown in table 1 in the lump.
＜embodiment 2 〉
Maximum temperature during except laminated body (1) heat treatment obtains the liquid crystal polyester film being 300 ℃ similarly to Example 1.Gained liquid crystal polyester film is not adhere to each other with aluminium base, does not have the film of flash of light.The characteristic of gained liquid crystal polyester film is shown in table 1 in the lump.
＜embodiment 3 〉
Except the aluminium base (M1) with rubber-like elasticity layer is stainless steel substrate (M2), obtain the liquid crystal polyester film similarly to Example 1.Gained liquid crystal polyester film is not adhere to each other with stainless steel substrate, does not have the film of flash of light.
＜comparative example 1 〉
Except being transferred to the soft aluminium foil (サ Application ア Le ミ ニ ウ system industry (strain) manufacturing) of thickness 100 μ m and obtaining, the contact-making surface with liquid crystal polyester precursor film and OPP film obtains the liquid crystal polyester film similarly to Example 1 the laminated body (1).Gained liquid crystal polyester film and soft aluminium foil are adhering to each other, can't peel off.
＜comparative example 2 〉
Use the film spreader, will according to＜contain the Production Example of the fluid composition of liquid crystal polyester and solvent the fluid composition that obtains is coated on the commercially available electrolytic copper foil (Copper Foils " 3EC-VLP " of the thickness 18 μ m that Mitsui Metal Co., Ltd.'s mining industry (strain) is made), in hot-air oven, 40 ℃ dry 24 hours down, thereby obtain the tape tree fat Copper Foil that the liquid crystal polyester precursor film by the Copper Foil of thickness 18 μ m and thickness 60 μ m constitutes.Then, gained tape tree fat Copper Foil in the hot-air oven under the nitrogen atmosphere, was warming up to 300 ℃ with 10 hours by 30 ℃, keeps down heat-treating in 3 hours at 300 ℃.By Copper Foil partially-etched remove of iron chloride, obtain the liquid crystal polyester film with gained tape tree fat Copper Foil.The characteristic of the liquid crystal polyester film that obtains thus is shown in table 1 in the lump.
The mensuration of the mechanical properties the during heating of＜liquid crystal polyester film 〉
For these embodiment 1,2 and comparative example 2, use ア イ テ イ one instrumentation system to drive the Measurement of Dynamic Viscoelasticity device " DVA-220 " that (strain) makes respectively, the mechanical properties when measuring the heating of liquid crystal polyester film by following condition determination.
Mode determination: stretch
Test film shape: length 10mm * width 4.5mm, the about 50 μ m of thickness
Static load: 650cN (static load is constant)
Dynamic strain/frequency number: 0.1% (10 μ m)/10Hz
Temperature program(me):, be warming up to 200 ℃ from 50 ℃ with 5 ℃/minute of programming rates
Measure: measure distance between primary stress and chuck, go out energy storage elastic modelling quantity, complex elastic modulus, tan δ, percentage elongation for per 1 ℃ by these data computation.Under the situation of test film fracture, adopt the value that is about under the fracture temperature before.
These measurement results are shown in table 1 in the lump.
Table 1
As shown in table 1, for being about to fracture energy storage elastic modelling quantity before, embodiment 1,2, and comparative example 2 is 2GPa, does not find significant difference between the three.On the other hand, for the percentage elongation that is about to before the fracture, comparative example 2 is 82%, and is 130% (that is, comparative example 2 about 1.6 times) in embodiment 1, is 159% (that is, about 1.9 times of comparative example 2) in embodiment 2.Clear and definite by this result, compare the mechanical properties excellence during embodiment 1,2 heating with comparative example 2.
[industrial applicability]
The present invention can use in purposes such as base material, surface coating (cover lay film), loudspeaker vibrations plates with base material, flexibility printed circuit board at heatproof zone.
Claims (6)
1. the manufacture method of a liquid crystal polyester film, it comprises: curtain coating contains the operation of the fluid composition of liquid crystal polyester and solvent on base material, will be on above-mentioned base material the fluid composition drying of curtain coating, thereby acquisition contains the operation of the liquid crystal polyester precursor film of above-mentioned solvent state, peel off the operation of above-mentioned liquid crystal polyester precursor film from above-mentioned base material, to the above-mentioned liquid crystal polyester precursor film of transfer printing on the metal base that has peel ply at least one interarea, above-mentioned liquid crystal polyester precursor film is contacted with above-mentioned peel ply, thereby acquisition comprises the operation of the 1st laminated body of this liquid crystal polyester precursor film and this metal base, above-mentioned the 1st laminated body is heat-treated, thereby obtain to comprise the operation of the 2nd laminated body of the liquid crystal polyester film that is substantially devoid of solvent and above-mentioned metal base, with the operation of peeling off above-mentioned liquid crystal polyester film from above-mentioned metal base.
2. the method for claim 1, wherein the material of above-mentioned metal base is aluminium, stainless steel, iron or copper.
3. method as claimed in claim 1 or 2, wherein, above-mentioned peel ply is the rubber-like elasticity layer.
4. as claim 1 or 3 described methods, wherein, the heat treatment of above-mentioned the 1st laminated body is carried out under atmosphere of inert gases.
