CN106164178B - Composition is used in manufacturing method and the resin film formation of resin film - Google Patents

Composition is used in manufacturing method and the resin film formation of resin film Download PDF

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Publication number
CN106164178B
CN106164178B CN201580017618.1A CN201580017618A CN106164178B CN 106164178 B CN106164178 B CN 106164178B CN 201580017618 A CN201580017618 A CN 201580017618A CN 106164178 B CN106164178 B CN 106164178B
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resin film
formula
polyimides
tetracarboxylic dianhydride
grain diameter
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CN106164178A (en
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叶镇嘉
何邦庆
末村尚彦
小出泰之
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Nissan Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The purpose of the present invention is to provide, not only excellent heat resistance, but also there is the resin film for postponing low such feature, especially it is suitable as the manufacturing method of the resin film of the substrate of flexible device and the resin film formation composition of the resin film and the such resin film of formation.Solution of the invention is to be related to a kind of manufacturing method of resin film, it is characterized in that, using containing polyimides, the resin film of silicon dioxide granule and organic solvent, which is formed, uses composition, the polyimides is to carry out polyamic acid obtained from imidizate, the polyamic acid is obtained from reacting tetracarboxylic dianhydride's ingredient comprising ester ring type tetracarboxylic dianhydride with the diamine component comprising fluorinated aromatic diamines, the average grain diameter of the silicon dioxide granule is 100nm or less, the average grain diameter is calculated by the specific surface area value measured using nitrogen adsorption method.

Description

Composition is used in manufacturing method and the resin film formation of resin film
Technical field
The resin obtained the present invention relates to the manufacturing method of resin film and resin film formation composition, by it is thin More specifically the method for the delay of film and reduction resin film is in particular to suitble to the displays such as flexible display substrate Composition is used in manufacturing method and the resin film formation of the resin film of the purposes of substrate.
Background technique
In recent years, with the rapid progress of the electronic equipments such as liquid crystal display, display of organic electroluminescence, device it is thin Type, lightweight and flexibility are gradually required.
In these devices, various electronic components are formed on glass substrate, for example, thin film transistor (TFT), transparent electrode etc., But by the way that the glass material is replaced with soft and light weight resin material, it can be achieved that the slimming of device itself, lightweight, soft Property.Moreover, the candidate as such resin material, polyimides causes concern, the various reports about polyimide film Announcement has all the time and (see, for example patent document 1,2).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 60-188427 bulletin
Patent document 2: Japanese Unexamined Patent Application 58-208322 bulletin
Patent document 3: No. 2011/149018 pamphlet of International Publication
Summary of the invention
Problems to be solved by the invention
In addition, using polyimide resin material as the substrate of display in use, expectation and be required of, not only should The resin material transparency is excellent, and is as the material for requiring the delay (retardation) of one of performance low.Even soft The case where property display base plate, other than high flexibility (flexibility), it is also necessary to meet these requirements performance.It is mentioned here Postpone (phase difference, phase delay), refers to the product of birefringent (difference of two orthogonal refractive index) and film thickness, it is the numerical value, special The delay for being thickness direction is the important numerical value for influencing viewing angle characteristic.Known big length of delay, which can become, leads to display The reason of display quality declines is (referring for example to patent document 3).
The present invention is given this situation to propose, its purpose is to provide, not only heat resistance and flexibility are excellent, But also there is the resin film for postponing low such feature, especially it is suitable as the resin film of the substrate of flexible device Composition is used in manufacturing method and the resin film and the resin film formation for forming such resin film.
Especially the object of the invention is also to provide a kind of manufacturing methods of resin film and the resin film and shape At the resin film formation composition of such resin film, not only heat resistance and flexibility are excellent for the resin film, but also Also have and postpone low such feature, and then the transparency is also excellent, is suitable as the basilar memebrane of display base plate, especially as The basilar memebrane of flexible display substrate and have excellent performance.
In addition, the present invention also aims to provide the resin that reduction can be used as the substrate of flexible device etc. and be used The method of the delay of film.
The method used for solving the problem
The present inventors have made intensive studies to achieve the goals above, as a result, it has been found that, to specific structure Cooperate resin film excellent heat resistance obtained by silica, delay low in the polyimides of monomeric unit and then also has soft Soft excellent such feature, it was found that, it is resistance to so as to realize by making the defined range of use level of the silica It is hot it is excellent, delay is low, flexibility is excellent and then the transparency also excellent resin film, so as to complete the present invention.
That is, as the 1st viewpoint, being related to a kind of manufacturing method of resin film about the present invention, which is characterized in that use Resin film formation composition containing polyimides, silicon dioxide granule and organic solvent,
The polyimides is obtained from polyamic acid is carried out imidizate, and the polyamic acid is made comprising alicyclic ring Obtained from tetracarboxylic dianhydride's ingredient of formula tetracarboxylic dianhydride is reacted with the diamine component comprising fluorinated aromatic diamines,
The average grain diameter of the silicon dioxide granule is 100nm hereinafter, the average grain diameter is by being surveyed using nitrogen adsorption method What the specific surface area value obtained calculated.
As the 2nd viewpoint, it is related to method described in the 1st viewpoint, aforementioned ester ring type tetracarboxylic dianhydride includes shown in formula (C1) Tetracarboxylic dianhydride.
(in formula (C1), B1Indicate the group of 4 valences in formula (X-1)~(X-12),
(in formula, multiple R indicate that hydrogen atom or methyl, * indicate associative key independently of each other.)〕
As the 3rd viewpoint, it is related to method described in the 1st viewpoint or the 2nd viewpoint, aforementioned fluorinated aromatic diamines includes formula (A1) diamines shown in.
H2N-B2-NH2 (A1)
(in formula, B2Indicate the group of the divalent in formula (Y-1)~(Y-34).)
(in formula, * indicates associative key.)
As the 4th viewpoint, it is related to method described in the 1st viewpoint, aforementioned polyimides includes monomer list shown in formula (2) Member.
As the 5th viewpoint, be related to method described in any one of the 1st viewpoint~the 4th viewpoint, aforementioned polyimides with it is aforementioned The mass ratio of silicon dioxide granule is 7:3~3:7.
As the 6th viewpoint, it is related to method described in any one of the 1st viewpoint~the 5th viewpoint, aforementioned average grain diameter is 60nm Below.
As the 7th viewpoint, it is related to resin film manufactured by the method as described in any one of the 1st viewpoint~the 6th viewpoint.
As the 8th viewpoint, be related to a kind of resin film formation composition, containing polyimides, silicon dioxide granule and Organic solvent,
The polyimides is obtained from polyamic acid is carried out imidizate, and the polyamic acid is made comprising alicyclic ring Obtained from tetracarboxylic dianhydride's ingredient of formula tetracarboxylic dianhydride is reacted with the diamine component comprising fluorinated aromatic diamines,
The average grain diameter of the silicon dioxide granule is 100nm hereinafter, the average grain diameter is by being surveyed using nitrogen adsorption method What the specific surface area value obtained calculated.
As the 9th viewpoint, it is related to resin film formation composition described in the 8th viewpoint, aforementioned ester ring type tetrabasic carboxylic acid two Acid anhydride includes tetracarboxylic dianhydride shown in formula (C1).
(in formula (C1), B1Indicate the group of 4 valences in formula (X-1)~(X-12).
(in formula, multiple R indicate that hydrogen atom or methyl, * indicate associative key independently of each other.)〕
As the 10th viewpoint, it is related to resin film formation composition described in the 8th viewpoint or the 9th viewpoint, it is aforementioned fluorine-containing Aromatic diamine includes diamines shown in formula (A1).
H2N-B2-NH2 (A1)
(in formula, B2Indicate the group of the divalent in formula (Y-1)~(Y-34).)
(in formula, * indicates associative key.)
As the 11st viewpoint, it is related to resin film formation composition described in the 8th viewpoint, aforementioned polyimides includes formula (2) monomeric unit shown in.
As the 12nd viewpoint, it is related to resin film formation composition described in any one of the 8th viewpoint~the 11st viewpoint, The mass ratio of aforementioned polyimides and aforementioned silicas particle is 7:3~3:7.
As the 13rd viewpoint, it is related to resin film formation composition described in any one of 8 viewpoints~the 12nd viewpoint, it is preceding Stating average grain diameter is 60nm or less.
As the 14th viewpoint, it is related to a kind of method of delay for reducing resin film, which is characterized in that using containing polyamides The resin film formation of imines, silicon dioxide granule and organic solvent forms resin film with composition,
The polyimides is obtained from polyamic acid is carried out imidizate, and the polyamic acid is made comprising alicyclic ring Obtained from tetracarboxylic dianhydride's ingredient of formula tetracarboxylic dianhydride is reacted with the diamine component comprising fluorinated aromatic diamines,
The average grain diameter of the silicon dioxide granule is 100nm hereinafter, the average grain diameter is by being surveyed using nitrogen adsorption method What the specific surface area value obtained calculated.
Invention effect
The resin film formation composition being related to using a scheme of the invention, a scheme according to the present invention are related to And resin film manufacturing method, can be formed well with reproducibility has low linear expansion coefficient, and excellent heat resistance has Low delay, and then the resin film that flexibility is excellent.
It is according to the present invention another especially with the resin film formation composition that another program of the invention is related to The manufacturing method for the resin film that scheme is related to, can be formed well with reproducibility has low linear expansion coefficient, and heat resistance is excellent It is different, there is high transparency and low delay, and then the resin film that flexibility is excellent.
Moreover, resin film of the present invention shows that low linear expansion coefficient, high transparency are (high light transmittance, low Yellowing), low latency, and then flexibility is also excellent, therefore can be suitable as the substrate of flexible device, particularly flexible display It uses.
