CN109922956A - Laminate comprising polyimide film and hard conating - Google Patents

Laminate comprising polyimide film and hard conating Download PDF

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Publication number
CN109922956A
CN109922956A CN201780069665.XA CN201780069665A CN109922956A CN 109922956 A CN109922956 A CN 109922956A CN 201780069665 A CN201780069665 A CN 201780069665A CN 109922956 A CN109922956 A CN 109922956A
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CN
China
Prior art keywords
repetitive unit
laminate
represented
chemical formula
polyimide film
Prior art date
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Pending
Application number
CN201780069665.XA
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Chinese (zh)
Inventor
冈卓也
中川美晴
久野信治
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Ube Corp
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Ube Industries Ltd
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Publication of CN109922956A publication Critical patent/CN109922956A/en
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Classifications

    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B05D7/02—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 to macromolecular substances, e.g. rubber
    • B05D7/04—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 to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens

Abstract

The present invention relates to a kind of laminates, it includes films and hard conating containing polyimides, in above-mentioned polyimides, the total content of repetitive unit represented by repetitive unit represented by following chemical formula (2-1) and/or following chemical formula (2-2) is 50 moles of % or more relative to whole repetitive units.

Description

Laminate comprising polyimide film and hard conating
Technical field
The present invention relates to a kind of laminates, it includes the film (polyimide film) containing polyimides and are formed in the polyamides Hard conating in imines film, and the hardness of hard coating surface is high.
Background technique
For polyimide film, heat resistance, chemical resistance, mechanical strength, electrology characteristic, dimensional stability etc. It is excellent, therefore be widely used in fields such as electrical/electronic devices field, semiconductor fields.On the other hand, in recent years, with The arrival of advanced information society, the fiber optics of optical communication field or optical waveguide etc., field of display devices liquid crystal orientation film or The exploitation of the optical materials such as colored filter protective film is constantly in progress.Especially in field of display devices as glass substrate Substitute, the research of light weight and flexible excellent plastic base, the exploitation for the display that can be bent or round are just prevailing.Separately Outside, the substitute as the protection glass of protection display display surface is also carrying out grinding for plastic emulsion sheet or cover film Study carefully.It is therefore desirable to can be used in the optical material of the higher performance of such purposes.
Aromatic polyimide is substantially colored as yellowish-brown due to intramolecular conjugation, the formation of the mobile complex compound of charge. Therefore, the method as inhibition coloring, such as propose following methods: by importing fluorine atom to intramolecular, being assigned to main chain Flexibility imports the formation that bulky group hinders the mobile complex compound of intramolecular conjugation, charge as side chain etc., to make It shows the transparency.
In addition, it is also proposed that poly- by using half ester ring type or full-cream ring type that do not form the mobile complex compound of charge theoretically Acid imide come make its show the transparency method.Many use aromatic tetracarboxylic dianhydride as tetracarboxylic acid in particular, proposing Sour component, the half ester ring type polyimides for using ester ring type diamines high as the transparency of diamine component；And alicyclic ring is used Formula tetracarboxylic dianhydride is poly- as tetracarboxylic acid sour component, half ester ring type for having used aromatic diamine high as the transparency of diamine component Acid imide.
For example, in patent document 1, as that can manufacture, colorless and transparent, linear expansion coefficient is low simultaneously and elongation is excellent Polyimide film polyimide precursor, disclose following polyimide precursors, have from 2,2 '-bis- (trifluoromethyls) The structure of benzidine (TFMB) has as diamines source structure from pyromellitic acid dianhydride (PMDA) and 4, and 4 '-oxygen are double adjacent The structure of phthalic acid dianhydride (ODPA), with come from 1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA) and/or 1,2,4,5- ring The structure of hexane tetracarboxylic dianhydride (H-PMDA) is as dicarboxylic anhydride source structure.Patent Document 2 discloses a kind of poly- (amides Acid-acid imide) copolymer, by 1 as tetracarboxylic acid sour component, 2,3,4- cyclobutane tetracarboxylic dianhydrides, as diamine component 2,2 '-bis- (trifluoromethyl) benzidine and specifically the diamines containing imide is polymerize and is obtained.
It is public in patent document 3 as the polyimides for obtaining the excellent, mechanical property of the transparency also excellent polyimide film Following polyimides have been opened, have been obtained by heating polyimide precursor composition, which includes Use 1,2,3,4- cyclobutane tetracarboxylic dianhydride as tetracarboxylic acid sour component, use 2,2 '-dimethyl -4,4 '-benzidine or The aromatic series two such as 2,2 '-dimethyl -4,4 '-benzidine and 2,2 '-bis- (trifluoromethyl) benzidine, 4,4 '-oxygen diphenylamines Precursor and imidazole compound and/or trialkylamine compound of the amine as the polyimides of diamine component.In patent document Following polyimides are also disclosed in 3, use 1,2,3,4- cyclobutane tetracarboxylic dianhydrides and norcamphane -2- loop coil-α-ring penta 5,5 ", 6,6 "-tetracarboxylic dianhydride of ketone-α '-loop coil -2 "-norcamphane-uses 2,2 '-dimethyl -4 as tetracarboxylic acid sour component, 4 '-benzidines are as diamine component.
In addition, disclosing following polyimides in patent document 4,1,2,3,4- cyclobutane tetracarboxylic dianhydrides and drop are used 5,5 ", 6,6 "-tetracarboxylic dianhydride of camphane -2- loop coil-α-cyclopentanone-α '-loop coil -2 "-norcamphane-as tetracarboxylic acid sour component, and Use 2,2 '-dimethyl -4,4 '-benzidine or 2,2 '-dimethyl -4,4 '-benzidine and 2,2 '-bis- (fluoroforms Base) aromatic diamines such as benzidine, bis- (4- amino-benzene oxygen) benzene of 1,4-, 4,4 '-oxygen diphenylamines are as diamine component.
Polyimide film is used for various uses, difference depending on the application, such as protecting display display surface In the case where emulsion sheet or cover film, hard conating is set on polyimide film in order to improve the marresistance on surface.
For example, Patent Document 5 discloses a kind of hard conating integrated membranes, by constituting by polyimide resin composition Polyimide film surface formed hard conating form, which contains using 1,2,4,5- hexamethylene four Carboxylic acid dianhydride as tetracarboxylic acid sour component, using 2,2 '-dimethylbenzidines (2,2 '-dimethyl -4,4 '-benzidine) and 2, Polyimide resin and silicon dioxide microparticle of 2 '-bis- (trifluoromethyl) benzidine as diamine component.In the reality of patent document 5 It applies and also describes a kind of hard conating integrated membrane in example 5, be not added with being made of above-mentioned polyimide resin for silicon dioxide microparticle The surface of polyimide film be formed with hard conating.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2014-139302 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2005-336243 bulletin
Patent document 3: International Publication No. 2016/063993
Patent document 4: International Publication No. 2016/063988
Patent document 5: International Publication No. 2016/060213
Summary of the invention
Problems to be solved by the invention
As described above, difference depending on the application, is arranged hard conating on polyimide film, purpose is formed for it, it is desirable that The hard conating has higher hardness.
In addition, although polyimides heat resistance and chemical resistance are excellent, but then with the adaptation of other layers, There are many situation of cementability deficiency, sometimes can not be in the setting hard conating directly on a surface of polyimide film.In addition, allowing to In the case where the hard conating of formation directly on a surface of polyimide film, the hardness of hard coating surface is also insufficient sometimes.
The purpose of the present invention is to provide a kind of comprising polyimide film and hard conating and hard coating surface it is with high hardness Laminate.In addition, the object of the invention is also to provide a kind of hardness comprising polyimide film and hard conating, hard coating surface High and transparent also excellent laminate.
It is further an object that providing a kind of comprising polyimide film and being formed directly into the polyimide film The laminate with high hardness of hard conating and hard coating surface on surface.In addition, the object of the invention is also to provide a kind of packets Hardness containing polyimide film and the hard conating, hard coating surface that are formed directly on the surface of the polyimide film it is high and Transparent also excellent laminate.
Means for solving the problems
The present invention relates to items below.
1. a kind of laminate is the laminate comprising the film containing polyimides and hard conating, which is characterized in that
In above-mentioned polyimides,
The total content of repetitive unit represented by the following general formula (1) is more than 90 moles of % relative to whole repetitive units, and And
Repetitive unit represented by repetitive unit represented by following chemical formula (2-1) and/or following chemical formula (2-2) Total content is 50 moles of % or more relative to whole repetitive units.
[changing 1]
(in formula, A be comprising aromatic rings or 4 member rings or 6 member rings (can be 6 member rings of composition carbon atom be bonded to each other and Form the crosslinking ring of cross-linked structure) alicyclic structure 4 valence groups, B be the divalent group comprising aromatic rings or alicyclic structure. Wherein, the A contained by each repetitive unit and B can be the same or different.)
[changing 2]
2. the laminate as described in above-mentioned item 1, which is characterized in that in above-mentioned polyimides, above-mentioned chemical formula (2-1) institute table The total content of repetitive unit represented by the repetitive unit and/or above-mentioned chemical formula (2-2) shown is relative to whole repetitive units 60 moles of % or more.
3. the laminate as described in above-mentioned item 1, which is characterized in that in above-mentioned polyimides, above-mentioned chemical formula (2-1) institute table The content of the repetitive unit shown is 50 moles of % or more relative to whole repetitive units.
4. the laminate as described in any one of above-mentioned item 1~3, which is characterized in that
Above-mentioned polyimides is by the repetitive unit and/or above-mentioned chemical formula (2-2) institute table represented by above-mentioned chemical formula (2-1) The repetitive unit shown is constituted, alternatively,
Above-mentioned polyimides is by the repetitive unit and/or above-mentioned chemical formula (2-2) institute table represented by above-mentioned chemical formula (2-1) One or more of repetitive unit represented by the repetitive unit shown and above-mentioned general formula (1) is constituted, and in above-mentioned general formula (1), A is packet Alicyclic ring containing 4 member rings or 6 member rings (the crosslinking ring that can be bonded to each other and form cross-linked structure to constitute the carbon atom of 6 member rings) 4 valence groups of structure, B are the divalent group comprising aromatic rings.
5. the laminate as described in any one of above-mentioned item 1~3, which is characterized in that above-mentioned polyimides includes above-mentionedization Repetitive unit represented by repetitive unit represented by formula (2-1) and/or above-mentioned chemical formula (2-2) and above-mentioned general formula (1) institute The repetitive unit of expression, in above-mentioned general formula (1), it (can be 6 member rings of composition that A, which is comprising aromatic rings or 4 member rings or 6 member rings, Carbon atom is bonded to each other and forms the crosslinking ring of cross-linked structure) alicyclic structure 4 valence groups, B be include two aromatic rings Pass through the divalent group for the structure that ehter bond (- O-) links.
6. the laminate as described in above-mentioned item 5, which is characterized in that represented by above-mentioned polyimides is by above-mentioned general formula (1) One or more of repetitive unit is constituted, and in above-mentioned general formula (1), it (can be to constitute 6 member rings that A, which is comprising 4 member rings or 6 member rings, Carbon atom is bonded to each other and forms the crosslinking ring of cross-linked structure) alicyclic structure 4 valence groups, B be following chemical formula (B-1) Divalent group represented by represented divalent group, following chemical formula (B-2) passes through ehter bond (- O-) comprising two aromatic rings The divalent group of the structure to link,
Wherein, repetition represented by repetitive unit and/or above-mentioned chemical formula (2-2) represented by above-mentioned chemical formula (2-1) The total content of unit is 50 moles of % or more relative to whole repetitive units.
[changing 3]
7. the laminate as described in any one of above-mentioned item 1~6, which is characterized in that the pencil of above-mentioned hard coating surface is hard Degree is 2H or more.
8. the laminate as described in any one of above-mentioned item 1~7, which is characterized in that above-mentioned hard conating is by curable resin It ingredient or is formed including at least the solidfied material of curable resin ingredient and the hardening resin composition of inorganic filler.
9. a kind of manufacturing method of laminate, which is characterized in that
It is with following processes:
The hardening resin composition for including at least curable resin ingredient is coated on the film containing polyimides Process, wherein in above-mentioned polyimides, the total content of repetitive unit represented by the following general formula (1) is relative to whole repetitions Unit is more than 90 moles of %, and repetitive unit represented by following chemical formula (2-1) and/or following chemical formula (2-2) institute table The total content of the repetitive unit shown is 50 moles of % or more relative to whole repetitive units；With
The process that the curing of coating of above-mentioned hardening resin composition is formed into hard conating.
[changing 4]
(in formula, A be comprising aromatic rings or 4 member rings or 6 member rings (can be 6 member rings of composition carbon atom be bonded to each other and Form the crosslinking ring of cross-linked structure) alicyclic structure 4 valence groups, B be the divalent group comprising aromatic rings or alicyclic structure. Wherein, the A contained by each repetitive unit and B can be the same or different.)
