CN106164178A - The manufacture method of resin film and resin film formation composition - Google Patents

The manufacture method of resin film and resin film formation composition Download PDF

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Publication number
CN106164178A
CN106164178A CN201580017618.1A CN201580017618A CN106164178A CN 106164178 A CN106164178 A CN 106164178A CN 201580017618 A CN201580017618 A CN 201580017618A CN 106164178 A CN106164178 A CN 106164178A
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resin film
formula
polyimides
film formation
tetracarboxylic dianhydride
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CN106164178B (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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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)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (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

It is an object of the invention to provide, not only excellent heat resistance, but also there is the resin film postponing low such feature, it is particularly suitable as the manufacture method of the resin film of the substrate of flexible device and the resin film formation composition of this resin film and the such resin film of formation.The solution of the present invention relates to the manufacture method of a kind of resin film, it is characterized in that, use and contain polyimides, the resin film formation composition of silicon dioxide granule and organic solvent, described polyimides is to carry out obtained from imidizate by polyamic acid, described polyamic acid is to make obtained from the tetracarboxylic dianhydride's composition comprising ester ring type tetracarboxylic dianhydride and the diamine component comprising fluorinated aromatic diamines react, the average grain diameter of described silicon dioxide granule is below 100nm, described average grain diameter is to be calculated by the specific surface area value utilizing nitrogen adsorption method to record.