In turn, the method for the delay for the reduction resin film being related to according to the present invention, can be effectively reduced resin film Delay.
Such manufacturing method of the present invention, composition, resin film and the reduction method of delay can be abundant The corresponding characteristics such as high flexibility, low linear expansion coefficient, high transparency (high light transmittance, low yellowing), low latency of requiring The progress in the field of flexible device substrate, particularly flexible display substrate.
Specific embodiment
It is described in detail below for the present invention.
The resin film formation composition used in the manufacturing method of resin film of the invention contains following specific Polyimides, silicon dioxide granule and organic solvent, which is also object of the invention with composition.
[polyimides]
Polyimides used in the present invention is that polyamic acid is carried out to polyimides obtained from imidizate, described poly- Amic acid is to make tetracarboxylic dianhydride's ingredient comprising ester ring type tetracarboxylic dianhydride and the diamine component comprising fluorinated aromatic diamines Obtained from reaction.
Wherein, aforementioned ester ring type tetracarboxylic dianhydride preferably comprises tetracarboxylic dianhydride shown in following formula (C1), aforementioned fluorine-containing Aromatic diamine preferably comprises diamines shown in following formula (A1).
(in formula, B1Indicate the group of 4 valences in formula (X-1)~(X-12).
(in formula, multiple R indicate that hydrogen atom or methyl, * indicate associative key independently of each other.)〕
H2N-B2-NH2 (A1)
(in formula, B2Indicate the group of the divalent in formula (Y-1)~(Y-34).)
(in formula, * indicates associative key.)
In tetracarboxylic dianhydride shown in above-mentioned formula (C1), the B in preferred formula1For formula (X-1), (X-4), (X-6), (X-7) Compound represented.
In addition, in diamines shown in above-mentioned (A1), the B in preferred formula2For formula (Y-12), (Y-13) compound represented.
As preferred example, make diamine reactant shown in tetracarboxylic dianhydride shown in above-mentioned formula (C1) and above-mentioned formula (A1) And polyamic acid is obtained, it includes shown in aftermentioned formula (2) which, which is carried out polyimides obtained from imidizate, Monomeric unit.
In order to obtain the characteristic, soft as the purpose of the present invention with low linear expansion coefficient, low latency and high transparency Soft excellent resin film, for the total mole number of tetracarboxylic dianhydride's ingredient, ester ring type tetracarboxylic dianhydride, such as on Stating tetracarboxylic dianhydride shown in formula (C1) is preferably 90 moles of % or more, more preferably 95 moles of % or more, particularly most preferably For all (100 moles of %) is tetracarboxylic dianhydride shown in above-mentioned formula (C1).
In addition, similarly, it is above-mentioned with low linear expansion coefficient, the characteristic of low latency and high transparency, softness in order to obtain The excellent resin film of property, for the total mole number of diamine component, fluorinated aromatic diamines, such as shown in formula (A1) Diamines is preferably 90 moles of % or more, more preferably 95 moles of % or more.In addition, diamine component can all (100 moles of %) For diamines shown in above-mentioned formula (A1).
An example as a preferred option, the present invention used in polyimides include following formula (1) shown in monomer list Member.
It is more excellent as monomeric unit shown in above-mentioned formula (1), preferably monomeric unit shown in formula (1-1) or formula (1-2) It is selected as monomeric unit shown in formula (1-1).
Preferred scheme according to the present invention, the present invention used in polyimides not only contain shown in previously described formula (1) Monomeric unit, also containing monomeric unit shown in formula (2).
It is more excellent as monomeric unit shown in above-mentioned formula (2), preferably monomeric unit shown in formula (2-1) or formula (2-2) It is selected as monomeric unit shown in formula (2-1).
The polyimides being used in the present invention includes monomer shown in monomeric unit shown in above-mentioned formula (1) and formula (2) In the case where unit, it is preferred that with the molar ratio computing in polyimides chain, preferably with monomeric unit shown in formula (1): formula (2) monomeric unit=10:1~1:10 ratio shown in includes more preferably to include with the ratio of 10:1~3:1.
In addition to as the aforementioned ester ring type tetracarboxylic dianhydride ingredient comprising tetracarboxylic dianhydride shown in formula (C1) and including formula (A1) monomeric unit derived from the diamine component of diamines shown in, for example, monomeric unit shown in above-mentioned formula (1) and formula (2) with Outside, polyimides of the invention can also include other monomeric units.As long as the content ratio of the other monomers unit is not damaged The characteristic for the resin film that evil is formed by resin film formation of the invention with composition, then can arbitrarily determine.About its ratio Example, relative to as the aforementioned ester ring type tetracarboxylic dianhydride ingredient comprising tetracarboxylic dianhydride shown in formula (C1) and including formula (A1) institute Monomeric unit derived from the diamine component of the diamines shown, such as the molal quantity of monomeric unit shown in formula (1), or including formula (2) in the case where monomeric unit shown in, relative to the total of monomeric unit shown in monomeric unit shown in formula (1) and formula (2) Molal quantity, preferably less than 20 moles of %, more preferably less than 10 moles of % are still more preferably less than 5 moles %.
As such other monomers unit, other lists with polyimide structures shown in such as formula (3) can be enumerated Body unit, but do not limited by the structural unit.
In formula (3), A indicates the organic group of 4 valences, preferably indicates shown in any of following formula (A-1)~(A-4) The group of 4 valences.In addition, B indicates the organic group of divalent, any in preferably expression (B-1)~(B-11) in above-mentioned formula (3) The group of divalent shown in a.In various, * indicates associative key.It should be noted that indicating following formula (A-1) in A in formula (3) In the case where the group of 4 valences shown in any of~(A-4), B can be any of previously described formula (Y-1)~(Y-34) Shown in divalent group.Alternatively, indicating divalent shown in any of following formula (B-1)~(B-11) in B in formula (3) In the case where group, A can be the group of 4 valences shown in any of previously described formula (X-1)~(X-12).
It can only include A and B in the case where in polyimides of the invention comprising monomeric unit shown in formula (3) The only monomeric unit that one of group illustrated by such as following formula is constituted, also may include at least one of A and B It is the two or more monomeric units of the two or more groups selected from following illustrations.
It should be noted that each monomeric unit combines in any order in polyimides used in the present invention.
As preferred an example, the polyimides with monomeric unit shown in above-mentioned formula (1) is by making as tetracarboxylic acid Bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic acid dianhydride of acid dianhydride component, with as diamine component following formula (4) shown in Diamines polymerize in organic solvent, by obtained polyamic acid carry out imidizate and obtain.
In addition, polyimides used in the present invention is other than the monomeric unit shown in above-mentioned formula (1) also containing upper In the case where stating monomeric unit shown in formula (2), the polyimides containing each monomeric unit shown in formula (1) and formula (2) is logical Cross make as the above-mentioned tetracarboxylic dianhydride of tetracarboxylic dianhydride's ingredient and 1,2,3,4- cyclobutanetetracarboxylic dianhydride, with as diamines at Diamines shown in the following formula (4) divided polymerize in organic solvent, and obtained polyamic acid is carried out imidizate and is obtained 's.
As diamines shown in above-mentioned formula (4), 2,2 '-bis- (trifluoromethyl) benzidine, 3,3 '-bis- (fluoroforms can be enumerated Base) benzidine, 2,3 '-bis- (trifluoromethyl) benzidine.
Wherein, as diamine component, and resin film lower from the linear expansion coefficient with resin film of the invention The higher viewpoint of the transparency set out, it is preferable to use 2 shown in following formula (4-1), 2 '-bis- (trifluoromethyl) benzidine or following 3 shown in formula (4-2), 3 '-bis- (trifluoromethyl) benzidine particularly preferably use 2,2 '-bis- (trifluoromethyl) benzidine.
In addition, the polyimides being used in the present invention has as the aforementioned rouge comprising tetracarboxylic dianhydride shown in formula (C1) Monomeric unit derived from ring type tetracarboxylic dianhydride ingredient and diamine component comprising diamines shown in formula (A1), such as above-mentioned formula (1) monomeric unit shown in monomeric unit and formula shown in (2) has other monomers list shown in above-mentioned formula (3) in addition to this In the case where member, the polyimides containing each monomeric unit shown in formula (1), formula (2) and formula (3) is by making as tetrabasic carboxylic acid Tetracarboxylic dianhydride shown in above-mentioned 2 kinds of tetracarboxylic dianhydrides of two anhydride components and following formula (5), with the above-mentioned formula as diamine component (4) diamines shown in diamines and following formula shown in (6) polymerize in organic solvent, and it is sub- that obtained polyamic acid is carried out acyl Amination and obtain.
The B in A and formula (6) in above-mentioned formula (5) is respectively indicated and the A and the identical meaning of B in previously described formula (3).
Specifically, pyromellitic acid anhydride, 3,3 ', 4,4 '-connection can be enumerated as tetracarboxylic dianhydride shown in formula (5) Pyromellitic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic acid dianhydrides, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic acid dianhydrides, 4,4 '-(hexafluoro isopropyl) two O-phthalic acid dianhydrides, 11,11- bis- (trifluoromethyls)- 1H- difluoro [3,4-b:3 ', 4 '-i]Ton -1,3,7,9- (11H- tetrone), 6,6 '-bis- (trifluoromethyls)-[5,5 '-two different benzene And furans] -1,1 ', 3,3 '-tetrones, two furans of 4,6,10,12- tetrafluoro simultaneously [3,4-b:3 ', 4 '-i] dibenzo [b, e] [1,4] TwoThe bis- two furans -1,3,5,7- tetrones of (trifluoromethoxy) benzo [1,2-c:4,5-c '] of English -1,3,7,9- tetrone, 4,8-, N, N '-[2,2 '-bis- (trifluoromethyl) xenyl -4,4 '-diyls] bis- (1,3- dioxa -1,3- dihydroisobenzofuran -5- first Amide) etc. aromatic tetracarboxylic acids；1,2- dimethyl -1,2,3,4- cyclobutanetetracarboxylic dianhydride, tetramethyl -1,2,3 1,2,3,4-, 4- cyclobutanetetracarboxylic dianhydride, 1,2,3,4- cyclopentane tetracarboxylic acid dianhydride, 1,2,3,4- cyclohexanetetracarboxylic acid dianhydride, 3,4- dicarboxyl The ester ring types tetracarboxylic dianhydrides such as base -1,2,3,4- tetrahydro -1- naphthalene succinic dianhydride；The fat such as 1,2,3,4- ethylene-dimalonic acid dianhydride Race tetracarboxylic dianhydride, but do not limited by these.