[changing 5]
10. the manufacturing method of the laminate as described in above-mentioned item 9, which is characterized in that above-mentioned hardening resin composition into One step includes inorganic filler.
11. a kind of emulsion sheet or cover film of display display surface, which is characterized in that it includes any in above-mentioned item 1~8 Laminate described in.
12. a kind of optical component, display member, touch panel component or touch sensor component, which is characterized in that its Include laminate described in any one of above-mentioned item 1~8.
The effect of invention
According to the present invention it is possible to provide it is a kind of comprising polyimide film and hard conating and hard coating surface it is with high hardness Laminate.In addition, according to one method of the present invention, one kind can be provided comprising polyimide film and be formed directly into the polyamides The laminate with high hardness of hard conating and hard coating surface on the surface of imines film.
In addition, according to one method of the present invention, can provide a kind of comprising polyimide film and hard conating, hard conating table The high and transparent also excellent laminate of the hardness in face.It may, furthermore, provide a kind of includes polyimide film and direct shape At the high and transparent also excellent laminate of the hardness in hard conating, hard coating surface on the surface of the polyimide film. For example, the emulsion sheet or cover film of claimed display display surface have high transparency according to one method of the present invention can To provide polyimide film/hard painting that one kind can be suitable as the emulsion sheet or cover film (protective film) of the display display surface Layer laminate.Laminate of the invention suitable for optical component, display member, touch panel component or can for example touch Sensor component.
Specific embodiment
Laminate of the invention has film (polyimide film) and hard conating formed thereon containing polyimides.Firmly Coating can be directly arranged on the surface of polyimide film, or can also be arranged across other layers such as priming coat.According to The difference of purposes, hard conating can only be formed in the single side of polyimide film, or can also be formed in two-sided.In addition, hard apply Layer can be formed in the whole surface of the unilateral or bilateral of polyimide film, can also only be formed in a part on surface.In addition, Laminate of the invention is also included within the laminate for forming or being laminated with other layers on polyimide film or hard conating, in addition, also Laminate including being formed with hard conating after using polyimide film to produce semi-finished product on the polyimide film.Of the invention Laminate is in addition to including the form (form as membrane product circulation) as the polyimide film for being formed with hard conating on surface It in addition, further include being present in the product such as electronic products, optical goods, display product (including in component, manufacturing process Semi-finished product etc.) in form etc..
<<polyimide film>>
Polyimide film used in the present invention is the film containing polyimides, can contain filler (dioxy as needed The inorganic particles such as SiClx or organic granular), antioxidant, ultraviolet absorbing agent, dyestuff, pigment, the coupling agents such as silane coupling agent, Bottom coating, fire proofing, levelling agent, remover, other are commonly used in various additives in polyimide film etc..A certain In embodiment, from the aspect of film-strength, the flatness of film surface, or from the aspect of ease of manufacturing, cost, Polyimide film of the invention does not preferably contain the inorganic particles such as silica and organic granular (filler).
The polyimides for constituting polyimide film used in the present invention is following polyimides: the following general formula (1) institute table The total content of the repetitive unit shown is more than 90 moles of % relative to whole repetitive units, also, following chemical formula (2-1) is represented Repetitive unit and/or following chemical formula (2-2) represented by repetitive unit total content relative to whole repetitive units be 50 Mole % or more.It should be noted that also including following chemical formula (2-1) institute in repetitive unit represented by the following general formula (1) Repetitive unit represented by the repetitive unit and following chemical formula (2-2) of expression.
[changing 6]
(in formula, A be comprising aromatic rings or 4 member rings or 6 member rings (can be 6 member rings of composition carbon atom be bonded to each other and Form the crosslinking ring of cross-linked structure) alicyclic structure 4 valence groups, B be the divalent group comprising aromatic rings or alicyclic structure. Wherein, the A contained by each repetitive unit and B can be the same or different.)
[changing 7]
Repetitive unit represented by above-mentioned general formula (1) (also includes repetitive unit and upper represented by above-mentioned chemical formula (2-1) State repetitive unit represented by chemical formula (2-2)) total content relative to whole repetitive units be more than 90 moles of %, more preferably 95 moles of %~100 mole %, more preferably 98 moles of %~100 mole %.In one embodiment, particularly preferably above-mentioned The total content of repetitive unit represented by general formula (1) is 100 moles of %, that is, polyimides used in the present invention is by above-mentioned logical Repetitive unit represented by formula (1) is constituted.
In addition, repetition represented by repetitive unit represented by above-mentioned chemical formula (2-1) and/or above-mentioned chemical formula (2-2) The total content of unit is 50 moles of % or more, more preferably 60 moles of % or more relative to whole repetitive units.In a certain implementation In mode, repetitive unit represented by repetitive unit represented by above-mentioned chemical formula (2-1) and/or above-mentioned chemical formula (2-2) Total content is more preferably 70 moles of % or more, more preferably 80 moles of % or more relative to whole repetitive units, is particularly preferably 85 moles of % or more.
In one embodiment, polyimides more preferably includes repetitive unit represented by above-mentioned chemical formula (2-1), on It is preferably 50 moles of % or more that the content of repetitive unit represented by chemical formula (2-1) is stated relative to whole repetitive units sometimes. With used comprising repetitive unit represented by above-mentioned chemical formula (2-2) and do not included weight represented by above-mentioned chemical formula (2-1) The content of repetitive unit represented by multiple unit or above-mentioned chemical formula (2-1) is rubbed relative to whole repetitive units less than 50 The laminate of the film of the polyimides of your % is compared, and the content phase of repetitive unit represented by above-mentioned chemical formula (2-1) has been used It is high for the hardness of the laminate hard coating surface sometimes of the film for the polyimides that whole repetitive units are 50 moles of % or more.
The A of above-mentioned general formula (1) be comprising aromatic rings or 4 member rings or 6 member rings (can be 6 member rings of composition carbon atom that This in conjunction with and form the crosslinking ring of cross-linked structure) alicyclic structure 4 valence groups, from the transparency of polyimide film, in turn From the aspect of the transparency of laminate of the invention comprising the polyimide film, A preferably includes 4 member rings or 6 member rings (can Think that the carbon atom for constituting 6 member rings is bonded to each other and forms the crosslinking ring of cross-linked structure) alicyclic structure 4 valence groups.
Herein, (crosslinking of cross-linked structure can be bonded to each other and formd to constitute the carbon atom of 6 member rings as 6 member rings Ring) alicyclic structure, for example, following structures.
[changing 8]
In the A of general formula (1), 1 of 6 member rings or 2 carbon atoms can with other rings (can be 6 member rings, or Ring other than 6 member rings) it is shared.
4 valence groups of the alicyclic structure comprising 4 member rings of the A as general formula (1), such as preferred following radicals.The formula (A- 1) 4 valence groups are equivalent to repetition represented by repetitive unit represented by above-mentioned chemical formula (2-1) and above-mentioned chemical formula (2-2) A in unit.
[changing 9]
A's as general formula (1) (can be bonded to each other to constitute the carbon atom of 6 member rings comprising 6 member rings and form crosslinking The crosslinking ring of structure) alicyclic structure 4 valence groups, such as preferred following radicals.
[changing 10]
The 4 valence groups comprising aromatic rings of A as general formula (1), such as preferred following radicals.
[changing 11]
(in formula, Z1It is bonded for Direct Bonding or hexafluoroisopropylidenyl.)
It should be noted that the A of general formula (1), i.e. tetracarboxylic acid sour component are not limited to above-mentioned substance, it can be according to required Characteristic, purposes suitably select.
As the tetracarboxylic acid sour component for the repetitive unit for providing above-mentioned general formula (1), it is not particularly limited, for example, 2, Bis- (3,4- dicarboxyphenyi) hexafluoropropane of 2-, 4- (2,5- dioxotetrahydro furans -3- base) -1,2,3,4-tetralin -1, 2- dicarboxylic acids, pyromellitic acid, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acids, 3,3 ', 4,4 '-biphenyltetracarboxyacid acids, 2,3,3 ', 4 '-connection Benzene tertacarbonic acid, 4,4 '-oxygen, two phthalic acid, 3,3 ', 4,4 '-diphenylsulfone acids, meta-terphenyl -3,4,3 ', 4 '-tetracarboxylic acids Acid, para-terpheny -3,4,3 ', 4 '-tetrabasic carboxylic acids, double carboxyl phenyl dimethylsilanes, double di carboxyl phenyloxy diphenyl sulfides, sulphonyl Two phthalic acid of base, two phenoxy group of isopropylidene double phthalic acid, hexamethylene -1,2,4,5- tetrabasic carboxylic acid, [1,1 '-bis- (rings Hexane)] -3,3 ', 4,4 '-tetrabasic carboxylic acids, [1,1 '-bis- (hexamethylenes)] -2,3,3 ', 4 '-tetrabasic carboxylic acids, [1,1 '-bis- (hexamethylenes)] - 2,2 ', 3,3 '-tetrabasic carboxylic acids, 4,4 '-di-2-ethylhexylphosphine oxides (hexamethylene -1,2- dicarboxylic acids), 4,4 '-(propane -2,2- diyl) bis- (hexamethylenes Alkane -1,2- dicarboxylic acids), 4,4 '-oxos bis- (hexamethylene -1,2- dicarboxylic acids), 4,4 '-thiobis (hexamethylene -1,2- dicarboxylic acids), 4,4 '-sulfonyls bis- (hexamethylene -1,2- dicarboxylic acids), 4,4 '-(dimethylsilane diyls) bis- (hexamethylene -1,2- dicarboxylic acids), 4,4 '-(tetrafluoropropane -2,2- diyls) bis- (hexamethylene -1,2- dicarboxylic acids), bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acid, It is bicyclic [2.2.1] heptane -2,3,5- tricarboxylic acids of 6- (carboxymethyl), bicyclic [2.2.2] octane -2,3,5,6- tetrabasic carboxylic acid, bicyclic [2.2.2] octyl- 5- alkene -2,3,7,8- tetrabasic carboxylic acid, tricyclic [4.2.2.02,5] decane -3,4,7,8- tetrabasic carboxylic acid, tricyclic [4.2.2.02,5] decyl- 7- alkene -3,4,9,10- tetrabasic carboxylic acid, 9- oxatricyclo [4.2.1.02,5] nonane -3,4,7,8- tetracarboxylic acid Acid, decahydro -1,4:5,8- dimethanonaphthalene -2,3,6,7- tetrabasic carboxylic acid, norcamphane -2- loop coil-α-cyclopentanone-α '-loop coil -2 "-drop Camphane -5,5 ", the derivative (tetracarboxylic dianhydride etc.) of 6,6 "-tetrabasic carboxylic acids, 1,2,3,4- cyclobutane tetrabasic carboxylic acid and these tetrabasic carboxylic acids Deng.Tetracarboxylic acid sour component can be used alone, and can also be used in combination of two or more.It should be noted that among these, (tetracarboxylic acid acids etc. indicates tetrabasic carboxylic acid and tetracarboxylic dianhydride, tetrabasic carboxylic acid silyl ester, four to 1,2,3,4- cyclobutane tetracarboxylic acid acids etc. The tetracarboxylic acid derivatives such as carboxylate, four carboxyl acyl chlorides) it is to provide repetitive unit and above-mentionedization represented by above-mentioned chemical formula (2-1) The tetracarboxylic acid sour component of repetitive unit represented by formula (2-2).
The B of above-mentioned general formula (1) is the divalent group comprising aromatic rings or alicyclic structure.In particular, being packet in the A of general formula (1) Alicyclic ring containing 4 member rings or 6 member rings (the crosslinking ring that can be bonded to each other and form cross-linked structure to constitute the carbon atom of 6 member rings) In the case where 4 valence groups of structure, B is preferably the divalent group for including aromatic rings.
The divalent group comprising aromatic rings of B as general formula (1), such as preferred following radicals.The formula (B-1) and formula (B- 2) divalent group is equivalent to repetition represented by repetitive unit represented by above-mentioned chemical formula (2-1) and above-mentioned chemical formula (2-2) B in unit.
[changing 12]
The divalent group comprising aromatic rings of B as general formula (1) further preferably passes through ehter bond (- O-) comprising two aromatic rings The divalent group (aromatic group of ether-containing key) of the structure to link.As long as the aromatic group of ether-containing key includes at least one Ehter bond, comprising 3 or more aromatic rings, also may include will by the bonding other than the ehter bonds such as Direct Bonding The structure that two aromatic rings link.In addition, aromatic rings can be replaced the substituent groups such as methyl, trifluoromethyl, phenyl.It needs It is noted that the position of substitution is not particularly limited.