Description

The manufacture method of resin film and resin film formation composition
Technical field
The present invention relates to the manufacture method of resin film and resin film formation composition, the resin being obtained by it thin The method of the delay of film and minimizing resin film, more specifically, particularly to displays such as applicable flexible display substrate The manufacture method of the resin film of the purposes of substrate and resin film formation composition.
Background technology
In recent years, rapid progressive with the electronic equipment such as liquid crystal display, display of organic electroluminescence, device thin Type, lightweight and flexibility are gradually required.
In these devices, glass substrate is formed with various electronic component, for example, thin film transistor (TFT), transparency electrode etc., But by this glass material is replaced with the resin material of softness and light weight, the slimming of device self, lightweight, soft can be realized Property.And, as the candidate of such resin material, polyimides causes concern, with regard to the various reports of polyimide film Accuse and have (see, for example patent document the 1st, 2) all the time.
Prior art literature
Patent document
Patent document 1: Japanese Laid-Open Patent Publication 60-188427 publication
Patent document 2: Japanese Laid-Open Patent Publication 58-208322 publication
Patent document 3: No. 2011/149018 pamphlet of International Publication
Content of the invention
Invent problem to be solved
In addition, when using polyimide resin material as the substrate of display, it is desirable to and be required of, not only should The resin material transparency is excellent, and is the material low as the delay (retardation) requiring one of performance.Even it is soft The situation of property display base plate, in addition to high flexibility (flexible), in addition it is also necessary to meet these requirements performance.Mentioned here Postpone (phase difference, phase delay), refer to the long-pending of birefringence (differences of two orthogonal refractive indexes) and thickness, this numerical value, especially Be the delay of thickness direction be the important numerical value affecting viewing angle characteristic.Known big length of delay can become and causes display The reason that display quality declines (referring for example to patent document 3).
The present invention proposes in view of such situation, its object is to provide, and not only heat resistance and flexibility are excellent, But also there is the resin film postponing low such feature, it is particularly suitable as the resin film of the substrate of flexible device Manufacture method and the resin film formation composition of this resin film and the such resin film of formation.
Particularly the present invention also aims to provide the manufacture method of a kind of resin film and this resin film and shape Becoming the resin film formation composition of such resin film, this resin film not only heat resistance and flexibility are excellent, and Also there is the low such feature of delay, 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 there is excellent performance.
Additionally, the present invention also aims to, provide and reduce the resin that can be used as the substrate of flexible device etc. The method of the delay of film.
For solving the method for problem
The present inventors conduct in-depth research to achieve these goals, it was found that to having ad hoc structure The polyimides of monomeric unit coordinates resin film excellent heat resistance obtained by silica, postpones low and then also have soft Soft excellent such feature, it was found that, by making the scope for regulation for the use level of this silica such that it is able to realize resistance to Hot excellent, postpone resin film low, that flexibility is excellent and then the transparency is also excellent, thus complete the present invention.
That is, with regard to the present invention, as the 1st viewpoint, the manufacture method of a kind of resin film is related to, it is characterised in that use Resin film formation composition containing polyimides, silicon dioxide granule and organic solvent,
Described polyimides is to carry out obtained from imidizate by polyamic acid, and described polyamic acid is to make to comprise alicyclic ring Obtained from tetracarboxylic dianhydride's composition of formula tetracarboxylic dianhydride and the diamine component comprising fluorinated aromatic diamines react,
The average grain diameter of described silicon dioxide granule is below 100nm, and described average grain diameter is by utilizing nitrogen adsorption method to survey The specific surface area value obtaining calculates.
As the 2nd viewpoint, relate to the method described in the 1st viewpoint, shown in aforementioned ester ring type tetracarboxylic dianhydride contained (C1) Tetracarboxylic dianhydride.
(in formula (C1), B1Represent the group of 4 valencys being selected from formula (X-1)～(X-12),
(in formula, multiple R represent hydrogen atom or methyl independently of each other, and * represents associative key.)〕
As the 3rd viewpoint, relating to the method described in the 1st viewpoint or the 2nd viewpoint, aforementioned fluorinated aromatic diamines is contained (A1) diamines shown in.
H2N-B2-NH2 (A1)
(in formula, B2Represent the group of the divalent being selected from formula (Y-1)～(Y-34).)
(in formula, * represents associative key.)
As the 4th viewpoint, relate to the method described in the 1st viewpoint, the monomer list shown in aforementioned polyimides contained (2) Unit.
As the 5th viewpoint, relate to the method according to any one of the 1st viewpoint～the 4th viewpoint, aforementioned polyimides with aforementioned The mass ratio of silicon dioxide granule is 7:3～3:7.
As the 6th viewpoint, relating to the method according to any one of the 1st viewpoint～the 5th viewpoint, aforementioned average grain diameter is 60nm Below.
As the 7th viewpoint, relate to by the resin film manufactured by the method according to any one of the 1st viewpoint～the 6th viewpoint.
As the 8th viewpoint, relate to a kind of resin film formation composition, containing polyimides, silicon dioxide granule and Organic solvent,
Described polyimides is to carry out obtained from imidizate by polyamic acid, and described polyamic acid is to make to comprise alicyclic ring Obtained from tetracarboxylic dianhydride's composition of formula tetracarboxylic dianhydride and the diamine component comprising fluorinated aromatic diamines react,
The average grain diameter of described silicon dioxide granule is below 100nm, and described average grain diameter is by utilizing nitrogen adsorption method to survey The specific surface area value obtaining calculates.
As the 9th viewpoint, relate to the resin film formation composition described in the 8th viewpoint, aforementioned ester ring type tetrabasic carboxylic acid two Tetracarboxylic dianhydride shown in acid anhydride contained (C1).
(in formula (C1), B1Represent the group of 4 valencys being selected from formula (X-1)～(X-12).
(in formula, multiple R represent hydrogen atom or methyl independently of each other, and * represents associative key.)〕
As the 10th viewpoint, relate to the resin film formation composition described in the 8th viewpoint or the 9th viewpoint, aforementioned fluorine-containing Diamines shown in aromatic diamine contained (A1).
H2N-B2-NH2 (A1)