Wherein, the A preferably in formula (5) is the group of 4 valences shown in any of previously described formula (A-1)~(A-4) Tetracarboxylic dianhydride, that is, bis- (the trifluoromethyl) -1H- difluoros of 11,11- [3,4-b:3 ', 4 '-i] can be enumeratedTon -1,3,7,9- (11H- tetrone), 6,6 '-bis- (trifluoromethyls)-[5,5 '-two isobenzofuran] -1,1 ', 3,3 '-tetrones, 4,6,10,12- tetra- Two furans of fluorine simultaneously [3,4-b:3 ', 4 '-i] dibenzo [b, e] [1,4] twoBis- (the trifluoro methoxies of English -1,3,7,9- tetrone, 4,8- Base) benzo [1,2-c:4,5-c '] two furans -1,3,5,7- tetrone as preferred compound.
In addition, such as 2- (trifluoromethyl) benzene-Isosorbide-5-Nitrae-diamines, 5- (fluoroform can be enumerated as diamines shown in formula (6) Base) benzene -1,3- diamines, 5- (trifluoromethyl) benzene -1,2- diamines, bis- (trifluoromethyl)-benzene -1,4- diamines of 2,5-, 2,3- bis- (three Methyl fluoride)-benzene -1,4- diamines, bis- (trifluoromethyl)-benzene -1,4- diamines of 2,6-, bis- (trifluoromethyl)-benzene -1,2- two of 3,5- Amine, four (trifluoromethyl) -1,4- phenylenediamines, 2- (trifluoromethyl) -1,3- phenylenediamine, 4- (trifluoromethyl) -1,3- phenylenediamine, 2- Methoxyl group -1,4- phenylenediamine, 2,5- dimethoxy -1,4- phenylenediamine, 2- hydroxyl -1,4- phenylenediamine, 2,5- dihydroxy -1,4- benzene Diamines, 2- fluorobenzene -1,4- diamines, 2,5- difluorobenzene -1,4- diamines, 2- chlorobenzene -1,4- diamines, 2,5- dichloro-benzenes -1,4- diamines, 2,3,5,6- phenyl tetrafluoride -1,4- diamines, 4,4 '-(perfluoropropane -2,2- diyl) diphenylamines, the bis- [3- (trifluoromethyl) of 4,4 '-oxygen Aniline], bis- (4- amino-benzene oxygen) benzene of 1,4-, 1,3 '-bis- (4- amino-benzene oxygen) benzene, bis- (3- amino-benzene oxygen) benzene of 1,4-, Benzidine, 2- methyl biphenyl amine, 3- methyl biphenyl amine, 2- (trifluoromethyl) benzidine, 3- (trifluoromethyl) benzidine, 2,2 '- Dimethylbenzidine (tolidine (m-TOLIDINE)), 3,3 '-dimethylbenzidines (o-tolidine (o- TOLIDINE)), 2,3 '-dimethylbenzidines, 2,2 '-dimethoxy benzidines, 3,3 '-dimethoxy benzidines, 2,3 '-two Methoxyl biphenyl amine, 2,2 '-dihydroxybiphenyl amine, 3,3 '-dihydroxybiphenyl amine, 2,3 '-dihydroxybiphenyl amine, 2,2 '-difluoros Benzidine, 3,3 '-DfBP amine, 2,3 '-DfBP amine, 2,2 '-dichloro-benzidine, 3,3 '-dichloro-benzidine, 2,3 '- Dichloro-benzidine, 4,4 '-diaminobenzene anilids, 4- aminophenyl -4 '-Aminobenzoate, octafluorobiphenyl amine, 2,2 ', 5,5 '-tetramethyl benzidines, 3,3 ', 5,5 '-tetramethyl benzidines, 2,2 ', 5,5 '-four (trifluoromethyl) benzidine, 3,3 ', 5, 5 '-four (trifluoromethyl) benzidine, 2,2 ', it is 5,5 '-tetrachloro benzidines, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, 4,4 '-bis- (3- amino-benzene oxygen) biphenyl, 4,4 '-{ [3,3 "-bis- (trifluoromethyls)-(1,1 ': 3 ', 1 "-terphenyl) -4,4 "-diyl] - Bis- (oxygen) } diphenylamines, 4,4 '-{ [(perfluoropropane -2,2- diyl) is bis- (4,1- phenylene)] bis- (oxygen) } diphenylamines, 1- (4- ammonia Base phenyl) -5 aromatic diamines such as (or 6) amine of -2,3- dihydro -1,3,3- trimethyl -1H- indenes；4,4 '-di-2-ethylhexylphosphine oxide (hexamethylenes Amine), 4,4 '-di-2-ethylhexylphosphine oxides (3- methyl cyclohexylamine), isophorone diamine, trans-1,4-cyclohexane diamines, cis- -1,4- ring Hexane diamine, 1,4- hexamethylene bis- (methyl amines), bicyclic (2.2.1) heptane of 2,5- bis- (amino methyls), bis- (the amino first of 2,6- Base) bicyclic (2.2.1) heptane, bis- (amino methyl) tricyclic (5.2.1.0) decane of 3,8-, 1,3- diamino adamantane, 2,2- be bis- Bis- (4- aminocyclohexyl) hexafluoropropane of (4- aminocyclohexyl) propane, 2,2-, 1,3- propanediamine, 1,4- tetramethylene two Amine, 1,5- five methylene diamine, 1,6- hexamethylene diamine, 1,7- heptamethylene diamines, eight methylene diamine of 1,8-, 1,9- nine The aliphatic diamines such as methylene diamine, but do not limited by these.
Wherein, the B preferably in formula (6) is the virtue of divalent group shown in any of previously described formula (B-1)~(B-11) Fragrant race's diamines, that is, 2,2 '-bis- (trifluoromethoxies)-(1,1 '-xenyls) -4 can be enumerated, 4 '-diamines are [also known as: 2,2 '-diformazans Oxygroup benzidine], 4,4 '-(perfluoropropane -2,2- diyl) diphenylamines, bis- (trifluoromethyl) benzene -1,4- diamines of 2,5-, 2- (three Methyl fluoride) benzene -1,4- diamines, 2- fluorobenzene -1,4- diamines, 4,4 '-oxygen bis- [3- (trifluoromethyl) aniline], 2,2 ', 3,3 ', 5, 5 ', 6,6 '-octafluoros [1,1 '-xenyl] -4,4 '-diamines [also known as: octafluorobiphenyl amine], 2,3,5,6- phenyl tetrafluoride -1,4- diamines, 4,4 '-[3,3 "-bis- (trifluoromethyls)-(1,1 ': 3 ', 1 "-terphenyl) -4,4 "-diyl]-bis- (oxygen) } diphenylamines, 4,4 ' - { [(perfluoropropane-2,2- diyl) is bis- (4,1- phenylene)] bis- (oxygen) } diphenylamines, 1- (4- aminophenyl) dihydro-1-2,3-, - 5 (or 6) amine of 3,3- trimethyl -1H- indenes is as preferred diamines.
<synthesis of polyamic acid>
As previously mentioned, polyimides used in the present invention be by polyamic acid carry out imidizate obtained from, it is described Polyamic acid is to make tetracarboxylic dianhydride's ingredient comprising ester ring type tetracarboxylic dianhydride shown in above-mentioned formula (C1) and comprising above-mentioned formula (A1) obtained from the diamine component reaction of fluorinated aromatic diamines shown in.
Specifically, being by making comprising bicyclic [3,3,0] octane -2,4,6,8- tetramethyls for example as preferred an example Acid dianhydride, 1,2,3,4- cyclobutanetetracarboxylic dianhydride according to circumstances and then the tetrabasic carboxylic acid according to shown in desired above-mentioned formula (5) Tetracarboxylic dianhydride's ingredient of dianhydride, with include diamines shown in above-mentioned formula (4) and the diamines according to shown in desired above-mentioned formula (6) The diamine component of ingredient polymerize in organic solvent, and resulting polyamic acid is carried out obtained from imidizate.
The above-mentioned reaction for generating polyamic acid by two kinds of ingredients can be easier to carry out in organic solvent, and not give birth to It produces and is advantageous on this aspect of by-product.
The addition of diamine component in the reacting of these tetracarboxylic dianhydride's ingredients and diamine component is to consider than (molar ratio) The molecular weight of polyamic acid, and then consider that the molecular weight etc. of polyimides obtained from the imidizate after is fitted When setting, but relative to diamine component 1, it can usually make tetracarboxylic dianhydride's ingredient 0.8~1.2 or so, such as 0.9~ 1.1 or so, preferably 0.95~1.02 or so.Same as common polycondensation reaction, closer to 1.0, generation gathers the molar ratio The molecular weight of amic acid is bigger.
As long as the organic solvent used when above-mentioned tetracarboxylic dianhydride's ingredient is reacted with diamine component does not generate reaction Adverse effect and by the polyamic acid of generation dissolve solvent be just not particularly limited.Its concrete example is enumerated below.