The aromatic rings for including in the aromatic group of ether-containing key is preferably phenyl ring.In one embodiment, it is sometimes preferred to For substituted or unsubstituted phenylene, further preferably unsubstituted phenylene.
The number for the aromatic rings for including in the aromatic group of ether-containing key is preferably 6 or less, more preferably 4 or less. In one embodiment, the number for the aromatic rings for including in the aromatic group of ether-containing key is preferably 3 or less sometimes.
The aromatic group of ether-containing key also may include the knot that 2 aromatic rings link by the bonding other than ehter bond Structure, generally, it is preferred to which all aromatic rings are linked by ehter bond.
The mutual coupling position of aromatic rings is not particularly limited, in general, relative to the amide groups (- CONH-) being bonded with A or The mutual connection group of person's aromatic rings is preferably bonded in 3 or 4.In one embodiment, relative to being bonded with A Amide groups (- CONH-) or the mutual connection group of aromatic rings are preferably bonded at 4 sometimes.
As the aromatic group of ether-containing key, such as preferred following radicals.
[changing 13]
(in formula, n1Indicate 1~3 integer, X1、X2Each independently represent selected from by hydrogen atom, methyl, trifluoromethyl, One of the group of phenyl composition.)
Divalent group as formula (B-3), wherein particularly preferred following radicals.
[changing 14]
(in formula, n2Indicate 1~3 integer.)
The divalent group comprising aromatic rings of B as general formula (1), for example, following radicals.Following formula (B-4) Represented group also includes that the group of above-mentioned formula (B-1) and above-mentioned formula (B-2) is shown following as illustration in addition to this Formula (B-4).
[changing 15]
(in formula, m1Indicate 0~3 integer, m2Indicate 0~3 integer.Y1、Y2、Y3It each independently represents selected from by hydrogen One of atom, methyl, group of trifluoromethyl composition, Q1、Q2It each independently represents Direct Bonding or selects free style :- One of NHCO- ,-CONH- ,-COO-, group of the composition of group represented by-OCO-.)
In the group represented by formula (B-4), the mutual coupling position of aromatic rings is not particularly limited, relative to A key The mutual connection group of the amide groups (- CONH-) or aromatic rings of conjunction is preferably bonded at 4 sometimes.Formula (B-4) is represented Group there is (m in the case where aromatic rings1And m2In the case where 0), it is sometimes preferred to can have substituent group (Y1) To phenylene.In addition, can replace on aromatic rings has methyl or trifluoromethyl, carboxyl, the position of substitution to be not particularly limited.
As the divalent group [except the divalent group of above-mentioned formula (B-1) and above-mentioned formula (B-2)] of formula (B-4), such as preferably Following radicals.
[changing 16]
The divalent group comprising alicyclic structure of B as general formula (1), preferably comprises the divalent base of the alicyclic structure of 6 member rings Group, such as preferred following radicals.
[changing 17]
It should be noted that B, the i.e. diamine component of general formula (1) is also not limited to above-mentioned substance, it can be according to required Characteristic, purposes suitably select.
As the diamine component for the repetitive unit for providing above-mentioned general formula (1), it is not particularly limited, for example, 2, 2 '-dimethyl -4,4 '-benzidine (tolidine), p-phenylenediamine, m-phenylene diamine (MPD), benzidine, 3,3 '-diamino-connection Benzene, 2,2 '-bis- (trifluoromethyl) benzidine, 3,3 '-bis- (trifluoromethyl) benzidine, 4,4 '-diaminobenzene formailides, 3, 4 '-diaminobenzene formailides, N, N '-bis- (4- aminophenyl) terephthalamides, N, N '-TOPOT 2,2′ p phenylenebis (p-aminophenyl Formamide), 4- amino-benzene oxygen -4- diaminobenzoic acid ester, bis- (4- aminophenyl) terephthalates, biphenyl -4,4 '-two Bis- (4- aminophenyl) esters of carboxylic acid, TOPOT 2,2′ p phenylenebis (P aminobenzoates), bis- (4- aminophenyls)-[1,1 '-biphenyl] -4, 4 '-dicarboxylic esters, [1,1 '-biphenyl] -4,4 '-diyls bis- (4-aminobenzoic acid esters), 4,4 '-oxygen diphenylamines, 3,4 '-oxygen hexichol Amine, 3,3 '-oxygen diphenylamines, (4- amino-benzene oxygen) benzene bis- to di-2-ethylhexylphosphine oxide (phenylenediamine), 1,3-, bis- (the 3- aminobenzene oxygen of 1,3- Base) benzene, bis- (4- amino-benzene oxygen) benzene of 1,4-, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, 4,4 '-bis- (3- amino-benzene oxygens) Bis- (4- (4- amino-benzene oxygen) phenyl) hexafluoropropane of biphenyl, 2,2-, bis- (4- aminophenyl) hexafluoropropane of 2,2-, bis- (4- ammonia Base phenyl) sulfone, 3,3 '-bis- (trifluoromethyl) benzidine, 3,3 '-bis- ((amino-benzene oxygen) phenyl) propane, 2,2 '-bis- (3- ammonia Base -4- hydroxy phenyl) hexafluoropropane, bis- (4- (4- amino-benzene oxygen) diphenyl) sulfones, bis- (4- (3- amino-benzene oxygen) hexichol Base) sulfone, octafluorobiphenyl amine, 3,3 '-dimethoxy-4 's, 4 '-benzidines, 3,3 '-two chloro- 4,4 '-benzidines, 3, 3 '-two fluoro- 4,4 '-benzidines, 1,4- diaminocyclohexane, 1,4- diamino -2- hexahydrotoluene, 1,4- diamino - 2- ethyl cyclohexane, 1,4- diamino -2- n-propyl hexamethylene, 1,4- diamino -2- isopropyl cyclohexane, 1,4- diamino - 2- n-butyl cyclohexane, 1,4- diamino -2- isobutyl butylcyclohexane, 1,4- diamino -2- sec-butyl hexamethylene, 1,4- diamino Bis- (amino methyl) hexamethylenes of base -2- t-butylcyclohexane, 1,2- diaminocyclohexane, 1,3- diamino cyclobutane, 1,4-, 1, Bis- (amino methyl) hexamethylenes of 3-, diamino bicyclic heptane, bis aminomethyl norbornane, diamino oxygroup norbornane, two Aminomethoxy norbornane, isophorone diamine, diamino tristane, bis aminomethyl tristane, bis- (aminocyclohexyls Base) methane, bis- (aminocyclohexyl) isopropylidenes, 6,6 '-bis- (3- amino-benzene oxygen) -3,3,3 ', 3 '-tetramethyl -1,1 '-spiral shells Double indanes, 6,6 '-bis- (4- amino-benzene oxygen) -3,3,3 ', 3 '-tetramethyl -1,1 '-spirobiindenes are full etc..Diamine component can be single Solely using one kind, can also be used in combination of two or more.It should be noted that among these, 2,2 '-dimethyl -4,4 '-two Aminobphenyl is to provide the diamine component of repetitive unit represented by above-mentioned chemical formula (2-1), 2,2 '-bis- (trifluoromethyl) biphenyl Amine is to provide the diamine component of repetitive unit represented by above-mentioned chemical formula (2-2).
As described above, also comprising weight represented by above-mentioned chemical formula (2-1) in repetitive unit represented by above-mentioned general formula (1) Repetitive unit represented by multiple unit and above-mentioned chemical formula (2-2).Repetitive unit represented by above-mentioned chemical formula (2-1) is that A is Repetition represented by above-mentioned general formula (1) of the 4 valence groups, B of above-mentioned chemical formula (A-1) for the divalent group of above-mentioned chemical formula (B-1) Unit, repetitive unit represented by above-mentioned chemical formula (2-2) be A be 4 valence groups of above-mentioned chemical formula (A-1), B is above-mentioned chemistry Repetitive unit represented by the above-mentioned general formula (1) of the divalent group of formula (B-2).
In one embodiment, the polyimides of polyimide film used in the present invention is constituted preferably by as four 1,2,3,4- cyclobutane tetracarboxylic acid acids of carboxylic acid composition etc. and 2,2 ' as diamine component-dimethyl -4,4 '-benzidine And/or 2,2 '-bis- (trifluoromethyl) benzidine obtain polyimides, i.e. by the repetition list represented by above-mentioned chemical formula (2-1) The polyimides that repetitive unit represented by first and/or above-mentioned chemical formula (2-2) is constituted.
In addition, in one embodiment, constitute the polyimides of polyimide film used in the present invention preferably by 1,2,3,4- cyclobutane tetracarboxylic acid acids as tetracarboxylic acid sour component etc. or 1,2,3,4- cyclobutane tetracarboxylic acid acids etc. in addition to this Comprising 4 member rings or 6 member rings (the crosslinking ring that can be bonded to each other and form cross-linked structure to constitute the carbon atom of 6 member rings) One or more of tetracarboxylic acid acids of alicyclic structure etc., as diamine component 2,2 '-dimethyl -4,4 '-benzidine and/ Or 2,2 '-bis- (trifluoromethyl) benzidine or 2,2 '-dimethyl -4,4 '-benzidine and/or 2,2 '-bis- (trifluoromethyls) The polyimides that one or more of benzidine and the diamines (i.e. aromatic diamine) comprising aromatic rings in addition to this obtain, i.e., The repetitive unit represented by the repetitive unit and/or above-mentioned chemical formula (2-2) represented by above-mentioned chemical formula (2-1) and except this with It (can be that the carbon atom of 6 member rings of composition is bonded to each other and forms the crosslinking of cross-linked structure that outer A, which is comprising 4 member rings or 6 member rings, Ring) 4 valence groups of alicyclic structure, in repetitive unit represented by the above-mentioned general formula (1) that B is the divalent group comprising aromatic rings More than one constitute polyimides.In the embodiment, diamine component contains 2,2 '-dimethyl -4,4 '-benzidines And/or 2, in the case that other other than 2 '-bis- (trifluoromethyl) benzidine include diamines of aromatic rings, preferably comprise comprising two The diamines that a aromatic rings passes through the ehter bond (- O-) structure to link.That is, the polyimides of composition polyimide film is packet by A Alicyclic ring containing 4 member rings or 6 member rings (the crosslinking ring that can be bonded to each other and form cross-linked structure to constitute the carbon atom of 6 member rings) 4 valence groups, the B of structure are divalent group represented by above-mentioned chemical formula (B-1), divalent base represented by above-mentioned chemical formula (B-2) Represented by the above-mentioned general formula (1) of the divalent group of group or the structure to be linked comprising two aromatic rings by ehter bond (- O-) One or more of repetitive unit is constituted, wherein [A is above-mentioned chemical formula to repetitive unit represented by above-mentioned chemical formula (2-1) (A-1) repetitive unit represented by the above-mentioned general formula (1) of 4 valence groups, the divalent group that B is above-mentioned chemical formula (B-1)] and/or [A is 4 valence groups of above-mentioned chemical formula (A-1) to repetitive unit represented by above-mentioned chemical formula (2-2), B is above-mentioned chemical formula (B- 2) repetitive unit represented by the above-mentioned general formula (1) of divalent group] total content relative to whole repetitive units be preferably 50 to rub You are % or more.
It, can rubbing less than 10 with whole repetitive units in the polyimides for constituting polyimide film used in the present invention Your the % range below of %, preferably 5 moles of % or less, more preferably 2 moles includes repetition list represented by above-mentioned general formula (1) Member (also including repetitive unit represented by repetitive unit and above-mentioned chemical formula (2-2) represented by above-mentioned chemical formula (2-1)) with One or more of other outer repetitive units.
As the tetracarboxylic acid sour component and diamine component of other repetitive units is provided, it is not particularly limited, other well known four Carboxylic acids, well known Diamines can be used.