5. as claim 1 or 3 described methods, wherein, also comprise the operation and the above-mentioned operation that is wound into the 1st laminated body of web-like of debatching that above-mentioned the 1st laminated body are wound into web-like, the 1st laminated body of above-mentioned debatching is carried out the heat treatment of above-mentioned the 1st laminated body.
6. as claim 1 or 3 described methods, wherein, the both ends that also are included in the width of above-mentioned the 1st laminated body are provided with the operation of sept and above-mentioned the 1st laminated body and above-mentioned sept are wound into the operation of web-like together, and above-mentioned the 1st laminated body that is wound into web-like is carried out the heat treatment of above-mentioned the 1st laminated body.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-030853 | 2010-02-16 | ||
| JP2010030853A JP5444581B2 (en) | 2010-02-16 | 2010-02-16 | Method for producing liquid crystal polyester film |
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| Publication Number | Publication Date |
|---|---|
| CN102218790A true CN102218790A (en) | 2011-10-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2011100669498A Pending CN102218790A (en) | 2010-02-16 | 2011-02-16 | Liquid crystal polyester film manufacturing method |
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| JP (1) | JP5444581B2 (en) |
| KR (1) | KR20110095162A (en) |
| CN (1) | CN102218790A (en) |
| TW (1) | TW201141922A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109628001A (en) * | 2018-11-09 | 2019-04-16 | 李梅 | A kind of sPS glue film and preparation method thereof for FPC industry |
| CN112440539A (en) * | 2019-08-27 | 2021-03-05 | 共同技研化学株式会社 | Laminated film and method for producing the same |
| CN113727843A (en) * | 2019-04-23 | 2021-11-30 | 株式会社可乐丽 | Thermoplastic liquid crystal polymer film, laminate, molded body, and method for producing same |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6086196B2 (en) * | 2012-09-28 | 2017-03-01 | 住友化学株式会社 | Method for producing liquid crystal polyester film |
| JP6332617B2 (en) * | 2014-04-16 | 2018-05-30 | 東洋紡株式会社 | Polyimide precursor film layer / inorganic substrate laminate, and method for producing the same, polyimide film layer / inorganic substrate laminate, and flexible electronic device |
| JP6332616B2 (en) * | 2014-04-16 | 2018-05-30 | 東洋紡株式会社 | Polymer precursor film layer / inorganic substrate laminate, and production method thereof, polymer film layer / inorganic substrate laminate production method, and flexible electronic device production method |
| JP6929555B2 (en) * | 2018-10-18 | 2021-09-01 | 共同技研化学株式会社 | Manufacturing method of metal-clad laminate |
| CN111196050B (en) | 2018-11-16 | 2021-09-14 | 佳胜科技股份有限公司 | Method and device for processing liquid crystal polymer film |
| TWI705995B (en) * | 2018-11-16 | 2020-10-01 | 佳勝科技股份有限公司 | Processing method of liquid crystal polymer film and device thereof |
| JP2021095520A (en) | 2019-12-18 | 2021-06-24 | 共同技研化学株式会社 | Liquid composition, liquid crystal polyester film and method for producing liquid crystal polyester film, and laminate film and method for producing laminate film |
| CN115477828A (en) | 2021-05-31 | 2022-12-16 | 富士胶片株式会社 | Polymer film and method for producing same, and laminate and method for producing same |
| JP2023006577A (en) | 2021-06-30 | 2023-01-18 | 富士フイルム株式会社 | Film and method for producing the same, and laminate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5529740A (en) * | 1994-09-16 | 1996-06-25 | Jester; Randy D. | Process for treating liquid crystal polymer film |
| JP5254901B2 (en) * | 1998-04-06 | 2013-08-07 | 株式会社クラレ | LIQUID CRYSTAL POLYMER FILM AND LAMINATE, PROCESS FOR PRODUCING THEM, AND MULTILAYER MOUNTED CIRCUIT BOARD |
| JP3968068B2 (en) * | 2003-09-30 | 2007-08-29 | 株式会社クラレ | Method for producing liquid crystal polymer film |
-
2010
- 2010-02-16 JP JP2010030853A patent/JP5444581B2/en active Active
-
2011
- 2011-02-15 KR KR1020110013127A patent/KR20110095162A/en not_active Application Discontinuation
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109628001A (en) * | 2018-11-09 | 2019-04-16 | 李梅 | A kind of sPS glue film and preparation method thereof for FPC industry |
| CN113727843A (en) * | 2019-04-23 | 2021-11-30 | 株式会社可乐丽 | Thermoplastic liquid crystal polymer film, laminate, molded body, and method for producing same |
| CN113727843B (en) * | 2019-04-23 | 2022-08-16 | 株式会社可乐丽 | Thermoplastic liquid crystal polymer film, laminate, molded body, and method for producing same |
| CN112440539A (en) * | 2019-08-27 | 2021-03-05 | 共同技研化学株式会社 | Laminated film and method for producing the same |
Also Published As
| Publication number | Publication date |
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| JP5444581B2 (en) | 2014-03-19 |
| JP2011167847A (en) | 2011-09-01 |
| TW201141922A (en) | 2011-12-01 |
| KR20110095162A (en) | 2011-08-24 |
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Application publication date: 20111019 |