It can enumerate for example, metacresol, 2-Pyrrolidone, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, N- second Alkenyl -2-Pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 3- methoxyl group-N, N- dimethylpropionamide, 3- ethyoxyl-N, N- dimethylpropionamide, 3- propoxyl group-N, N- dimethylpropionamide, 3- isopropoxy-N, N- dimethyl propionyl Amine, 3- butoxy-N, N- dimethylpropionamide, 3- sec-butoxy-N, N- dimethylpropionamide, 3- tert-butoxy-N, N- diformazan Base propionamide, gamma-butyrolacton, N- methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl are sub- Sulfone, isopropanol, methoxy amylalcohol, dipentene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isopentyl Ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, the third two Alcohol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, two Ethylene glycol acetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, two Propylene glycol monoethyl, dipropylene glycol monoacetate list ethylether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list third Base ether, 3- methyl -3- methoxybutyl acetic acid esters, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanol, Di Iso Propyl Ether, Ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, Hexyl ether, twoAlkane, n-hexane, pentane, normal octane, Anaesthetie Ether, cyclohexanone, ethylene carbonate, propene carbonate, Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list ethylether, methyl pyruvate, Ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3- methoxypropionate, 3- ethoxy-c Acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, diethylene glycol dimethyl ether (Diglyme), 4- Hydroxy-4-methyl-2-pentanone etc., but do not limited by these.These solvents can two or more uses alone or in combination.
In turn, even the solvent for dissolving polyamic acid, the model that can not also be precipitated in polyamic acid generated It is mixed into above-mentioned solvent and uses in enclosing.In addition, moisture in organic solvent inhibits polymerization reaction, and then becomes and make to generate The reason of polyamic acid hydrolyzes, therefore it is preferable to use the solvents dehydrated as far as possible for organic solvent.
As the method for reacting above-mentioned tetracarboxylic dianhydride's ingredient in organic solvent with diamine component, can enumerate diamines Dispersion liquid made of ingredient is dispersed or dissolved in organic solvent or solution are stirred, and directly add tetracarboxylic dianhydride thereto The side of dispersion liquid made of tetracarboxylic dianhydride's ingredient is dispersed or dissolved in organic solvent by ingredient or addition or solution Method；Diamines is added in the dispersion liquid to made of being dispersed or dissolved in organic solvent tetracarboxylic dianhydride's ingredient or solution in turn The method of ingredient；And tetracarboxylic dianhydride's ingredient and the method for diamine compound ingredient etc. are alternately added, it can be these methods Any one of.
In addition, in the case where tetracarboxylic dianhydride's ingredient and/or diamine component include multiple compounds, it can be to mix in advance The state of conjunction makes its reaction, it can be made individually successively to be reacted, and can also make obtained by individually successively being reacted Low-molecular weight carries out hybrid reaction and high molecular weight body is made.
As long as above-mentioned polyamic acid synthesize when temperature in the range of from fusing point to the boiling point of the above-mentioned solvent used into Row is suitably set, such as can choose -20 DEG C~150 DEG C of optional temperature, but good, and -5 DEG C~100 DEG C, logical It is often 0~100 DEG C or so, preferably 0~70 DEG C or so.
Due to the reaction time depend on reaction temperature, the reactivity of raw material, cannot without exception depending on, but be usually 1~100 hour or so.
In addition, reaction can be carried out with optional concentration, but if concentration is too low, then it is not readily available the poly- of high molecular weight Close object；If excessive concentration, the viscosity of reaction solution becomes excessively high, it is difficult to uniformly stirred, therefore tetracarboxylic dianhydride at Dividing with total concentration in the reaction solution of diamine component is preferably 1~50 mass %, more preferably 5~40 mass %.Reaction Initial stage is carried out with high concentration, can also add organic solvent later.
<imidizate of polyamic acid>
As the method for making polyamic acid carry out imidizate, can enumerate the direct-fired hot acyl of the solution of polyamic acid Imidization, the catalyst imidizate that catalyst is added into the solution of polyamic acid.
100 DEG C of temperature~400 DEG C, preferably 120 in the case where making polyamic acid hot-imide in the solution DEG C~250 DEG C, preferably carried out while the water generated by imidization reaction is discharged to outside system.
Chemistry (catalyst) imidizate of polyamic acid can be by adding base catalysis in the solution to polyamic acid Agent and acid anhydrides will be stirred to carry out under the conditions of -20~250 DEG C, preferably 0~180 DEG C of temperature in system.
The amount of basic catalyst is 0.5~30 mole times, preferably 1.5~20 moles of the amide acidic group of polyamic acid Times, the amount of acid anhydrides is 1~50 mole times, preferably 2~30 moles times of the amide acidic group of polyamic acid.
As basic catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine, 1- ethyl piperidine etc. can be enumerated, Middle pyridine has appropriate alkalinity for carrying out reaction, is therefore preferred.
As acid anhydrides, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be enumerated, wherein if using acetic acid Acid anhydride, then purification after reaction becomes easy, and is therefore preferred.
It can be by adjusting catalytic amount and reaction temperature, reaction time using the acid imide rate of catalyst imidizate To control.
In for polyimide resin of the invention, the dehydration closed-loop rate (acid imide rate) of amide acidic group is not necessarily required 100%, can depending on the application, purpose optionally could be adjusted to using.Particularly preferably 50% or more.
In the present invention, it using its filtrate or can be directly diluted or dense after by the filtering of above-mentioned reaction solution Contracting, cooperates aftermentioned silica etc. thereto and resin film formation composition is made.In the feelings like this by filtering Under condition, heat resistance, flexibility or linear expansion coefficient the characteristic deterioration that can become resulting resin film can not only be reduced as far as possible The reason of impurity be mixed into, additionally it is possible to efficiency obtains resin film formation composition well.
In addition, about for polyimides of the invention, it is contemplated that the intensity of resin film, behaviour when forming resin film The property made, uniformity of resin film etc. are divided equally again obtained by the polystyrene conversion preferably by gel permeation chromatography (GPC) Son amount (Mw) is 5,000~200,000.
<polymer recovery>
In the case that recycling component of polymer carrys out use in the reaction solution from polyamic acid and polyimides, as long as will Reaction solution, which is put into poor solvent, to be precipitated.As the poor solvent for precipitating, can enumerate methanol, acetone, Hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene, water etc..Put into poor solvent In precipitate it polymer after filtering and recycling, under normal or reduced pressure, carry out room temperature or heat drying.
In addition, if the polymer for recycling precipitating is re-dissolved in organic solvent, the operation of reprecipitation recycling repeats 2 ~10 times, then it can reduce the impurity in polymer.As poor solvent at this time, if using such as alcohols, ketone, hydrocarbon etc. 3 kinds or more of poor solvent then further improves the efficiency of purification, is therefore preferred.
The organic solvent for dissolving resin component in reprecipitation recovery process is not particularly limited.It, can as concrete example Enumerate N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- methyl caprolactam, 2- pyrroles Alkanone, N- ethyl pyrrolidone, n-vinyl pyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl Sulfoxide, gamma-butyrolacton, 1,3- dimethyl-2-imidazolidinone, dipentene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, first Base isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propene carbonate, diethylene glycol dimethyl ether, 4- hydroxyl -4- Methyl -2 pentanone etc..These solvents can mix two or more come using.
[silica]
It is not particularly limited to for silica (silica) of the invention, but the silica of particle shape, such as flat Equal partial size is 100nm hereinafter, such as 5nm~100nm, preferably 5nm~55nm, more highly transparent is obtained from reproducibility well Film from the perspective of, preferably 5nm~50nm, more preferably 5nm~45nm are still more preferably 5nm~35nm, into One step is preferably 5nm~30nm.
In the present invention, the average grain diameter of so-called silicon dioxide granule is by using silicon dioxide granule, utilizing N2 adsorption The average size that the specific surface area value of method measurement calculates.
Especially in the present invention it is preferable to use the colloidal silicon dioxide of the value with above-mentioned average grain diameter, as The colloidal silicon dioxide, can be used silica solution.As silica solution, it can be used using sodium silicate aqueous solution as raw material, pass through public affairs The water silica sol and the water as the decentralized medium of the water silica sol is replaced into organic solvent and is obtained that the method known manufactures Organic silicon sol.
Further, it is also possible to using in the organic solvents such as alcohol, in catalyst (for example, ammonia, organic amine compound, hydroxide The basic catalysts such as sodium) in the presence of, silicon obtained by the alkoxy silanes such as methyl silicate, silester are hydrolyzed, are condensed Colloidal sol or the organic silicon sol that silica solution progress solvent is replaced into other organic solvents.
Wherein, present invention preferably uses the organic silicon sols that decentralized medium is organic solvent.
As the example of the organic solvent in above-mentioned organic silicon sol, it is rudimentary that methanol, ethyl alcohol, isopropanol etc. can be enumerated Alcohol；The linears class such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide；The cyclic amides such as n-methyl-2-pyrrolidone Class；The ethers such as gamma-butyrolacton；The glycols such as ethyl cellosolve, ethylene glycol, acetonitrile etc..The displacement can by using the way of distillation, The usual way of ultrafiltration etc. carries out.
The viscosity of above-mentioned organic silicon sol is 0.6mPas~100mPas or so at 20 DEG C.