As the tetracarboxylic acid sour component of other repetitive units is provided, for example, 2,2- bis- (3,4- dicarboxyphenyis) six Fluoro-propane, 4- (2,5- dioxotetrahydro furans -3- base) -1,2,3,4-tetralin -1,2- dicarboxylic acids, pyromellitic acid, 3,3 ', The adjacent benzene two of 4,4 '-benzophenone tetrabasic carboxylic acids, 3,3 ', 4,4 '-biphenyltetracarboxyacid acids, 2,3,3 ', 4 '-biphenyltetracarboxyacid acids, 4,4 '-oxygen two Formic acid, 3,3 ', 4,4 '-diphenylsulfone acids, meta-terphenyl -3,4,3 ', 4 '-tetrabasic carboxylic acids, para-terpheny -3,4,3 ', 4 '-tetracarboxylic acids Sour, double carboxyl phenyl dimethylsilanes, double di carboxyl phenyloxy diphenyl sulfides, two phthalic acid of sulfonyl, isopropylidene two The double phthalic acid of phenoxy group, hexamethylene -1,2,4,5- tetrabasic carboxylic acid, [1,1 '-bis- (hexamethylenes)] -3,3 ', 4,4 '-tetrabasic carboxylic acids, [1,1 '-bis- (hexamethylenes)] -2,3,3 ', 4 '-tetrabasic carboxylic acids, [1,1 '-bis- (hexamethylenes)] -2,2 ', 3,3 '-tetrabasic carboxylic acids, 4,4 '-Asias Methyl bis- (hexamethylene -1,2- dicarboxylic acids), 4,4 '-(propane -2,2- diyls) bis- (hexamethylene -1,2- dicarboxylic acids), 4,4 '-oxos Bis- (hexamethylene -1,2- dicarboxylic acids), 4,4 '-thiobis (hexamethylene -1,2- dicarboxylic acids), 4,4 '-sulfonyls it is bis- (hexamethylene -1, 2- dicarboxylic acids), 4,4 '-(dimethylsilane diyls) bis- (hexamethylene -1,2- dicarboxylic acids), 4,4 '-(tetrafluoropropane -2,2- diyls) Bis- (hexamethylene -1,2- dicarboxylic acids), octahydro pentalene -1,3,4,6- tetrabasic carboxylic acid, bicyclic [2.2.1] heptane -2,3,5,6- Bicyclic [2.2.1] heptane -2,3,5- tricarboxylic acids of tetrabasic carboxylic acid, 6- (carboxymethyl), bicyclic [2.2.2] octane -2,3,5,6- tetrabasic carboxylic acid, Bicyclic [2.2.2] octyl- 5- alkene -2,3,7,8- tetrabasic carboxylic acid, tricyclic [4.2.2.02,5] decane -3,4,7,8- tetrabasic carboxylic acid, tricyclic [4.2.2.02,5] decyl- 7- alkene -3,4,9,10- tetrabasic carboxylic acid, 9- oxatricyclo [4.2.1.02,5] nonane -3,4,7,8- tetracarboxylic acid Acid, decahydro -1,4:5,8- dimethanonaphthalene -2,3,6,7- tetrabasic carboxylic acid, norcamphane -2- loop coil-α-cyclopentanone-α '-loop coil -2 "-drop Camphane -5,5 ", 6,6 "-tetrabasic carboxylic acids, 1,2,3,4- cyclobutane tetrabasic carboxylic acid, 1,2,3,4- pentamethylene tetrabasic carboxylic acid and these tetrabasic carboxylic acids Derivative (tetracarboxylic dianhydride etc.) etc..In addition, the diamine component being combined is not to provide the repetitive unit of above-mentioned general formula (1) Diamine component in the case where, the tetracarboxylic acid sour component of other repetitive units may be as providing the repetition of above-mentioned general formula (1) Substance illustrated by the tetracarboxylic acid sour component of unit.
As the diamine component of other repetitive units is provided, for example, 2,2 '-dimethyl -4,4 '-diamino connection Benzene (tolidine), p-phenylenediamine, m-phenylene diamine (MPD), benzidine, 3,3 '-diamino-biphenyl, 2,2 '-bis- (trifluoromethyls) connection Aniline, 3,3 '-bis- (trifluoromethyl) benzidine, 4,4 '-diaminobenzene formailides, 3,4 '-diaminobenzene formailides, N, N '-bis- (4- aminophenyl) terephthalamides, N, N '-TOPOT 2,2′ p phenylenebis (Para Amino Benzamide), 4- amino-benzene oxygen -4- It is diaminobenzoic acid ester, bis- (4- aminophenyl) terephthalates, bis- (4- aminophenyl) esters of biphenyl -4,4 '-dicarboxylic acids, right Phenylene bis- (P aminobenzoates), bis- (4- aminophenyls)-[1,1 '-biphenyl] -4,4 '-dicarboxylic esters, [1,1 '-connection Benzene] it is -4,4 '-diyls bis- (4-aminobenzoic acid esters), 4,4 '-oxygen diphenylamines, 3,4 '-oxygen diphenylamines, 3,3 '-oxygen diphenylamines, right Bis- (4- amino-benzene oxygen) benzene of di-2-ethylhexylphosphine oxide (phenylenediamine), 1,3-, bis- (3- amino-benzene oxygen) benzene of 1,3-, bis- (the 4- amino of 1,4- Phenoxy group) benzene, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, 4,4 '-bis- (3- amino-benzene oxygen) biphenyl, bis- (4- (the 4- ammonia of 2,2- Phenoxyl) phenyl) hexafluoropropane, bis- (4- aminophenyl) hexafluoropropane of 2,2-, bis- (4- aminophenyl) sulfones, 3,3 '-bis- (three Methyl fluoride) benzidine, 3,3 '-bis- ((amino-benzene oxygen) phenyl) propane, 2,2 '-bis- (3- amino-4-hydroxylphenyl) hexafluoros third Alkane, bis- (4- (4- amino-benzene oxygen) diphenyl) sulfones, bis- (4- (3- amino-benzene oxygen) diphenyl) sulfones, octafluorobiphenyl amine, 3,3 '- Dimethoxy-4 ', 4 '-benzidines, 3,3 '-two chloro- 4,4 '-benzidines, 3,3 '-two fluoro- 4,4 '-benzidines, 1,4- diaminocyclohexane, 1,4- diamino -2- hexahydrotoluene, 1,4- diamino -2- ethyl cyclohexane, 1,4- diamino - 2- n-propyl hexamethylene, 1,4- diamino -2- isopropyl cyclohexane, 1,4- diamino -2- n-butyl cyclohexane, 1,4- diamino Base -2- isobutyl butylcyclohexane, 1,4- diamino -2- sec-butyl hexamethylene, 1,4- diamino -2- t-butylcyclohexane, 1,2- bis- Bis- (amino methyl) hexamethylenes of aminocyclohexane, 1,3- diamino cyclobutane, 1,4-, bis- (amino methyl) hexamethylenes of 1,3-, two Amino norbornane, bis aminomethyl norbornane, diamino oxygroup norbornane, diamino ylmethoxy norbornane, different Buddhist That ketone diamines, diamino tristane, bis aminomethyl tristane, bis- (aminocyclohexyl) methane, bis- (aminocyclohexyls) Isopropylidene, 6,6 '-bis- (3- amino-benzene oxygen) -3,3,3 ', 3 '-tetramethyl -1,1 '-spirobiindenes are full, 6,6 '-bis- (4- amino Phenoxy group) -3,3,3 ', 3 '-tetramethyls -1,1 '-spirobiindene is full etc..In addition, the tetracarboxylic acid sour component being combined is not to provide In the case where the tetracarboxylic acid sour component for stating the repetitive unit of general formula (1), the diamine component of other repetitive units may be as mentioning Substance illustrated by diamine component for the repetitive unit of above-mentioned general formula (1).
Polyimide film can for example manufacture as follows.Wherein, the manufacturing method of polyimide film of the invention is not limited to Manufacturing method below.
Firstly, reacting tetracarboxylic acid sour component and synthesis of polyimides precursor with diamine component, polyimide precursor is obtained Solution (polyimide precursor composition).Polyimide precursor can classify are as follows: 1) polyamic acid (or also referred to as polyamide Acid)；2) poly amic acid ester (at least part of the H of the carboxyl of polyamic acid is alkyl)；3) 4) polyamic acid silyl ester (at least part of the H of the carboxyl of polyamic acid is aIkylsilyl groups).Polyimide precursor can be according to each classification It is easily made using manufacturing method below.
1) polyamic acid
For polyimide precursor of the invention, make in a solvent as tetracarboxylic acid sour component tetracarboxylic dianhydride and diamines at Point with substantially equimolar, preferably diamine component relative to tetracarboxylic acid sour component molar ratio [molal quantity/tetrabasic carboxylic acid of diamine component at Point molal quantity] be preferably 0.90~1.10, more preferably 0.95~1.05 ratio it is for example below relatively low at 120 DEG C At a temperature of inhibit imidizate while reacted, so as in the form of polyimide precursor solution composition suitably Obtain polyimide precursor.
This is not limited, more specifically, diamines is dissolved in organic solvent, while stirring into the solution Tetracarboxylic dianhydride is added at leisure, the stirring 1 hour~72 hours in the range of 0~120 DEG C, preferably 5 DEG C~80 DEG C, thus Obtain polyimide precursor.In the case where being reacted for 80 DEG C or more, molecular weight is sent out dependent on temperature history when polymerizeing It changes dynamic, and since heat carries out imidizate, it is therefore possible to can not steadily manufacture polyimide precursor.Above-mentioned system The order of addition for making the diamines and tetracarboxylic dianhydride in method is easy to improve the molecular weight of polyimide precursor, therefore is preferred 's.Alternatively, it is also possible to make above-mentioned manufacturing method diamines and tetracarboxylic dianhydride order of addition on the contrary, precipitate reduce, therefore It is preferred.
In addition, tetracarboxylic acid sour component and the molar ratio of diamine component are to be added as needed in the case that diamine component is superfluous The carboxylic acid derivates of roughly the same amount with the superfluous molal quantity of diamine component can make rubbing for tetrabasic carboxylic acid ingredient and diamine component You are than close substantially equivalent.As carboxylic acid derivates herein, viscosity, the i.e. reality of polyimide precursor solution is not increased substantially The extended tetrabasic carboxylic acid of strand is not involved in matter or function as end-capping reagent tricarboxylic acids and its acid anhydrides, dicarboxylic acids and Its acid anhydrides etc. is suitable.
2) poly amic acid ester
It reacts tetracarboxylic dianhydride with arbitrary alcohol, obtains diester dicarboxylic acids, then make itself and chlorination reagent (thionyl Chlorine, oxalyl chloride etc.) reaction, obtain diester dicarboxyl acyl chlorides.By the diester dicarboxyl acyl chlorides and diamines -20 DEG C~120 DEG C, preferably It is stirred 1 hour~72 hours in the range of being -5 DEG C~80 DEG C, thus obtains polyimide precursor.It is reacted at 80 DEG C or more In the case where, molecular weight changes dependent on temperature history when polymerizeing, and since heat carries out imidizate, because This is possible to steadily manufacture polyimide precursor.In addition, making two using phosphorus system condensing agent, carbodiimides condensing agent etc. Ester dicarboxylic acids and diamines dehydrating condensation, thus also can easily obtain polyimide precursor.
3) polyamic acid silyl ester (indirect method)
It in advance reacts diamines and silylating agent, obtains silylated diamines.Distillation etc. is utilized as needed Carry out the purifying of silylated diamines.Then, it is first dissolved in silylated diamines in advance in the solvent of dehydration, on one side Stirring adds tetracarboxylic dianhydride on one side at leisure, the stirring 1 hour~72 in the range of 0~120 DEG C, preferably 5 DEG C~80 DEG C Hour, thus obtain polyimide precursor.Temperature in the case where being reacted for 80 DEG C or more, when molecular weight is dependent on polymerization Course and change, and since heat carries out imidizate, it is therefore possible to it steadily can not manufacture polyimides before Body.
As silylating agent used herein, using the silylating agent for not containing chlorine, then without to monosilane The diamines of base is purified, therefore is appropriate.As the silylating agent for not containing chlorine atom, N can be enumerated, O- is bis- (trimethyl silyl) trifluoroacetamide, N, bis- (trimethyl silyl) acetamides of O-, hexamethyldisilazane.Due to not Containing fluorine atom and at low cost, thus bis- (trimethyl silyl) acetamides of particularly preferred N, O-, hexamethyldisilazane.
In addition, pyridine, piperidines, triethylamine etc. can be used in the silylation reactive of diamines in order to promote to react Amine system catalyst.The catalyst can be used directly as the polymerization catalyst of polyimide precursor.
4) polyamic acid silyl ester (direct method)
Will using 1) the obtained polyamic acid solution of method and silylating agent mix, 0~120 DEG C, preferably It is stirred 1 hour~72 hours in the range of being 5 DEG C~80 DEG C, thus obtains polyimide precursor.It is reacted at 80 DEG C or more In the case where, molecular weight changes dependent on temperature history when polymerizeing, and since heat carries out imidizate, because This is possible to steadily manufacture polyimide precursor.
As silylating agent used herein, using the silylating agent for not containing chlorine, then without to monosilane The polyamic acid of base or obtained polyimides are purified, therefore are appropriate.As the first for not containing chlorine atom Silane-based agent can enumerate N, bis- (trimethyl silyl) trifluoroacetamides of O-, N, bis- (trimethyl silyl) second of O- Amide, hexamethyldisilazane.Due to without containing fluorine atom and at low cost, thus the bis- (trimethyl silyls of particularly preferred N, O- Base) acetamide, hexamethyldisilazane.
Above-mentioned manufacturing method can be carried out suitably in organic solvent, and therefore, result can be readily derived packet Solution or liquid composite (polyimide precursor composition) containing polyimide precursor.