The example of commercially available product as above-mentioned organic silicon sol, can enumerating such as trade name MA-ST-S, (methanol dispersed silicon is molten Glue, Nissan Chemical Industries (strain) system), trade name MT-ST (methanol disperse silica solution, Nissan Chemical Industries (strain) system), trade name MA-ST-UP (methanol disperses silica solution, Nissan Chemical Industries (strain) system), (methanol disperses silica solution, daily output to trade name MA-ST-M Chemical industry (strain) system), trade name MA-ST-L (methanol disperse silica solution, Nissan Chemical Industries (strain) system), trade name IPA- ST-S (isopropanol disperses silica solution, Nissan Chemical Industries (strain) system), (isopropanol disperses silica solution, daily output to trade name IPA-ST Chemical industry (strain) system), trade name IPA-ST-UP (isopropanol disperse silica solution, Nissan Chemical Industries (strain) system), trade name IPA-ST-L (isopropanol disperses silica solution, Nissan Chemical Industries (strain) system), (isopropanol dispersed silicon is molten by trade name IPA-ST-ZL Glue, Nissan Chemical Industries (strain) system), trade name NPC-ST-30 (n-propyl cellosolve disperse silica solution, Nissan Chemical Industries (strain) system), trade name PGM-ST (1- methoxy-2-propanol disperse silica solution, Nissan Chemical Industries (strain) system), trade name DMAC-ST (dimethyl acetamide disperses silica solution, Nissan Chemical Industries (strain) system), trade name XBA-ST (dimethylbenzene-n-butanol Mixed solvent disperse silica solution, Nissan Chemical Industries (strain) system), trade name EAC-ST (ethyl acetate disperse silica solution, daily outputization Learn industrial (strain) system), (propylene glycol monomethyl ether disperses silica solution, Nissan Chemical Industries (strain) to trade name PMA-ST System), trade name MEK-ST (methyl ethyl ketone disperse silica solution, Nissan Chemical Industries (strain) system), trade name MEK-ST-UP (first Base ethyl ketone disperse silica solution, Nissan Chemical Industries (strain) system), trade name MEK-ST-L (methyl ethyl ketone disperse silica solution, day Produce chemical industry (strain) system) and trade name MIBK-ST (hexone dispersion silica solution, Nissan Chemical Industries (strain) System) etc., but do not limited by these.
In the present invention, the said goods that can be used by silica, for example as organic silicon sol are enumerated like that Silica in two or more mixing use.
[organic solvent]
Resin film formation composition of the invention is other than aforementioned polyimides and silica, also comprising organic Solvent.The organic solvent is not particularly limited, and can be enumerated for example, used when with above-mentioned modulation polyamic acid and polyimides The same solvent of the concrete example of reaction dissolvent.More specifically, n,N-Dimethylformamide, N, N- dimethylacetamide can be enumerated Amine, n-methyl-2-pyrrolidone, 1,3- dimethyl-2-imidazolinone, N- ethyl-2-pyrrolidone, gamma-butyrolacton etc..It needs Illustrate, organic solvent can be used alone, can also combine two or more come using.
Wherein, if it is considered that reproducibility obtains the high resin film of flatness well, then preferred N, N- dimethylacetamide Amine, n-methyl-2-pyrrolidone, gamma-butyrolacton.
[resin film, which is formed, uses composition]
The present invention is the resin film formation composition containing aforementioned polyimides, silica and organic solvent.This In resin film formation of the invention with composition be it is uniform, do not observe the composition mutually separated.
In resin film formation composition of the invention, the match ratio of aforementioned polyimides and aforementioned silicas with Mass ratio meter, preferably polyimides: silica=10:1~1:10, more preferably 8:2~2:8, such as 7:3~3:7.
In addition, resin film formation of the invention is usually 0.5~30 with the use level of the solid content in composition Quality % or so, preferably 5~25 mass % or so.If solid component concentration is less than 0.5 mass %, thin in production resin In terms of film, film efficiency is lower, and resin film forms the viscosity for using composition, and therefore, it is difficult to obtain surface uniformly to apply Film.In addition, if solid component concentration is more than 30 mass %, then the viscosity of resin film formation composition becomes excessively high, also It is to have the worry that film forming efficiency deteriorates, the surface uniformity of film is short of.It should be noted that solid component mentioned here Amount indicates the gross mass of the ingredient other than organic solvent, even monomer of liquid etc. is also included in weight as solid component It is interior.
It should be noted that the viscosity of resin film formation composition is the thickness etc. for considering made resin film And suitably set, but for the purpose of obtaining especially 5~50 μm or so of the resin film of thickness well by reproducibility In the case of, it is 500~50,000mPas or so, preferably 1,000~20,000mPas or so usually at 25 DEG C.
In order to assign resin film formation composition processing characteristics of the invention, various functionality, other can be cooperated The low molecule or high-molecular compound of various organic or inorganics.It is, for example, possible to use catalyst, defoaming agent, levelling agent, surface are living Property agent, dyestuff, plasticizer, particle, coupling agent, sensitizer etc..Such as catalyst can be in delay, the line to reduce resin film The coefficient of expansion adds when being purpose.It should be noted that other than aforementioned polyimides, silica and organic solvent, also Resin film formation composition comprising catalyst may be object of the invention.
The polyimides and dioxy that resin film formation composition of the invention can will be obtained by above-mentioned method SiClx is dissolved in above-mentioned organic solvent and obtains, and can also add titanium dioxide into the reaction solution after modulation polyimides Silicon further adds aforementioned organic solvents according to expectation and is made.
[resin film]
The resin film formation of present invention mentioned above is coated on substrate with composition, by the way that heating is dried And organic solvent is removed, it can obtain with high-fire resistance, high transparency, the flexibility of appropriateness and appropriate linear expansion coefficient And the small resin film of delay.
Moreover, above-mentioned resin film, i.e., the resin containing above-mentioned polyimides and above-mentioned inorganic silica compound is thin Film is also object of the invention.It in turn, also include the resin film of catalyst other than aforementioned polyimides and silica It is also object of the invention.
As the substrate of the manufacture for resin film, can enumerate for example, plastics (polycarbonate, polymethacrylates, Polystyrene, polyester, polyolefin, epoxy resin, melamine, Triafol T, ABS, AS, norbornene resin etc.), Metal, stainless steel (SUS), timber, paper, glass, silicon wafer, slabstone etc..
Especially in the case where the baseplate material application as electronic device, from can use sight as existing device Point sets out, and the substrate of application is preferably glass, silicon wafer, additionally due to obtained resin film shows good fissility, Therefore further preferred glass.It should be noted that the linear expansion coefficient of the substrate as application, from sticking up for the substrate after coating From the perspective of song, it is further preferred that, 30ppm/ DEG C or less, further preferably 20ppm/ DEG C or less.
It is not particularly limited, can be enumerated for example, painting of casting to the rubbing method of substrate coating resin film formation composition (relief printing plate, is put down at intaglio plate for cloth method, method of spin coating, knife coating, dip coating, rolling method, stick coating method, die coating method, ink-jet method, print process Version, silk-screen printing etc.) etc., these methods can be suitably used according to purpose.
Heating temperature is preferably 300 DEG C or less.If it exceeds 300 DEG C, then obtained resin film becomes fragile, and sometimes cannot Obtain the resin film for being particularly suitable for display base plate purposes.
In addition, if considering the heat resistance and linear expansion coefficient characteristic of obtained resin film, then it is desirable that, will After the resin film formation of coating has carried out heating in 5 minutes~2 hours with composition at 40 DEG C~100 DEG C, the state is maintained Increase heating temperature stage, it is final to be greater than 175 DEG C and 280 DEG C or less progress heating in 30 minutes~2 hours.Pass through as a result, So that this 2 temperature more than stage of stage of the stage of solvent seasoning and promotion molecularly oriented are heated, its table can be made Existing low thermal expansion characteristics.
In particular, the resin film formation of coating is preferably carried out 5 minutes~2 hours with 40 DEG C~100 DEG C with composition After heating, heat within 5 minutes~2 hours to be greater than 100 DEG C and 175 DEG C or less, then to be greater than 175 DEG C and 280 DEG C or less Heat within 5 minutes~2 hours.
Utensil for heating can be enumerated such as heating plate, baking oven.Heating atmosphere can be under air, be also possible to Under the non-active gas such as nitrogen, furthermore, it is possible under normal pressure or under reduced pressure, furthermore, it is possible to be applied in each stage of heating Different pressure.
About the thickness of resin film, especially in the case where being used as flexible display with substrate, usually 1~ 60m or so, preferably 5~50 μm or so adjust the thickness of the film before heating to form the resin film of desired thickness.
It should be noted that be not particularly limited as the method for removing the resin film being thusly-formed from substrate, It can enumerate and the resin film is carried out to method cooling, to film introducing gap to removing together with substrate, or be applied via roller Add tension to method of removing etc..
The light under wavelength 400nm may be implemented in the resin film that a thus obtained preferred scheme of the invention is related to Transmissivity is 75% or more the transparency high in this way.
In turn, which can have the linear expansion coefficient at such as 50 DEG C~200 DEG C as 60ppm/ DEG C or less, spy It is not 10ppm/ DEG C~35ppm/ DEG C value low in this way, the linear expansion coefficient that furthermore can have at such as 200 DEG C~250 DEG C is 80ppm/ DEG C or less, particularly 15ppm/ DEG C~55ppm/ DEG C value low in this way, the tree of excellent in dimensional stability when being heating Membrane of lipoprotein.
Especially the advantages of resin film is delay R in face0With thickness direction retardation RthIt is very small, postpone R in face0 By the wavelength in incident light be 590nm when birefringent (difference of 2 orthogonal refractive index in face) and film thickness product representation, thickness Direction postpones Rth2 when in terms of the section of thickness direction it is birefringent (2 refractive index in face respectively with the folding of thickness direction Penetrate the difference of rate) it is indicated respectively multiplied by the average value of 2 phase differences obtained from film thickness.In the average film of resin film of the invention In the case that thickness is 15 μm~40 μm, the delay R with thickness directionthLess than 700nm, for example, 660nm hereinafter, being, for example, 10nm~660nm postpones R in face0Less than 4, for example, 0.3~3.9, birefringence n less than 0.02, for example, 0.0003~ The low-down value such as 0.019.
Resin film is formed with composition by using resin film formation of the invention as a result, can reduce the tree The method of the delay of membrane of lipoprotein, the in this way delay of reduction resin film is also object of the invention.
The resin film of present invention mentioned above has above-mentioned characteristic, therefore meets as flexible display substrate Each condition required for basilar memebrane can be used particularly suitable as the basilar memebrane of flexible display substrate.
Embodiment
Enumerate embodiment below to further illustrate the present invention, but the present invention is not limited by following embodiments.
The meaning of the abbreviation number used below in an example is as follows.
<acid dianhydride>
BODA: bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic acid dianhydride
CBDA:1,2,3,4- cyclobutanetetracarboxylic dianhydride
TCA:2,3,5- tricarboxylic cyclopentyl acetic acid -1,4:2,3- dianhydride
BODAxx: bicyclic [2,2,2] octane -2,3,5,6- tetracarboxylic acid dianhydride
<diamines>
Bis- (trifluoromethyl) benzidine of TFMB:2,2 '-
- 5 (or 6) amine of TMDA:1- (4- aminophenyl) -2,3- dihydro -1,3,3- trimethyl -1H- indenes
<organic solvent>
DMAc:N, N- dimethyl acetamide
NMP:N- N-methyl-2-2-pyrrolidone N
DMF:N, dinethylformamide
IPA: isopropanol
GBL: gamma-butyrolacton
<silica solution>
IPA-ST: isopropanol disperses silica solution, and (silica average grain diameter: 10~15nm, silica solid ingredient are dense Degree: 30 mass %) Nissan Chemical Industries (strain) system
DMAC-ST:N, N- dimethyl acetamide disperse silica solution (silica average grain diameter: 10~15nm, silica Solid component concentration: 20 mass %), Nissan Chemical Industries (strain) system
GBL-ZL: gamma-butyrolacton disperses silica solution (silica solid constituent concentration: 25 mass %)
GBL-L: gamma-butyrolacton disperses silica solution (silica solid constituent concentration: 25 mass %)
GBL-M: gamma-butyrolacton disperses silica solution (silica solid constituent concentration: 30 mass %)
GBL-ST: gamma-butyrolacton disperses silica solution (silica solid constituent concentration: 30 mass %)
GBL-S: gamma-butyrolacton disperses silica solution (silica solid constituent concentration: 25 mass %)
GBL-UP: gamma-butyrolacton disperses silica solution (chain type, silica solid constituent concentration: 20 mass %)
It should be noted that above-mentioned gamma-butyrolacton disperses silica solution (GBL-ZL, GBL-L, GBL-M, GBL-ST, GBL-S And GBL-UP) it is as obtained from aftermentioned method, this method is respectively to disperse Nissan Chemical Industries (strain) preparing isopropanol Silica solution (IPA-ST-ZL, IPA-ST-L, IPA-ST) and Nissan Chemical Industries (strain) methanol processed dispersion silica solution (MA-ST-M, MA-ST-S, MA-ST-UP) in as solvent isopropanol or methanol carry out solvent be replaced into gamma-butyrolacton.
In addition, the silica average grain diameter in above-mentioned IPA-ST and DMAC-ST is goods catalogue value, what is specifically used In silica solution, the average grain diameter calculated by the specific surface area value using determination of nitrogen adsorption is as follows.Specifically, using ユ ア サ ア イ オ ニ Network ス society system, specific area measuring device モ ノ ソ ー Block MS-16 measure the specific surface of the dried powder of silica solution Product, uses the specific surface area S (m of measurement2/ g), average primary particle diameter calculated by formula D (nm)=2720/S.
It should be noted that in embodiment, device and condition for the modulation of sample and the analysis of physical property and evaluation It is as follows.
1) measurement of number-average molecular weight and weight average molecular weight
The number-average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) of polymer are using following Condition measurement, device: Showa electrician (strain) system, Showdex GPC-101, column: KD803 and KD805, column temperature: 50 DEG C, dissolution Solvent: DMF, flow: 1.5ml/ minutes, standard curve: standard polystyren.
2) film thickness
The film thickness of resulting resin film is that (strain) テ Network ロ ッ Network thickness gauge is utilized to measure.
3) linear expansion coefficient (CTE)
Using TA イ Application ス ツルメン Star society TMA Q400, by resin film be cut into width be 5mm, length 16mm Size is heated up with 10 DEG C/min first and is heated to 50~350 DEG C (heating for the first time), then dropped with 10 DEG C/min Temperature is simultaneously cooled to 50 DEG C, is then heated up with 10 DEG C/min and is heated to 50~420 DEG C (second of heating), by measuring this When second heating 50 DEG C~200 DEG C at linear expansion coefficient (CTE [ppm/ DEG C]) and 200 DEG C~250 DEG C at line The value of the coefficient of expansion (CTE [ppm/ DEG C]) and find out.It should be noted that by heating for the first time, cooling and second is heated, Apply loading 0.05N.
4) 5% weight reduces temperature (Td5%)
5% weight reduces temperature (Td5%[DEG C]) be by using TA イ Application ス ツルメン Star society TGA Q500, In nitrogen, resin film about 5~10mg is warming up to 50~800 DEG C with 10 DEG C/min and is measured and finds out.
5) light transmittance (transparency) (T400nm、T550nm) and CIE b value (CIE b*)
Light transmittance (the T of wavelength 400nm and 550nm400nm、T550nm[%]) and CIE b value (CIE b*) be using Japanese industrial (strain) SA4000 spectrometer processed of electricity color, is measured at room temperature with air reference.
6) postpone (Rth、R0)
Machine (strain) system, KOBURA 2100ADH are measured using prince, measures thickness direction retardation (R at room temperatureth) and Postpone (R in face0)。
It should be noted that thickness direction retardation (Rth) and face in postpone (R0) calculated using following formula.
R0=(Nx-Ny) × d=Δ Nxy × d
Rth=[(Nx+Ny)/2-Nz] × d=[(Δ Nxz × d)+(Δ Nyz × d)/2
Nx, Ny: (Nx is also known as slow axis (slow axis) 2 orthogonal refractive index by Nx > Ny, and Ny is referred to as fast in face Axis (Fast axis)).
Nz: the refractive index in thickness (vertical) direction for face
D: film thickness
Δ Nxy: the difference (Nx-Ny) (birefringent) of 2 refractive index in face
Δ Nxz: the refractive index Nz of refractive index Nx and thickness direction in face difference (birefringent)
Δ Nyz: the refractive index Nz of refractive index Ny and thickness direction in face difference (birefringent)
7) birefringent (Δ n)
Use the thickness direction retardation (R for passing through 6) delay acquisition above-mentionedth) value, calculated using following formula.
Δ N=[Rth/ d (film film thickness)]/1000
[1] the modulation example of silica solution
(modulation of modulation example 1:GBL-M)
Nissan Chemical Industries (strain) methanol dispersion silica solution processed: MA-ST-M 350g is put into the round-bottomed flask of 1000mL (silica solid constituent concentration: 40.4 mass %) and gamma-butyrolacton 329.93g.Then, make the flask and vacuum evaporator It connects and will be depressurized in flask, impregnate 20~50 minutes in about 35 DEG C of tepidarium, set to obtain solvent by methanol Change silica solution (GBL-M) about 471g (silica solid constituent concentration: 30 mass %) of gamma-butyrolacton into.
(modulation of modulation example 2:GBL-ZL)
Nissan Chemical Industries (strain) preparing isopropanol dispersion silica solution: IPA-ST-ZL is put into the round-bottomed flask of 1000mL 350g (silica solid constituent concentration: 30 mass %) and gamma-butyrolacton 315g.Then, make the flask and be equipped with resistance toization The vacuum evaporator of the property learned vacuum pump is connected and will be depressurized in flask, and 30~60 points are impregnated in about 35 DEG C of tepidarium Clock, to obtain silica solution (GBL-ZL) about 420g (silica solid ingredient that solvent is replaced as gamma-butyrolacton by isopropanol Concentration: 25 mass %).
(modulation of modulation example 3:GBL-L)
Nissan Chemical Industries (strain) preparing isopropanol dispersion silica solution: IPA-ST-L is put into the round-bottomed flask of 1000mL 350g (silica solid constituent concentration: 30 mass %) and gamma-butyrolacton 315g.Then, make the flask and be equipped with resistance toization The vacuum evaporator of the property learned vacuum pump is connected and will be depressurized in flask, and 30~60 points are impregnated in about 35 DEG C of tepidarium Clock, to obtain silica solution (GBL-L) about 420g (silica solid ingredient that solvent is replaced as gamma-butyrolacton by isopropanol Concentration: 25 mass %).
(modulation of modulation example 4:GBL-ST)
Nissan Chemical Industries (strain) preparing isopropanol dispersion silica solution: IPA-ST is put into the round-bottomed flask of 1000mL 350g (silica solid constituent concentration: 30 mass %) and gamma-butyrolacton 245g.Then, make the flask and be equipped with resistance toization The vacuum evaporator of the property learned vacuum pump is connected and will be depressurized in flask, and 30~60 points are impregnated in about 35 DEG C of tepidarium Clock, to obtain silica solution (GBL-ST) about 350g (silica solid ingredient that solvent is replaced as gamma-butyrolacton by isopropanol Concentration: 30 mass %).