The solvent used when for preparing polyimide precursor, such as preferred n,N-Dimethylformamide, N, N- dimethyl The non-protonic solvents such as acetamide, n-methyl-2-pyrrolidone, 1,3-Dimethyl-2-imidazolidinone, dimethyl sulfoxide, especially It is preferred that n,N-dimethylacetamide, if starting monomer ingredient and polyimide precursor generated dissolution, any kind of molten Agent without problem uses, therefore its structure is not particularly limited.As solvent, it is preferred to use N, N- dimethyl The amide solvents such as formamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone；Gamma-butyrolacton, gamma-valerolactone, δ-penta The ring-type ester solvent such as lactone, γ-hexalactone, 6-caprolactone, Alpha-Methyl-gamma-butyrolacton；Ethylene carbonate, propylene carbonate etc. Carbonate solvent；Two alcohol series solvent such as triethylene glycol；The phenol systems solvents such as metacresol, paracresol, 3- chlorophenol, 4- chlorophenol；Benzene second Ketone, 1,3- dimethyl-2-imidazolinone, sulfolane, dimethyl sulfoxide etc..Further, the organic of other routines also can be used Solvent, i.e. phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetic acid esters, ethyl cellosolve, Butyl cellosolve, 2- methylcellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, diformazan Oxygroup ethane, diethoxyethane, butyl oxide, diethylene glycol dimethyl ether, methyl iso-butyl ketone (MIBK), diisobutyl ketone, cyclopentanone, Cyclohexanone, methyl ethyl ketone, acetone, butanol, ethyl alcohol, dimethylbenzene, toluene, chlorobenzene, terpenes, mineral essential oil, petroleum naphtha system Solvent etc..It should be noted that solvent can also be used in combination of two or more.
The log viscosities of polyimide precursor are not particularly limited, it is preferred that 30 DEG C of concentration be 0.5g/dL N, Log viscosities in N- dimethylacetamide solution are 0.2dL/g or more, more preferably 0.3dL/g or more, are particularly preferably 0.4dL/g or more.When log viscosities are 0.2dL/g or more, the molecular weight of polyimide precursor is high, obtained polyimides Mechanical strength, excellent heat resistance.
In polyimide precursor composition used in the present invention, relative to solvent, tetracarboxylic acid sour component and diamine component The total amount of total amount, tetracarboxylic acid sour component and diamine component is 5 mass % or more, preferably 10 mass % or more, more preferably 15 matter It is suitable for measuring the ratio of % or more.It should be noted that in general, relative to the total of solvent, tetracarboxylic acid sour component and diamine component The total amount of amount, tetracarboxylic acid sour component and diamine component is 60 mass % or less, preferably 50 mass % or less are suitable.The concentration It is the concentration of the substantially approximate solid component concentration due to polyimide precursor, when the concentration is too low, such as is difficult to control sometimes The film thickness of the polyimide film obtained when system manufacture polyimide film.
The viscosity (rotary viscosity) of polyimide precursor composition is not particularly limited, using E type rotational viscometer 25 DEG C temperature, 20 seconds-1Shear velocity under the rotary viscosity that measures be preferably 0.01Pa seconds~1000Pa seconds, more preferably 0.1Pa seconds~100Pa seconds.In addition, thixotropy can also be assigned as needed.In the viscosity of above range, applied It is easily processed when cloth or film, and can inhibit repulsion, levelability is excellent, thus good overlay film can be obtained.
Polyimide precursor composition used in the present invention can according to need addition imidizate and promote catalyst (miaow Azole compounds etc.), chemical imidization agent (amine compounds such as the acid anhydrides such as acetic anhydride, pyridine, isoquinolin), antioxidant, purple The coupling agents such as ultraviolet absorbers, filler (inorganic particles such as silica etc.), dyestuff, pigment, silane coupling agent, bottom coating, Fire proofing, defoaming agent, levelling agent, rheology control agent (flowing adjuvant), remover etc..
Polyimide precursor composition used in the present invention preferably comprises imidazole compound and/or trialkylamine sometimes Compound.The total repetition preferably with respect to polyimide precursor of the content of imidazole compound and/or trialkylamine compound 1 mole of unit is more preferably 0.05 mole or more 1 mole or less less than 4 moles.Pass through the weight relative to polyimide precursor 1 mole of multiple unit to be preferably less than 4 moles, be more preferably 0.05 mole or more 1 mole of ratio below for imidazoles system chemical combination Object and/or trialkylamine compound are added in polyimide precursor composition, sometimes can be while keeping high transparency Improve the mechanical property of obtained polyimide film.
Imidazole compound used in the present invention is not particularly limited as long as the compound with imidazole skeleton.Make For imidazole compound used in the present invention, be not particularly limited, can enumerate 1,2- methylimidazole, 1- methylimidazole, 2-methylimidazole, 2- phenylimidazole, imidazoles, benzimidazole etc., preferably 1,2- methylimidazole, 1- methylimidazole, 2- methyl miaow Azoles, imidazoles etc., particularly preferred 1,2- methylimidazole, 1- methylimidazole.Imidazole compound can be used alone, can also To be used in combination of two or more.
Trialkylamine compound used in the present invention, is not particularly limited, be preferably 1~5 with carbon atom number, The compound for the alkyl that more preferable carbon atom number is 1~4, can enumerate trimethylamine, triethylamine, Tri-n-Propylamine, tri-n-butylamine etc..Three Alkyl ammonium compounds can be used alone, and can also be used in combination of two or more.Furthermore it is possible to by more than one miaow Azole compounds and more than one trialkylamine compound are shared.
Using imidazole compound and/or trialkylamine compound, the miaow of polyimide precursor composition The content of azole compounds and/or trialkylamine compound is relative to 1 mole of repetitive unit of polyimide precursor preferably smaller than 4 Mole.If 1 mole of repetitive unit relative to polyimide precursor of the content of imidazole compound and/or trialkylamine compound It is 4 moles or more, then the storage stability of polyimide precursor composition is deteriorated.Imidazole compound and/or trialkyl amination 1 mole of repetitive unit preferably 0.05 mole or more of the content of object relative to polyimide precursor is closed, in addition, relative to polyamides 1 mole of repetitive unit of imines precursor is more preferably 2 moles or less, particularly preferably 1 mole or less.It should be noted that this Place, 1 mole of repetitive unit of polyimide precursor are corresponding with 1 mole of tetracarboxylic acid sour component.
Polyimide precursor composition comprising imidazole compound and/or trialkylamine compound can be by utilizing Imidazole compound and/or trialkylamine are added in the polyimide precursor solution or liquid composite that above-mentioned manufacturing method obtains It is prepared by compound.Alternatively, it is also possible to which tetracarboxylic acid sour component (tetracarboxylic dianhydride etc.), diamine component and imidazoles system are added in a solvent Compound and/or trialkylamine compound, make in the presence of imidazole compound and/or trialkylamine compound tetrabasic carboxylic acid at Divide and reacted with diamine component, thus also available includes polyimide precursor and imidazole compound and/or trialkyl The polyimide precursor composition of amine compounds.
Then, by comprising the polyimide precursor composition of polyimide precursor and solvent curtain coating in for example ceramics (glass, Silicon, aluminium oxide etc.), metal (copper, aluminium, stainless steel etc.), on the substrates such as heat resistant plastice film (polyimide film etc.), in a vacuum, In the non-active gas such as nitrogen or in air, using hot wind or infrared ray at 20 DEG C~180 DEG C, preferably 20 DEG C~150 DEG C Temperature range is dried.Then, by obtained polyimide precursor film on substrate or by polyimide precursor film from It is removed on substrate and the end of the film is fixed, in this state, in a vacuum, in the non-active gas such as nitrogen or empty In gas, using hot wind or infrared ray such as 200 DEG C~500 DEG C, more preferably 250 DEG C~460 DEG C or so at a temperature of carry out Imidizate is heated, it is possible thereby to manufacture polyimide film/substrate laminate or polyimide film.It can also be by polyamides Asia Amine precursor film carries out heating imidizate on substrate and obtains polyimide film/substrate laminate, later by polyimide film It is removed from substrate, to obtain polyimide film.It should be noted that oxygen occurs for obtained polyimide film in order to prevent Change deterioration, heating imidizate preferably carries out in a vacuum or in non-active gas.If heating the temperature of imidizate only Height can also then carry out in air.
In addition, also can replace as described above based on heating for the imidization reaction of polyimide precursor The heating imidizate of processing and carried out by following chemical treatments: that is, in the presence of the tertiary amines such as pyridine or triethylamine, will gather It is medium that imide precursor is impregnated into the solution containing the cyclodehydrations reagent such as acetic anhydride.In addition, these cyclodehydration reagents are pre- It first puts into polyimide precursor composition and is stirred, is cast on substrate and is dried, thus can also make The polyimide precursor for making part imidizate, by the polyimide precursor film of obtained part imidizate on substrate, Or polyimide precursor film is removed from substrate and the end of the film is fixed, further progress is such as in this state The upper heat treatment, it is hereby achieved that polyimide film/substrate laminate or polyimide film.
The thickness of polyimide film used in the present invention is different depending on the application, usually, preferably 0.1 μm~250 μm, more Preferably 5 μm~200 μm, more preferably 10 μm~150 μm.In light such as display applications through polyimide film on the way making In the case where, if polyimide film is blocked up, light transmittance is likely to decrease；If excessively thin, mechanical property is reduced, it is possible to nothing Method is suitably used as film.In addition, in the case where being used as emulsion sheet or cover film, if polyimide film is thin, impact resistance Property reduce, be unable to fully sometimes protection inside device.
In particular, when the light such as display applications penetrate used in the purposes of polyimide film, it is desirable to which polyamides is sub- The transparency of amine film is high.The YI (yellow chromaticity) of polyimide film used in the present invention is not particularly limited, can be preferably 4 with Under, more preferably 3.5 or less, more preferably 3 or less, further preferably 2.8 or less, particularly preferably 2.5 or less.
The mist degree of polyimide film used in the present invention is not particularly limited, and can be preferably 3% or less, be more preferably 2% or less, it is more preferably 1.5% or less, is particularly preferably less than 1%.Such as the situation used in display applications Under, if mist degree up to more than 3%, has the time that scattering occurs and keeps image fuzzy.
Light transmittance of the polyimide film used in the present invention at wavelength 400nm is not particularly limited, and can be preferably 77% or more, it is more preferably 80% or more, is more preferably 82% or more, particularly preferably more than 82%.In display applications etc. Used in the case of, need to enhance light source if light transmittance is low, lead to the problem of expend energy etc. sometimes.
<<priming coat>>
In laminate of the invention, hard conating can be formed directly on the surface of polyimide film, for example, can be Priming coat is formed on the surface of polyimide film, and is formed on hard conating.Priming coat can according to need poly- in order to improve It the adaptation of acid imide film and hard conating or is configured to improve weatherability, impact resistance or aesthetics.
The material for forming priming coat is not particularly limited, and conventionally used material can be used.
Priming coat such as consolidating by the primer composition containing curable resin ingredient (including monomer or oligomer) Compound is formed.As the curable resin of priming coat, for example, silicone-based resin, acrylic resin, Polyester tree Rouge, epoxy system resin, carbamate system resin, chlorinated polyolefin hydrocarbon system resin etc..
As needed, other than curable resin ingredient, primer composition also contain solvent and curing agent (light or Thermal polymerization).In addition, primer composition can contain various additives.As various additives, such as can lift Silane coupling agent, sensitizer, ultraviolet absorbing agent, light stabilizer, fire retardant, levelling agent, delustering agent, antistatic agent, antifog out Agent, plasticizer, lubricant, waterproofing agent etc..
Priming coat for example can be formed: will contain above-mentioned curable resin ingredient, solvent as needed and solidification The primer composition of agent (light or thermal polymerization) etc. is coated on the surface of polyimide film, as needed does solvent After dry and removing, solidified, it is possible thereby to form priming coat.Solidification is for example irradiated by light or is heated to carry out.? In the case where photocuring, as the light irradiated when its solidification is made, luminous ray and ultraviolet light, X-ray, electronics can be enumerated The ionizing ray of ray, alpha ray, β ray and gamma-rays etc.In the case of thermal curing, make heat treatment when its solidification Temperature is not particularly limited, and usually 80 DEG C~200 DEG C or so.Come alternatively, it is also possible to carry out both light irradiation and heat treatment Solidify primer composition.
As the material (primer composition) for forming priming coat, commercially available material also can be used.As commercially available product, For example, the UVPUD (carbamate resins/acrylic resin is blended) of Ube Industries, Ltd's manufacture, great achievement ([acrylate copolymer side chain is alcoxyl to the silicone cross-linked silicone modified acrylate copolymer of type to the 8SQ of fine chemistry industry company manufacture Base silicyl]), great achievement fine chemistry industry company manufacture the (urethane-modified acrylic's polymer [side of acrylic acid 8UA Chain is carbamate]), Moment company manufacture SHP401 (polymethyl methacrylate solution (1- methoxy-2-propanol, Diacetone alcohol) etc..
The thickness of priming coat is not particularly limited, usually 5nm~20 μm or so, preferably 10nm~10 μm.If primary coat The thickness of layer thickens, and when being formed on hard conating, the hardness on surface is sometimes insufficient.
<<hard conating>>
In the present invention, hard conating is direct or is formed on polyimide film across priming coat etc..
Hard conating of the invention can be by organic material (solidified resin), inorganic material, organic-inorganic hybrid-type material (solidified resin containing inorganic materials etc.) etc. is formed.Its forming method can be selected according to each material.
In the present invention, hard conating preferably and by curable resin ingredient or including at least curable resin ingredient inorganic fill out The solidfied material of the hardening resin composition of material is formed.
Hardening resin composition at least contains curable resin ingredient, is solidified by light or heat, and it is (poly- to become solidfied material Close object, cross-linking agent).Hardening resin composition contains curing agent as needed, and (crosslinking agent, light or thermal polymerization are total to instead Answer agent).Hardening resin composition further preferably includes inorganic filler.Other than curable resin, hardening resin composition Also it may include solvent-dry type resin.In addition, also may include solvent as needed.In this specification, curable resin group Close object include the substance for the liquid that each ingredient mixes, coated shaped liquid film substance, eliminate solvent but without final Cured membranaceous substance etc. does not receive the substance of final curing process.
Curable resin with photo-curable can enumerate the substance at least one optical polymerism functional group.This theory " optical polymerism functional group " in bright book refers to the functional group that row polymerization reaction can be injected by illumination.As optical polymerism function Group, for example, the ethylenic double bonds such as (methyl) acryloyl group, vinyl, allyl.As specific photo-curable tree Rouge ingredient can enumerate multi-functional (methyl) acrylate monomer, (methyl) acrylic ester prepolymer, have photocuring The polymer etc. of property.Multi-functional (methyl) acrylate monomer and (methyl) acrylic ester prepolymer respectively can be independent It uses, the two can also be shared.It is irradiated as when solidifying hardening resin composition (in the case where photo-curable) Light, the ionization of luminous ray and ultraviolet light, X-ray, electron ray, alpha ray, β ray and gamma-rays etc can be enumerated Ray.
Heat-curing resin with Thermocurable has at least one Thermocurable functional group.Using Thermocurable tree In the case that rouge is as curable resin ingredient, as the heat-curing resin being able to use, epoxy system resin can be enumerated, gathered Imide series resin, phenol resin, silicone-based resin, cyanate ester based resin, bismaleimide-triazine resin, allylation are poly- Phenylene ether resins (Thermocurable PPE), diaion, unsaturated polyester (UP) or their copolymer etc..
As inorganic filler, silica, aluminium oxide, boehmite, talcum, calcium carbonate, titanium oxide, oxidation can be enumerated The powder of iron, silicon carbide, boron nitride, zirconium oxide etc., by the obtained pearl of their spheroidizations, mono-crystlling fibre and glass fibre etc., They can be used alone or are use mixing two or more.Among these, preferably silica, aluminium oxide, boehmite, oxidation Titanium, zirconium oxide etc., more preferable silica, titanium oxide and zirconium oxide.It is repaired in addition, inorganic filler has preferably carried out surface sometimes Decorations.As this particularly preferred inorganic filler, active silica can be exemplified.
In this specification " active silica " refer to using have photo-curable unsaturated group organic compound into The silicon dioxide microparticle of surface modification is gone.It is above-mentioned to have carried out table using the organic compound with photo-curable unsaturated group Face modification silicon dioxide microparticle (active silica) for example can usually obtain as follows: for average grain diameter be 0.5nm~ 500nm or so, preferably average grain diameter be 1nm~200nm silica particle surface silanol group, make have can be with this The organic compound of the unsaturated group containing photo-curable of functional group that silanol group is reacted and (methyl) acryloyl group into Row reaction, it is hereby achieved that.
The average grain diameter of inorganic filler used in present embodiment be preferably 1nm~200nm, particularly preferably 10nm~ 200nm, more preferably 20nm~200nm.By making the average grain diameter 1nm or more of inorganic filler, combine curable resin Hard conating made of object solidification has higher surface hardness.In addition, if inorganic filler average grain diameter be 200nm hereinafter, if It is difficult to happen the scattering of light in obtained hard conating, the transparency of hard conating improves.
The content of inorganic filler in hard conating relative to hard conating be preferably 10 volume of volume %~85 %, more preferably 20 volume of volume %~80 %, further preferably 40 volume of volume %~70 %, particularly preferably 45 bodies of volume %~65 Product %.By making the 10 volume % of content or more of inorganic filler, the surface hardness assigned to hard conating is further increased.Separately On the one hand, by making the 85 volume % of content of inorganic filler hereinafter, the formation of hard conating is easy.
In addition to the above ingredients, hardening resin composition can also contain various additives.As various additives, For example, ultraviolet absorbing agent, antioxidant, light stabilizer, antistatic agent, silane coupling agent, age resister, thermal resistance Poly- agent, colorant, surfactant, preserving stabilizer, plasticizer, lubricant, defoaming agent, organic system packing material, wetability Modifying agent, coated face modifying agent etc..
The hard conating formed by the solidfied material of hardening resin composition for example can be formed: include at least above-mentioned The surface that the hardening resin composition of curable resin ingredient is coated on polyimide film (is formed on the surface of polyimide film It is its surface in the case where having priming coat etc.), as needed by after solvent seasoning and removing, by hardening resin composition Curing of coating, it is possible thereby to be formed.Solidification is for example irradiated by light or is heated to carry out.Alternatively, it is also possible to carry out illumination It penetrates and heats the two and solidify hardening resin composition.
The thickness of hard conating is not particularly limited, and for example, 1 μm~50 μm, preferably 5 μm~40 μm.In a certain embodiment party In formula, from the aspect of the resistance to deflection of laminate, the thickness of hard conating is more preferably 30 μm or less, particularly preferably 20 μm Below.By make hard conating with a thickness of 1 μm or more, sufficient surface hardness can be assigned to laminate of the invention.It is another Aspect, by make hard conating with a thickness of 50 μm hereinafter, the resistance to deflection of laminate of the invention it is excellent, processing be easy, remove this It can prevent laminate from unnecessarily thickeing in addition, manufacturing cost increases.
<<laminate>>
As described above, laminate of the invention can be manufactured by forming hard conating on polyimide film.
The pencil hardness of hard coating surface in laminate of the invention is not particularly limited, preferably 2H or more, more excellent It is selected as 3H or more.
In particular, when the light such as display applications penetrate used in the purposes of laminate, it is desirable to polyimide film/ The transparency of hard conating laminate is high.The YI (yellow chromaticity) of laminate of the invention is not particularly limited, can be preferably 5 with Under, more preferably 4.5 or less, more preferably 4 or less, particularly preferably 3.5 or less.
The mist degree of laminate of the invention is not particularly limited, can be preferably 3% or less, more preferably 2% or less, into One step is preferably 1.5% or less, is particularly preferably less than 1%.Such as used in the display applications, if mist degree is high Keep image fuzzy to more than 3%, then there is time generation to scatter.
The surface hardness of laminate of the invention is high and the transparency is also excellent, such as can be aobvious suitable for display Show the emulsion sheet or cover film (protective film) in face.Other than the emulsion sheet or cover film as display display surface, the present invention Laminate can also be suitable in display member, touch panel component or touch sensor component, optical component etc..
Embodiment
Hereinafter, by embodiment and comparative example, invention is further explained.It should be noted that the present invention is unlimited Due to following embodiment.
In following example, evaluated using following methods.
<evaluation of polyimide film>
[pencil hardness]
According to JIS K5600-5-4, the measurement of the pencil hardness of polyimide film is carried out.Load is set as 750g.
<evaluation of polyimide film/hard conating laminate>
[YI (yellow chromaticity)]
According to ASTM E313, the measurement of polyimide film/hard conating laminate YI is carried out.
[mist degree]
Using nephelometer/NDH2000 (Japan's electricity color industry manufactures), according to the standard test polyimides of JIS K7136 Film/hard conating laminate mist degree.
[pencil hardness]
According to JIS K5600-5-4, the pencil hardness of polyimide film/hard conating laminate hard coating surface is carried out Measurement.Load is set as 750g.
Abbreviation, purity of raw material used in following example etc. are as described below.
[diamine component]
M-TD:2,2 '-dimethyl -4,4 '-benzidine [purity: 99.85% (GC analysis)]
Bis- (trifluoromethyl) benzidine of TFMB:2,2 '-[purity: 99.83% (GC analysis)]
4,4 '-ODA:4,4 '-oxygen diphenylamines [purity: 99.9% (GC analysis)]
Bis- (4- amino-benzene oxygen) benzene of TPE-Q:1,4-
3,5-DABA:3,5- diaminobenzoic acid
[tetracarboxylic acid sour component]
CBDA:1,2,3,4- cyclobutane tetracarboxylic dianhydride [purity: 99.9% (GC analysis)]
CpODA: norcamphane -2- loop coil-α-cyclopentanone-α '-loop coil -2 "-norcamphane -5,5 ", 6,6 "-tetracarboxylic dianhydrides
PMDA-H:1,2,4,5- cyclopentanetetracarboxylic dianhydride [purity: 99.9% (GC analysis)]
6FDA:4,4 '-(2,2- hexafluoro isopropyl alkene) double O-phthalic acid dianhydrides [purity 99.77% (H-NMR analysis)]
S-BPDA:3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides [purity 99.9% (H-NMR analysis)]
CPDA:1,2,3,4- pentamethylene tetracarboxylic dianhydride
[imidazolium compounds]
1,2-DMz:1,2- methylimidazole
[solvent]
DMAc:N, N- dimethyl acetamide
The structural formula of tetracarboxylic acid sour component used in embodiment, comparative example is described in table 1-1, describes reality in table 1-2 The structural formula of diamine component used in example, comparative example is applied, imidazoles used in embodiment, comparative example is described in table 1-3 Close the structural formula of object.
[table 1-1]
[table 1-2]
[table 1-3]
Hard conating used in following example is as described below.
[hard conating]
It uses
The chemical conversion manufacture of hard conating a: Teng Cang FUJIHARD (registered trademark) HO3313U-8
Hard conating b: STR-SiA (registered trademark) TA-3090N of great achievement fine chemistry industry company manufacture.Relative to STR-SiA 100g adds IRUGACURE (registered trademark) 184 of the 3g as photoinitiator, is stirred at room temperature, obtains hard conating use Solution (hard conating b).
[embodiment 1]
M-TD 2.12g (10 mMs) are added into the reaction vessel that benefit is preferably replaced with nitrogen, the monomer that feeds intake is added Gross mass (summation of diamine component and carboxylic acid composition) reaches the 36.76g DMAc of the amount of 10 mass %, and it is small to be stirred at room temperature 1 When.CBDA 1.96g (10 mMs) are slowly added into the solution.It is stirred at room temperature 12 hours, later, holds to reaction The mixed solution of 1,2- methylimidazole 0.19g Yu DMAc 0.19g are added in device, is stirred at room temperature 30 minutes, obtains uniformly And sticky polyimide precursor solution.It is calculated according to inventory, the repetitive unit 1 relative to polyimide precursor rubs You, 1,2- methylimidazole is 0.2 mole.
The polyimide precursor solution filtered using PTFE film filter is coated on the emerging production strain formula meeting in space portion Polyimide film, UPILEX (registered trademark) -125S (being hereinafter denoted as " 125S ") of society's manufacture, (oxygen is dense in a nitrogen atmosphere Spend 200ppm or less) 260 DEG C are heated to by room temperature directly on 125S, hot-imide is carried out, colorless and transparent polyamides is obtained Imines film/125S laminate.Then, obtained polyimide film is removed from 125S, it is sub- obtains the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-1.
In such a way that the film thickness of the hard conating after drying is about 10 μm, using bar coater, by hard conating a, (Teng Cang chemical conversion is made Make FUJIHARD HO3313U-8) it is coated on obtained polyimide film.Then, 10 minutes dry at 80 DEG C, it uses High-pressure sodium lamp is 1000mJ/cm with accumulated light2Mode irradiate ultraviolet light, obtain polyimide film/hard conating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-1.