(modulation of modulation example 5:GBL-S)
Nissan Chemical Industries (strain) methanol dispersion silica solution processed: MA-ST-S 350g is put into the round-bottomed flask of 1000mL (silica solid constituent concentration: 25 mass %) and gamma-butyrolacton 262.5g.Then, make the flask and be equipped with chemically-resistant Property vacuum pump vacuum evaporator connection and will be depressurized in flask, impregnated 20~50 minutes in about 35 DEG C of tepidarium, To obtain solvent by methanol replacement at gamma-butyrolacton silica solution (GBL-S) about 350g (silica solid constituent concentration: 25 mass %).
(modulation of modulation example 6:GBL-UP)
Nissan Chemical Industries (strain) methanol dispersion silica solution processed: MA-ST-UP is put into the round-bottomed flask of 1000mL 350g (silica solid constituent concentration: 20 mass %) and gamma-butyrolacton 280g.Then, make the flask and be equipped with resistance toization The vacuum evaporator of the property learned vacuum pump is connected and will be depressurized in flask, and 20~50 points are impregnated in about 35 DEG C of tepidarium Clock, to obtain solvent, by methanol replacement, at silica solution (GBL-UP) about 350g of gamma-butyrolacton, (silica solid ingredient is dense Degree: 20 mass %).
[2] synthesis example
[synthesis example 1]
Sequentially added in into the flask for the 2,000mL for being equipped with mechanical agitator TFMB58g (0.1811mol), DMAc188.23g starts to stir.BODA36.25g (0.1448mol) is added thereto, nitrogen displacement is carried out, then at 70 DEG C It is lower stir within 3 hours, then, reaction mixture is cooled to 50 DEG C, adds CBDA7.103g (0.0362mol) thereto, It stirs within further progress 2 hours.Then, reaction mixture is cooled to room temperature, the stirring of one night of further progress.Then, to anti- It answers and adds DMAc in mixture, the concentration (concentration of the ingredient other than organic solvent) for being diluted to solid component is 5 mass %.
Acetic anhydride 73.96g (0.7244mol) and pyridine 42.97g are added into the reaction mixture after dilution (0.5433mol), carries out stirring for 3 hours at 90~100 DEG C.
After stirring, reaction mixture is cooled to room temperature, the mixture cooled down is added to methanol 7.094kg In, resulting slurry stir within 30 minutes.Then, filtrate is recovered by filtration.It then, will be resulting in order to refine Filtrate is again added in methanol 7.094kg, is obtained slurry, is stirred and filters by the same method.Then into one Step is filtered addition, stirring and filtering of the object into methanol to refine again.
Finally, by resulting filtrate under reduced pressure, carry out drying in 8 hours at 100 DEG C, obtain the polyamides Asia as target Amine A1 76g (yield: 76%, Mw:59,302, Mn:25,923).
[synthesis example 2]
It is put into the three-neck flask for being equipped with the 2,000mL with nitrogen injection/outlet mechanical agitator TFMB115g(0.3591mol).The gamma-butyrolacton (GBL) for adding 468.9g immediately after, starts to stir.Diamines (TFMB) is complete Fully dissolved is added BODA71.88g (0.2872mol) after solvent, carries out stirring for 3 hours at 70 DEG C in a nitrogen atmosphere.It connects , reaction mixture is cooled to 50 DEG C, adds CBDA14.08g (0.071mol) thereto, is stirred within further progress 2 hours. Then, reaction mixture is cooled to room temperature to and is maintained temperature, is further stirred overnight in a nitrogen atmosphere.Then, Xiang Fanying GBL is added in mixture, the concentration (concentration of the ingredient other than organic solvent) for being diluted to solid component is 5 mass %.
Acetic anhydride 146.65g (1.436mol) and pyridine 85.21g are added into the reaction mixture after dilution (1.077mol), carries out stirring for 3 hours at 90~100 DEG C.
After stirring, reaction mixture is cooled to room temperature, the mixture cooled down is added to methanol 2.5kg In, resulting slurry stir within 30 minutes.Then, filtrate is recovered by filtration.It then, will be resulting in order to refine Filtrate is again added in methanol 2.5kg, is obtained slurry, is stirred and filters by the same method.Then further In order to refine, it is filtered addition, stirring and filtering of the object into methanol 2.5kg again.
Finally, making resulting filtrate in vacuum drying oven, carrying out drying in 8 hours at 120 DEG C, obtain as target Polyimides A2 153g (yield: 76.5%, Mn:44,460, Mw:96,641).
Above-mentioned polyimides A2 is dissolved in GBL, slowly carries out pressurizeing by resulting solution using 5 μm of filters Filter, the concentration for modulating solid component is the solution (polyimides A2 solution) of 12 mass %.
[synthesis example 3]
To injected with nitrogen/three-neck flask of the 250mL for being equipped with mechanical agitator of outlet in be added TFMB16.9g (0.052mol) and TMDA1.598g (0.006mol).The gamma-butyrolacton of 124.46g is added immediately after (GBL), start to stir.After diamines (TFMB and TMDA) is dissolved completely in solvent, add TCA6.725g (0.03mol), in nitrogen It carries out stirring for 5 hours under atmosphere, at 100 DEG C.Then, reaction mixture is cooled to 50 DEG C, adds CBDA5.883g thereto (0.03mol) is stirred for further progress 3 hours.Then, reaction mixture is cooled to room temperature to and is maintained temperature, is further existed It is stirred overnight under nitrogen atmosphere.Then, GBL is added into reaction mixture, be diluted to solid component concentration (organic solvent with The concentration of outer ingredient) it is 4 mass %.
Acetic anhydride 24.5g (0.24mol) and pyridine 14.23g (0.18mol) are added into the reaction mixture after dilution, It carries out stirring for 6 hours at 60~70 DEG C.
After stirring, reaction mixture is cooled to room temperature, the mixture cooled down is added to methanol 0.7kg In, resulting slurry stir within 30 minutes.Then, filtrate is recovered by filtration.It then, will be resulting in order to refine Filtrate is again added in methanol 0.7kg, is obtained slurry, is stirred and filters by the same method.Then further In order to refine, it is filtered addition, stirring and filtering of the object into methanol 0.7kg again.
Finally, making resulting filtrate in vacuum drying oven, carrying out drying in 8 hours at 120 DEG C, obtain as target Polyimides B 24.26g (yield: 78%, Mn:65,425, Mw:138,024).
Above-mentioned polyimides B is dissolved in GBL, slowly carries out pressurizeing by resulting solution using 5 μm of filters Filter, the concentration for modulating solid component is the solution (polyimides B solution) of 11.17 mass %.
[synthesis example 4]
To injected with nitrogen/three-neck flask of the 100mL for being equipped with mechanical agitator and cooler of outlet in plus Enter TFMB25.61g (0.08mol).The gamma-butyrolacton (GBL) for adding 173.86g immediately after, starts to stir.Diamines (TFMB) After being dissolved completely in solvent, BODAxx10g (0.04mol) and CBDA7.84g (0.04mol) are added, is heated in a nitrogen atmosphere To 140 DEG C.Then, the 1- ethyl piperidine of 1.739g is added in reaction solution, carried out at 210 DEG C 4.5 hours in nitrogen Heating stirring under gas atmosphere.
Reaction mixture is added in methanol 0.9kg, resulting slurry stir within 30 minutes.Then, passed through Filter recycling filtrate.Then, in order to refine, resulting filtrate is again added in methanol 0.9kg, slurry is obtained, passes through Same method is stirred and filters.Then further for purification, it is filtered object adding into methanol 0.9kg again Add, stir and filters.
Finally, making resulting filtrate in vacuum drying oven, carrying out drying in 8 hours at 120 DEG C, obtain as target Polyimides C 31.16g (yield: 74%, Mn:40,465, Mw:281,382).
Above-mentioned polyimides C is dissolved in GBL, slowly carries out pressurizeing by resulting solution using 5 μm of filters Filter, the concentration for modulating solid component is the solution (polyimides C solution) of 13.5 mass %.
[3] modulation (1) of substrate film composite
[embodiment 1]
At room temperature, it is dissolved in polyimides A1 3g in DMAc22g to modulate polyimide solution, uses 5 μm of mistake Resulting solution is slowly carried out pressure filtration by filter.Then, IPA-ST silica solution 6.67g is added into filtrate and carries out 30 points Clock stirring, is then placed the mixture after stirring with a night stationary state, to obtain resin combination.
[embodiment 2~3]
It is replaced respectively using GBL-ST silica solution 6.67g (embodiment 2), DMAC-ST silica solution 10.00g (embodiment 3) IPA-ST silica solution 6.67g obtains resin combination using method similarly to Example 1 in addition to this.
[embodiment 4]
DMAc22g is replaced using NMP22g, in addition to this, obtains resin combination using method similarly to Example 1 Object.
[embodiment 5~6]
Replace DMAc22g using NMP22g (embodiment 5), GBL22g (embodiment 6) respectively, in addition to this, using with The same method of embodiment 2 obtains resin combination.
[embodiment 7]
Make the usage amount 2.5g of GBL-ST silica solution, in addition to this, obtains resin using method similarly to Example 2 Composition.
[embodiment 8~9]
Replace DMAc22g using NMP22g (embodiment 8), GBL22g (embodiment 9) respectively, in addition to this, using with The same method of embodiment 7 obtains resin combination.
[embodiment 10]
At room temperature, it is dissolved in polyimides A1 3g in GBL22g to modulate polyimide solution, uses 5 μm of mistake Resulting solution is slowly carried out pressure filtration by filter.Then, GBL-ST silica solution 6.67g is added into filtrate and carries out 30 points The oxygen as catalyst is added in clock stirring thereto in a manner of being then 0.5 mass % using the quality relative to composition totality Bis- ((3- aminopropyl) dimethylsilanes), stir within 3 minutes, obtain resin combination.
[embodiment 11~12]
It is replaced respectively using GBL-UP silica solution 10g (embodiment 11), GBL-M silica solution 6.67g (embodiment 12) GBL-ST silica solution 6.67g obtains resin combination using method similarly to Example 6 in addition to this.