[embodiment 2]
TFMB 3.20g (10 mMs) are added into the reaction vessel that benefit is preferably replaced with nitrogen, the monomer that feeds intake is added Gross mass (summation of diamine component and carboxylic acid composition) reaches the 20.65g DMAc of the amount of 20 mass %, and it is small to be stirred at room temperature 1 When.CBDA 1.96g (10 mMs) are slowly added into the solution.It is stirred at room temperature 12 hours, later, holds to reaction The mixed solution of 1,2- methylimidazole 0.19g Yu DMAc 0.19g are added in device, is stirred at room temperature 30 minutes, obtains uniformly And sticky polyimide precursor solution.It is calculated by inventory, relative to 1 mole of repetitive unit of polyimide precursor, DMIZ 1,2 dimethylimidazole is 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-1.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-1.
[embodiment 3]
M-TD 1.06g (5 mMs) and 4,4 '-ODA are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) of feeding intake reaches 12 mass % is added in 1.00g (5 mMs) 29.51g DMAc is stirred at room temperature 1 hour.CBDA 1.96g (10 mMs) are slowly added into the solution.In room temperature Lower stirring 12 hours, later, the mixed solution of 1,2- methylimidazole 0.19g Yu DMAc 0.19g is added into reaction vessel, It is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.It is calculated by inventory, relative to poly- 1 mole of the repetitive unit of imide precursor, 1,2- methylimidazole are 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-1.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-1.
[embodiment 4]
TFMB 1.60g (5 mMs) and 4,4 '-ODA are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) of feeding intake reaches 12 mass % is added in 1.00g (5 mMs) 33.47g DMAc is stirred at room temperature 1 hour.CBDA 1.96g (10 mMs) are slowly added into the solution.In room temperature Lower stirring 12 hours, later, the mixed solution of 1,2- methylimidazole 0.19g Yu DMAc 0.19g is added into reaction vessel, It is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.It is calculated by inventory, relative to poly- 1 mole of the repetitive unit of imide precursor, 1,2- methylimidazole are 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-1.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-1.
[embodiment 5]
M-TD 2.12g (10 mMs) are added into the reaction vessel that benefit is preferably replaced with nitrogen, the monomer that feeds intake is added Gross mass (summation of diamine component and carboxylic acid composition) reaches the 18.19g DMAc of the amount of 19 mass %, and it is small to be stirred at room temperature 1 When.CBDA 1.77g (9 mMs) and CpODA0.38g (1 mM) are slowly added into the solution.It is stirred at room temperature 12 hours, later, the mixed solution of 1,2- methylimidazole 0.10g Yu DMAc 0.10g are added into reaction vessel, in room temperature Lower stirring 30 minutes, obtains uniform and sticky polyimide precursor solution.It is calculated by inventory, relative to polyimides 1 mole of the repetitive unit of precursor, 1,2- methylimidazole are 0.1 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-1.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-1.
[embodiment 6]
M-TD 2.12g (10 mMs) are added into the reaction vessel that benefit is preferably replaced with nitrogen, the monomer that feeds intake is added Gross mass (summation of diamine component and carboxylic acid composition) reaches the 18.19g DMAc of the amount of 19 mass %, and it is small to be stirred at room temperature 1 When.CBDA1.77g (9 mMs) and CpODA 0.38g (1 mM) are slowly added into the solution.It is stirred at room temperature 12 hours, obtain uniform and sticky polyimide precursor solution.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-1.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-1.
[embodiment 7]
M-TD 1.27g (6 mMs) and TPE-Q 1.17g are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) of feeding intake reaches 19 mass % is added in (4 mMs) 19.57g DMAc is stirred at room temperature 1 hour.CBDA 1.77g (9 mMs) and CpODA is slowly added into the solution 0.38g (1 mM).Be stirred at room temperature 12 hours, later, be added into reaction vessel 1,2- methylimidazole 0.38g with The mixed solution of DMAc 0.38g is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.By throwing Doses is calculated, and relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.4 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-1.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-1.
[embodiment 8]
TFMB 3.20g (10 mMs) are added into the reaction vessel that benefit is preferably replaced with nitrogen, the monomer that feeds intake is added Gross mass (summation of diamine component and carboxylic acid composition) reaches the 21.41g DMAc of the amount of 20 mass %, and it is small to be stirred at room temperature 1 When.CBDA1.77g (9 mMs) and CpODA 0.38g (1 mM) are slowly added into the solution.It is stirred at room temperature 12 hours, later, the mixed solution of 1,2- methylimidazole 0.19g Yu DMAc 0.19g are added into reaction vessel, in room temperature Lower stirring 30 minutes, obtains uniform and sticky polyimide precursor solution.It is calculated by inventory, relative to polyimides 1 mole of the repetitive unit of precursor, 1,2- methylimidazole are 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-1.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-1.
[embodiment 9]
TFMB 2.24g (7 mMs) and TPE-Q 0.88g are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) of feeding intake reaches 22 mass % is added in (3 mMs) 18.68g DMAc is stirred at room temperature 1 hour.CBDA 1.77g (9 mMs) and CpODA is slowly added into the solution 0.38g (1 mM).Be stirred at room temperature 12 hours, later, be added into reaction vessel 1,2- methylimidazole 0.19g with The mixed solution of DMAc 0.19g is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.By throwing Doses is calculated, and relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-1.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-1.
[embodiment 10]
M-TD 0.637g (3 mMs) and TFMB 1.60g are added into the reaction vessel that benefit is preferably replaced with nitrogen (5 mMs) and TPE-Q 0.58g (2 mMs), addition feed intake monomer gross mass (summation of diamine component and carboxylic acid composition) The 22.63g DMAc for reaching the amount of 18 mass % is stirred at room temperature 1 hour.CBDA is slowly added into the solution 1.77g (9 mMs) and CpODA 0.38g (1 mM).It is stirred at room temperature 12 hours, later, is added into reaction vessel The mixed solution of 1,2- methylimidazole 0.19g and DMAc 0.19g is stirred at room temperature 30 minutes, obtains uniform and sticky Polyimide precursor solution.It is calculated by inventory, relative to 1 mole of repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-1.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-1.
[embodiment 11]
M-TD 1.91g (9 mMs) and 4,4 '-ODA are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) of feeding intake reaches 12 mass % is added in 0.20g (1 mM) 31.24g DMAc is stirred at room temperature 1 hour.CBDA 1.77g (9 mMs) and CpODA is slowly added into the solution 0.38g (1 mM).Be stirred at room temperature 12 hours, later, be added into reaction vessel 1,2- methylimidazole 0.19g with The mixed solution of DMAc 0.19g is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.By throwing Doses is calculated, and relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-2.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-2.
[embodiment 12]
M-TD 1.91g (9 mMs) and 4,4 '-ODA are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) of feeding intake reaches 20 mass % is added in 0.20g (1 mM) 16.40g DMAc is stirred at room temperature 1 hour.CBDA 1.77g (9 mMs) and PMDA-H is slowly added into the solution 0.22g (1 mM).Be stirred at room temperature 12 hours, later, be added into reaction vessel 1,2- methylimidazole 0.19g with The mixed solution of DMAc 0.19g is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.By throwing Doses is calculated, and relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-2.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-2.
[embodiment 13]
M-TD 1.91g (9 mMs) and 4,4 '-ODA are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) of feeding intake reaches 12 mass % is added in 0.20g (1 mM) 31.68g DMAc is stirred at room temperature 1 hour.CBDA 1.77g (9 mMs) and 6FDA is slowly added into the solution 0.44g (1 mM).Be stirred at room temperature 12 hours, later, be added into reaction vessel 1,2- methylimidazole 0.19g with The mixed solution of DMAc 0.19g is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.By throwing Doses is calculated, and relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-2.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-2.
[embodiment 14]
M-TD 1.91g (9 mMs) and 4,4 '-ODA are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) of feeding intake reaches 12 mass % is added in 0.20g (1 mM) 30.58g DMAc is stirred at room temperature 1 hour.CBDA 1.77g (9 mMs) and s-BPDA is slowly added into the solution 0.29g (1 mM).Be stirred at room temperature 12 hours, later, be added into reaction vessel 1,2- methylimidazole 0.19g with The mixed solution of DMAc 0.19g is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.By throwing Doses is calculated, and relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-2.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-2.
[comparative example 1]
TFMB 0.96g (3 mMs) and TPE-Q 2.05g are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) of feeding intake reaches 16 mass % is added in (7 mMs) 26.08g DMAc is stirred at room temperature 1 hour.CBDA 1.96g (10 mMs) are slowly added into the solution.In room temperature Lower stirring 12 hours, later, the mixed solution of 1,2- methylimidazole 0.19g Yu DMAc 0.19g is added into reaction vessel, It is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.It is calculated by inventory, relative to poly- 1 mole of the repetitive unit of imide precursor, 1,2- methylimidazole are 0.1 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-2.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-2.
[comparative example 2]
TFMB 1.60g (5 mMs) and TPE-Q 1.46g are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) of feeding intake reaches 22 mass % is added in (5 mMs) 22.49g DMAc is stirred at room temperature 1 hour.CBDA 0.59g (3 mMs) and CpODA is slowly added into the solution 2.69g (7 mMs).Be stirred at room temperature 12 hours, later, be added into reaction vessel 1,2- methylimidazole 0.10g with The mixed solution of DMAc 0.10g is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.By throwing Doses is calculated, and relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.1 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-2.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-2.
[comparative example 3]
M-TD 1.06g (5 mMs) and TPE-Q 1.46g are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) of feeding intake reaches 18 mass % is added in (5 mMs) 23.00g DMAc is stirred at room temperature 1 hour.CBDA 1.37g (7 mMs) and CpODA is slowly added into the solution 1.15g (3 mMs).Be stirred at room temperature 12 hours, later, be added into reaction vessel 1,2- methylimidazole 0.10g with The mixed solution of DMAc 0.10g is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.By throwing Doses is calculated, and relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.1 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-2.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-2.
[comparative example 4]
M-TD 1.06g (5 mMs) and TPE-Q 1.46g are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) of feeding intake reaches 18 mass % is added in (5 mMs) 24.72g DMAc is stirred at room temperature 1 hour.CBDA 0.98g (5 mMs) and CpODA is slowly added into the solution 1.92g (5 mMs).Be stirred at room temperature 12 hours, later, be added into reaction vessel 1,2- methylimidazole 0.10g with The mixed solution of DMAc 0.10g is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.By throwing Doses is calculated, and relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.1 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-2.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-2.
[comparative example 5]
M-TD 1.91g (9 mMs) and 4,4 '-ODA are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) of feeding intake reaches 25 mass % is added in 0.20g (1 mM) 12.16g DMAc is stirred at room temperature 1 hour.CBDA 1.77g (9 mMs) and CPDA is slowly added into the solution 0.21g (1 mM).Be stirred at room temperature 12 hours, later, be added into reaction vessel 1,2- methylimidazole 0.19g with The mixed solution of DMAc 0.19g is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.By throwing Doses is calculated, and relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-2.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-2.
[comparative example 6]
M-TD 1.70g (8 mMs) and TFMB 0.64g (2 are added into the reaction vessel that benefit is preferably replaced with nitrogen MM), the 16.24g that the monomer gross mass (summation of diamine component and carboxylic acid composition) that feeds intake reaches the amount of 22 mass % is added DMAc is stirred at room temperature 1 hour.PMDA-H 2.24g (10 mMs) are slowly added into the solution.It stirs at room temperature It mixes 12 hours, later, the mixed solution of 1,2- methylimidazole 0.19g Yu DMAc 0.19g is added into reaction vessel, in room Temperature lower stirring 30 minutes, obtain uniform and sticky polyimide precursor solution.It is calculated by inventory, relative to polyamides Asia 1 mole of the repetitive unit of amine precursor, 1,2- methylimidazole are 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-2.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-2.
[embodiment 15]
M-TD 1.06g (5 mMs) and TFMB 1.60g (5 are added into the reaction vessel that benefit is preferably replaced with nitrogen MM), the 21.18g that the monomer gross mass (summation of diamine component and carboxylic acid composition) that feeds intake reaches the amount of 18 mass % is added DMAc is stirred at room temperature 1 hour.CBDA1.77g (9 mMs) and CpODA0.38g (1 milli are slowly added into the solution Mole).It is stirred at room temperature 12 hours, later, 1,2- methylimidazole 0.19g and DMAc 0.19g is added into reaction vessel Mixed solution, be stirred at room temperature 30 minutes, obtain uniform and sticky polyimide precursor solution.It is counted by inventory It calculates, relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 30 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-3.
In addition, being used in such a way that the film thickness of the hard conating after drying is about 10 μm using obtained polyimide film Bar coater is coated with hard conating b (STR-SiA of great achievement fine chemistry industry company manufacture).Then, 10 minutes dry at 80 DEG C, it uses High-pressure sodium lamp is 1000mJ/cm according to accumulated light2Mode irradiate ultraviolet light.Later, it heats 10 minutes, obtains at 150 DEG C To polyimide film/hard conating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-3.
[embodiment 16]
TFMB 3.20g (10 mMs) are added into the reaction vessel that benefit is preferably replaced with nitrogen, the monomer that feeds intake is added Gross mass (summation of diamine component and carboxylic acid composition) reaches the 21.18g DMAc of the amount of 18 mass %, and it is small to be stirred at room temperature 1 When.CBDA 1.77g (9 mMs) and CpODA 0.38g (1 mM) are slowly added into the solution.It is stirred at room temperature 12 hours, later, the mixed solution of 1,2- methylimidazole 0.19g Yu DMAc 0.19g are added into reaction vessel, in room temperature Lower stirring 30 minutes, obtains uniform and sticky polyimide precursor solution.It is calculated by inventory, relative to polyimides 1 mole of the repetitive unit of precursor, 1,2- methylimidazole are 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-3.
In addition, carrying out operation similarly to Example 15 using obtained polyimide film and hard conating b, being gathered Acid imide film/hard conating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-3.
[embodiment 17]
M-TD 1.06g (5 mMs) and TFMB 1.44g (5 are added into the reaction vessel that benefit is preferably replaced with nitrogen MM), the 21.18g that the monomer gross mass (summation of diamine component and carboxylic acid composition) that feeds intake reaches the amount of 18 mass % is added DMAc is stirred at room temperature 1 hour.CBDA 1.77g (9 mMs) and CpODA 0.38g (1 is slowly added into the solution MM).It is stirred at room temperature 12 hours, later, 1,2- methylimidazole 0.19g and DMAc is added into reaction vessel The mixed solution of 0.19g is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.By inventory It is calculated, relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-3.
In addition, carrying out operation similarly to Example 15 using obtained polyimide film and hard conating b, being gathered Acid imide film/hard conating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-3.
[embodiment 18]
M-TD 1.49g (7 mMs) and TFMB 0.96g (3 are added into the reaction vessel that benefit is preferably replaced with nitrogen MM), the 24.15g that the monomer gross mass (summation of diamine component and carboxylic acid composition) that feeds intake reaches the amount of 16 mass % is added DMAc is stirred at room temperature 1 hour.CBDA 1.77g (9 mMs) and CpODA 0.38g (1 is slowly added into the solution MM).It is stirred at room temperature 12 hours, later, 1,2- methylimidazole 0.19g and DMAc is added into reaction vessel The mixed solution of 0.19g is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.By inventory It is calculated, relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-3.
In addition, carrying out operation similarly to Example 15 using obtained polyimide film and hard conating b, being gathered Acid imide film/hard conating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-3.
[embodiment 19]
M-TD 1.91g (9 mMs) and TFMB 0.32g (1 are added into the reaction vessel that benefit is preferably replaced with nitrogen MM), the 26.91g that the monomer gross mass (summation of diamine component and carboxylic acid composition) that feeds intake reaches the amount of 14 mass % is added DMAc is stirred at room temperature 1 hour.CBDA 1.77g (9 mMs) and CpODA 0.38g (1 is slowly added into the solution MM).It is stirred at room temperature 12 hours, later, 1,2- methylimidazole 0.19g and DMAc is added into reaction vessel The mixed solution of 0.19g is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.By inventory It is calculated, relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 45 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-3.
In addition, carrying out operation similarly to Example 15 using obtained polyimide film and hard conating b, being gathered Acid imide film/hard conating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-3.
[embodiment 20]
M-TD 1.80g (8.5 mMs) and 3,5-DABA are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) that feeds intake reaches 16 mass % is added in 0.23g (1.5 mMs) 26.13g DMAc, be stirred at room temperature 1 hour.Be slowly added into the solution CBDA 1.77g (9 mMs) and CpODA 0.38g (1 mM).It is stirred at room temperature 12 hours, later, 1,2- methylimidazole is added into reaction vessel The mixed solution of 0.19g and DMAc 0.19g are stirred at room temperature 30 minutes, it is molten to obtain uniform and sticky polyimide precursor Liquid.It is calculated by inventory, relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole rubs for 0.2 You.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-3.
In addition, carrying out operation similarly to Example 15 using obtained polyimide film and hard conating b, being gathered Acid imide film/hard conating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-3.
[embodiment 21]
TFMB 3.20g (10 mMs) are added into the reaction vessel that benefit is preferably replaced with nitrogen, the monomer that feeds intake is added Gross mass (summation of diamine component and carboxylic acid composition) reaches the 20.65g DMAc of the amount of 20 mass %, and it is small to be stirred at room temperature 1 When.CBDA 1.96g (10 mMs) are slowly added into the solution.12 hours, later, 1,2- diformazan are stirred at room temperature The mixed solution of base imidazoles 0.19g and DMAc 0.19g is added into reaction vessel, is stirred at room temperature 30 minutes, obtains uniformly And sticky polyimide precursor solution.It is calculated by inventory, relative to 1 mole of repetitive unit of polyimide precursor, DMIZ 1,2 dimethylimidazole is 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 50 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-3.
In addition, carrying out operation similarly to Example 15 using obtained polyimide film and hard conating b, being gathered Acid imide film/hard conating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-3.
[embodiment 22]
M-TD 2.12g (10 mMs) are added into the reaction vessel that benefit is preferably replaced with nitrogen, the monomer that feeds intake is added Gross mass (summation of diamine component and carboxylic acid composition) reaches the 18.19g DMAc of the amount of 19 mass %, and it is small to be stirred at room temperature 1 When.CBDA 1.77g (9 mMs) and CpODA 0.38g (1 mM) are slowly added into the solution.It is stirred at room temperature 12 hours, later, the mixed solution of 1,2- methylimidazole 0.10g Yu DMAc 0.10g are added into reaction vessel, in room temperature Lower stirring 30 minutes, obtains uniform and sticky polyimide precursor solution.It is calculated by inventory, relative to polyimides 1 mole of the repetitive unit of precursor, 1,2- methylimidazole are 0.1 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 80 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-3.
In addition, carrying out operation same as Example 1 using obtained polyimide film and hard conating a, obtaining polyamides Imines film/hard conating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-3.
[embodiment 23]
M-TD 1.70g (8 mMs) and TPE-Q 0.58g are added into the reaction vessel that benefit is preferably replaced with nitrogen The amount that the monomer gross mass (summation of diamine component and carboxylic acid composition) of feeding intake reaches 18 mass % is added in (2 mMs) 23.00g DMAc is stirred at room temperature 1 hour.CBDA 1.57g (8 mMs) and CpODA is slowly added into the solution 0.77g (2 mMs).Be stirred at room temperature 12 hours, later, be added into reaction vessel 1,2- methylimidazole 0.19g with The mixed solution of DMAc 0.19g is stirred at room temperature 30 minutes, obtains uniform and sticky polyimide precursor solution.By throwing Doses is calculated, and relative to 1 mole of repetitive unit of polyimide precursor, 1,2- methylimidazole is 0.2 mole.
Using the polyimide precursor solution, operation same as Example 1 is carried out, it is sub- to obtain the polyamides that film thickness is 20 μm Amine film.
The result being measured to the characteristic of the polyimide film is shown in table 2-3.
In addition, carry out operation same as Example 1 using obtained polyimide film, polyimide film/hard is obtained Coating laminate.
The result being measured to the polyimide film/hard conating laminate characteristic is shown in table 2-3.
Industrial applicibility
According to the present invention it is possible to provide it is a kind of comprising polyimide film and be formed on the polyimide film hard conating, And the laminate with high hardness of hard coating surface.Furthermore it is possible to provide one kind comprising polyimide film and be formed in the polyamides The high and transparent also excellent laminate of the hardness of hard conating, hard coating surface in imines film.The laminate for example can be with Emulsion sheet or cover film (protective film) etc. particularly suitable for display display surface.

Claims (12)

1. a kind of laminate is the laminate comprising the film containing polyimides and hard conating, which is characterized in that
In the polyimides,
The total content of repetitive unit represented by the following general formula (1) is more than 90 moles of % relative to whole repetitive units, also,
Repetitive unit represented by repetitive unit represented by following chemical formula (2-1) and/or following chemical formula (2-2) always contains Amount is 50 moles of % or more relative to whole repetitive units,
[changing 1]
In formula, A is 4 valence groups of the alicyclic structure comprising aromatic rings or 4 member rings or 6 member rings, wherein 6 member rings can be structure The crosslinking ring of cross-linked structure is bonded to each other and formd at the carbon atom of 6 member rings, and B is the divalent comprising aromatic rings or alicyclic structure Group, wherein A and B contained by each repetitive unit can be the same or different,
[changing 2]
2. laminate as described in claim 1, which is characterized in that in the polyimides, the chemical formula (2-1) is represented Repetitive unit and/or the chemical formula (2-2) represented by repetitive unit total content relative to whole repetitive units be 60 Mole % or more.
3. laminate as described in claim 1, which is characterized in that in the polyimides, the chemical formula (2-1) is represented Repetitive unit content relative to whole repetitive units be 50 moles of % or more.
4. laminate according to any one of claims 1 to 3, which is characterized in that
The polyimides is represented by the repetitive unit and/or the chemical formula (2-2) represented by the chemical formula (2-1) Repetitive unit is constituted, alternatively,
The polyimides is represented by the repetitive unit and/or the chemical formula (2-2) represented by the chemical formula (2-1) One or more of repetitive unit represented by repetitive unit and the general formula (1) is constituted, and in the general formula (1), A is to include 4 4 valence groups of the alicyclic structure of member ring or 6 member rings, wherein 6 member rings can be bonded to each other and shape to constitute the carbon atom of 6 member rings At the crosslinking ring of cross-linked structure, B is the divalent group comprising aromatic rings.
5. laminate according to any one of claims 1 to 3, which is characterized in that the polyimides includes the chemistry Repetitive unit represented by repetitive unit represented by formula (2-1) and/or the chemical formula (2-2) and the general formula (1) institute table The repetitive unit shown, in the general formula (1), A is 4 valence groups of the alicyclic structure comprising aromatic rings or 4 member rings or 6 member rings, Wherein, 6 member rings can be bonded to each other and form the crosslinking ring of cross-linked structure to constitute the carbon atom of 6 member rings, and B is to include two The divalent group that aromatic rings passes through the ehter bond (- O-) structure to link.
6. laminate as claimed in claim 5, which is characterized in that the polyimides is by the weight represented by the general formula (1) One or more of multiple unit is constituted, and in the general formula (1), A is 4 valence groups of the alicyclic structure comprising 4 member rings or 6 member rings, Wherein, 6 member rings can be bonded to each other and form the crosslinking ring of cross-linked structure to constitute the carbon atom of 6 member rings, and B is following chemistry Divalent group represented by formula (B-1), divalent group represented by following chemical formula (B-2) pass through ether comprising two aromatic rings The divalent group for the structure that key (- O-) links,
Wherein, repetitive unit represented by repetitive unit and/or the chemical formula (2-2) represented by the chemical formula (2-1) Total content relative to whole repetitive units be 50 moles of % or more,
[changing 3]
7. such as laminate according to any one of claims 1 to 6, which is characterized in that the pencil hardness of the hard coating surface For 2H or more.
8. such as laminate according to any one of claims 1 to 7, which is characterized in that the hard conating by curable resin at Divide or is formed including at least the solidfied material of curable resin ingredient and the hardening resin composition of inorganic filler.
9. a kind of manufacturing method of laminate, which is characterized in that
It is with following processes:
The hardening resin composition for including at least curable resin ingredient is coated on the process on the film containing polyimides, Wherein, in the polyimides, the total content of repetitive unit represented by the following general formula (1) is super relative to whole repetitive units Cross 90 moles of %, and weight represented by repetitive unit represented by following chemical formula (2-1) and/or following chemical formula (2-2) The total content of multiple unit is 50 moles of % or more relative to whole repetitive units；With
The process that the curing of coating of the hardening resin composition is formed into hard conating,
[changing 4]
In formula, A is 4 valence groups of the alicyclic structure comprising aromatic rings or 4 member rings or 6 member rings, wherein 6 member rings can be structure The crosslinking ring of cross-linked structure is bonded to each other and formd at the carbon atom of 6 member rings, and B is the divalent comprising aromatic rings or alicyclic structure Group, wherein A and B contained by each repetitive unit can be the same or different,
[changing 5]
10. the manufacturing method of laminate as claimed in claim 9, which is characterized in that the hardening resin composition is into one Step includes inorganic filler.
11. a kind of emulsion sheet or cover film of display display surface, which is characterized in that it includes any one of claims 1~8 The laminate.
12. a kind of optical component, display member, touch panel component or touch sensor component, which is characterized in that it includes Laminate according to any one of claims 1 to 8.
CN201780069665.XA 2016-11-11 2017-11-10 Laminate comprising polyimide film and hard conating Pending CN109922956A (en)

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