[embodiment 13]
At room temperature, it is dissolved in polyimides A1 3g in GBL22g to modulate polyimide solution, uses 5 μm of mistake Resulting solution is slowly carried out pressure filtration by filter.Then, GBL-ST silica solution 3.33g and GBL-UP silicon are added into filtrate Colloidal sol 5g, stir within 30 minutes, then places the mixture after stirring with a night stationary state, to obtain resin combination Object.
[embodiment 14~15]
GBL- is replaced using GBL-M silica solution 3.33g (embodiment 14), GBL-S silica solution 4g (embodiment 15) respectively UP silica solution 5g obtains resin combination using method similarly to Example 13 in addition to this.
[4] production (1) of resin film
[embodiment 16]
The resin combination obtained by embodiment 1 is coated on glass substrate, makes film 30 minutes, 140 DEG C at 50 DEG C Carry out within 60 minutes at lower 30 minutes, 200 DEG C heating successively to obtain resin film.It should be noted that heating uses in advance 3 baking ovens of setting at a desired temperature.
Resulting resin film is removed by mechanical cutting, for evaluation later.
[embodiment 17~30]
The resin combination obtained by embodiment 1 is replaced using the resin combination obtained by 2~embodiment of embodiment 15, In addition to this, resin film is obtained using method similarly to Example 16.
[5] evaluation (1) of resin film
About the heat resistance and optical characteristics of each resin film made through the above steps, i.e., linear expansion coefficient (50~ 200 DEG C), 5% weight reduce temperature, light transmittance and CIE b value (yellow evaluation) and delay, divide according to above-mentioned steps It is not evaluated.Show the result in table 1.
As shown in table 1, can be confirmed the linear expansion coefficient [ppm/ DEG C] (50~200 DEG C) of resin film of the invention it is low, Furthermore yellowing is small represented by light transmittance [%] height and then CIE b* value of 400nm and 550nm after solidifying, postpones quilt It is suppressed to low value.In addition, show " content of silica solution is more, and linear expansion coefficient is lower and light transmittance is higher " this The tendency of sample.
In addition, by the resin film of the invention that above-described embodiment 16~30 obtains all have even if by them with two hands It takes and is bent high flexibility required by also not broken, flexible display substrate in the case where (30 degree or so) at an acute angle.
[6] modulation (2) of substrate film composite
[embodiment 31]
At room temperature, using 5 μm of filter, by the polyimides A2 solution 4.457g modulated by synthesis example 2, (polyamides is sub- Amine A2 solid content: 0.534g) slowly carry out pressure filtration.Then into filtrate add GBL-ZL silica solution 1.426g and Gamma-butyrolacton (GBL) 0.059g, stir within 30 minutes, then places the mixture after stirring with a night stationary state, from And obtain resin combination.
[32~embodiment of embodiment 38]
Make the addition of polyimides A2 solution (usage amount that the numerical value in table is solution form) modulated by synthesis example 2 The additive amount of amount, the type of silica solution and additive amount and gamma-butyrolacton is shown in following table 2, in addition to this, using with reality It applies the same method of example 31 and obtains resin combination.
[embodiment 39]
At room temperature, the polyimides B solution 2.146g (polyimides that will be modulated by synthesis example 3 using 5 μm of filter B solid content: 0.239g) slowly carry out pressure filtration.Then GBL-ZL silica solution 0.639g and γ-fourth are added into filtrate Lactone (GBL) 0.544g, stir within 30 minutes, then places the mixture after stirring with a night stationary state, to obtain Obtain resin combination.
[40~embodiment of embodiment 48]
Make the polyimides B solution (usage amount that the numerical value in table is solution form) modulated by synthesis example 3 additive amount, The additive amount of the type and additive amount of silica solution and gamma-butyrolacton is shown in following Table 3, in addition to this, utilization and embodiment 39 same methods obtain resin combination.
[embodiment 49]
At room temperature, using 5 μm of filter, by the polyimides C solution 2.5147g modulated by synthesis example 4, (polyamides is sub- Amine C solid content: 0.339g) slowly carry out pressure filtration.Then into filtrate add GBL-ZL silica solution 0.905g and GBL0.165g, stir within 30 minutes, then places the mixture after stirring with a night stationary state, to obtain resin Composition.
[50~embodiment of embodiment 64]
Make the polyimides C solution (usage amount that the numerical value in table is solution form) modulated by synthesis example 4 additive amount, The additive amount of the type and additive amount of silica solution and gamma-butyrolacton is shown in following table 4, in addition to this, utilization and embodiment 49 same methods obtain resin combination.
[7] production (2) of resin film
The resin combination obtained by embodiment 31 is coated on glass substrate, makes film 30 minutes, 140 DEG C at 50 DEG C Carry out within 60 minutes at 60 minutes, 280 DEG C at lower 30 minutes, 220 DEG C heating successively to obtain resin film.It needs to illustrate It is that heating uses 4 baking ovens preset at a desired temperature.
Resulting resin film is removed by mechanical cutting, for evaluation later.
In addition, replacing the resin obtained by embodiment 31 using the resin combination obtained by 32~embodiment of embodiment 64 Composition obtains each resin film using method similar to the above in addition to this.
[8] evaluation (2) of resin film
About the heat resistance and optical characteristics of each resin film made through the above steps, i.e. linear expansion coefficient, 5% weight Amount reduces temperature, light transmittance and CIE b value (yellow evaluation) and delay, is evaluated respectively according to above-mentioned steps.It will As a result it is shown in 2~table of table 4.
As shown in 2~table of table 4, the linear expansion coefficient [ppm/ DEG C] (especially 50 of resin film of the invention can be confirmed ~200 DEG C) it is low, furthermore solidify after 400nm and 550nm light transmittance [%] is high so that CIE b* value represented by Huang Spend that small, to be suppressed to low value, birefringent value Δ n also extremely low for delay.In addition, showing that " content of silica solution is more, and line is swollen Swollen coefficient is lower " such tendency.
In addition, the resin film of the invention obtained as described above all has even if they are being taken and bent to two hands Also high flexibility required by not broken, flexible display substrate in the case where acute angle (30 degree or so).

Claims (12)

1. a kind of manufacturing method of resin film, which is characterized in that using containing polyimides, silicon dioxide granule and organic molten The resin film of agent, which is formed, uses composition,
The polyimides is obtained from polyamic acid is carried out imidizate, and the polyamic acid is made comprising ester ring type four Obtained from tetracarboxylic dianhydride's ingredient of carboxylic acid dianhydride is reacted with the diamine component comprising fluorinated aromatic diamines,
The average grain diameter of the silicon dioxide granule is 100nm hereinafter, the average grain diameter is by being measured using nitrogen adsorption method What specific surface area value calculated,
The mass ratio of the polyimides and the silicon dioxide granule is 7:3~3:7.
2. according to the method described in claim 1, the ester ring type tetracarboxylic dianhydride include formula (C1) shown in tetracarboxylic dianhydride,
In formula (C1), B1Indicate the group of 4 valences in formula (X-1)~(X-12),
In formula, multiple R indicate that hydrogen atom or methyl, * indicate associative key independently of each other.
3. method according to claim 1 or 2, the fluorinated aromatic diamines includes diamines shown in formula (A1),
H2N-B2-NH2 (A1)
In formula, B2Indicate the group of the divalent in formula (Y-1)~(Y-34),
In formula, * indicates associative key.
4. according to the method described in claim 1, the polyimides include formula (2) shown in monomeric unit,
5. method according to claim 1 or 2, the average grain diameter is 60nm or less.
6. a kind of resin film is manufactured by method according to any one of claims 1 to 5.
7. a kind of resin film, which is formed, uses composition, containing polyimides, silicon dioxide granule and organic solvent,
The polyimides is obtained from polyamic acid is carried out imidizate, and the polyamic acid is made comprising ester ring type four Obtained from tetracarboxylic dianhydride's ingredient of carboxylic acid dianhydride is reacted with the diamine component comprising fluorinated aromatic diamines,
The average grain diameter of the silicon dioxide granule is 100nm hereinafter, the average grain diameter is by being measured using nitrogen adsorption method What specific surface area value calculated,
The mass ratio of the polyimides and the silicon dioxide granule is 7:3~3:7.
8. resin film according to claim 7, which is formed, uses composition, the ester ring type tetracarboxylic dianhydride includes formula (C1) Shown in tetracarboxylic dianhydride,
In formula (C1), B1Indicate the group of 4 valences in formula (X-1)~(X-12),
In formula, multiple R indicate that hydrogen atom or methyl, * indicate associative key independently of each other.
9. resin film according to claim 7 or 8, which is formed, uses composition, the fluorinated aromatic diamines includes formula (A1) Shown in diamines,
H2N-B2-NH2 (A1)
In formula, B2Indicate the group of the divalent in formula (Y-1)~(Y-34),
In formula, * indicates associative key.
10. resin film according to claim 7, which is formed, uses composition, the polyimides includes single shown in formula (2) Body unit,
11. resin film according to claim 7 or 8, which is formed, uses composition, the average grain diameter is 60nm or less.
12. a kind of method for the delay for reducing resin film, which is characterized in that use and contain polyimides, silicon dioxide granule Resin film formation with organic solvent forms resin film with composition,
The polyimides is obtained from polyamic acid is carried out imidizate, and the polyamic acid is made comprising ester ring type four Obtained from tetracarboxylic dianhydride's ingredient of carboxylic acid dianhydride is reacted with the diamine component comprising fluorinated aromatic diamines,
The average grain diameter of the silicon dioxide granule is 100nm hereinafter, the average grain diameter is by being measured using nitrogen adsorption method What specific surface area value calculated.
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