(in formula, B2Represent the group of the divalent being selected from formula (Y-1)～(Y-34).)
(in formula, * represents associative key.)
As the 11st viewpoint, relating to the resin film formation composition described in the 8th viewpoint, aforementioned polyimides is contained (2) monomeric unit shown in.
As the 12nd viewpoint, relate to the resin film formation composition according to any one of the 8th viewpoint～the 11st viewpoint, Aforementioned polyimides is 7:3～3:7 with the mass ratio of aforementioned silicas particle.
As the 13rd viewpoint, relate to the resin film formation composition according to any one of 8 viewpoints～the 12nd viewpoint, front Stating average grain diameter is below 60nm.
As the 14th viewpoint, relate to a kind of method of delay reducing resin film, it is characterised in that use and contain polyamides The resin film formation composition of imines, silicon dioxide granule and organic solvent forms resin film,
Described polyimides is to carry out obtained from imidizate by polyamic acid, and described polyamic acid is to make to comprise alicyclic ring Obtained from tetracarboxylic dianhydride's composition of formula tetracarboxylic dianhydride and the diamine component comprising fluorinated aromatic diamines react,
The average grain diameter of described silicon dioxide granule is below 100nm, and described average grain diameter is by utilizing nitrogen adsorption method to survey The specific surface area value obtaining calculates.
Invention effect
Using the resin film formation composition that a scheme of the present invention relates to, according to the present invention a scheme relates to And the manufacture method of resin film, can be formed well with repeatability and there is low linear expansion coefficient, excellent heat resistance, have Low delay, and then the resin film that flexibility is excellent.
The resin film formation composition relating to especially with another program of the present invention, according to another of the present invention The manufacture method of the resin film that scheme relates to, can form well with repeatability and have low linear expansion coefficient, and heat resistance is excellent Different, there is high transparent and low delay, and then the resin film that flexibility is excellent.
And, the resin film that the present invention relates to display low linear expansion coefficient, high transparent are (high light transmittance, low Yellowing), low latency, and then flexibility is also excellent, therefore, it is possible to be suitable as the substrate of flexible device, particularly flexible display Use.
And then, the method for the delay according to the reduction resin film that the present invention relates to, resin film can be effectively reduced Delay.
The reduction method of such manufacture method, composition, resin film and delay that the present invention relates to can be abundant Correspondence requires the characteristics such as high flexibility, low linear expansion coefficient, high transparent (high light transmittance, low yellowing), low latency The progress of flexible device substrate, the particularly field of flexible display substrate.
Detailed description of the invention
It is described in detail below for the present invention.
The resin film formation composition using in the manufacture method of the resin film of the present invention contains following specific Polyimides, silicon dioxide granule and organic solvent, this resin film formation composition is also the object of the present invention.
[polyimides]
The polyimides using in the present invention is that polyamic acid carries out polyimides obtained from imidizate, described poly- Amic acid is to make the tetracarboxylic dianhydride's composition 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 the tetracarboxylic dianhydride shown in following formula (C1), aforementioned fluorine-containing Aromatic diamine preferably comprises the diamines shown in following formula (A1).
(in formula, B1Represent the group of 4 valencys being selected from formula (X-1)～(X-12).
(in formula, multiple R represent hydrogen atom or methyl independently of each other, and * represents associative key.)〕
H2N-B2-NH2 (A1)
(in formula, B2Represent the group of the divalent being selected from formula (Y-1)～(Y-34).)
(in formula, * represents 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) Shown compound.
Additionally, in the diamines shown in above-mentioned (A1), the B in preferred formula2Compound shown in formula (Y-12), (Y-13).
As preferred example, make the tetracarboxylic dianhydride shown in above-mentioned formula (C1) and the diamine reactant shown in above-mentioned formula (A1) And obtain polyamic acid, this polyamic acid is carried out polyimides obtained from imidizate and comprises shown in formula described later (2) Monomeric unit.
In order to obtain the characteristic with low linear expansion coefficient, low latency and high transparent as the purpose of the present invention, soft Soft excellent resin film, for the total mole number of tetracarboxylic dianhydride's composition, ester ring type tetracarboxylic dianhydride, for example, go up State the tetracarboxylic dianhydride shown in formula (C1) and be preferably 90 moles of more than %, more preferably 95 moles more than %, especially most preferably For whole (100 moles of %) is the tetracarboxylic dianhydride shown in above-mentioned formula (C1).
Additionally, similarly, in order to obtain above-mentioned there is low linear expansion coefficient, low latency and high transparent characteristic, softness The excellent resin film of property, for the total mole number of diamine component, shown in fluorinated aromatic diamines, such as formula (A1) Diamines is preferably 90 moles of more than %, more preferably 95 moles more than %.Additionally, diamine component can all (100 moles of %) Diamines shown in above-mentioned formula (A1).
As a case of preferred scheme, the polyimides using in the present invention comprises the monomer list shown in following formula (1) Unit.
As the monomeric unit shown in the monomeric unit shown in above-mentioned formula (1), preferably formula (1-1) or formula (1-2), more excellent Elect the monomeric unit shown in formula (1-1) as.
According to the preferred scheme of the present invention, the polyimides using in the present invention does not contain only shown in previously described formula (1) Monomeric unit, possibly together with the monomeric unit shown in formula (2).
As the monomeric unit shown in the monomeric unit shown in above-mentioned formula (2), preferably formula (2-1) or formula (2-2), more excellent Elect the monomeric unit shown in formula (2-1) as.
The polyimides using in the present invention comprises the monomeric unit shown in above-mentioned formula (1) and the monomer shown in formula (2) In the case of unit, it is preferred that with the molar ratio computing in polyimides chain, preferably with the monomeric unit shown in formula (1): formula (2) ratio of the monomeric unit=10:1～1:10 shown in comprises, and the more preferably ratio with 10:1～3:1 comprises.
Except by ester ring type tetracarboxylic dianhydride's composition of the tetracarboxylic dianhydride shown in aforementioned contained (C1) and contained (A1) the derivative monomeric unit of the diamine component of the diamines shown in, such as the monomeric unit shown in above-mentioned formula (1) and formula (2) with Outward, the polyimides of the present invention can also comprise other monomeric unit.As long as the content ratio of this other monomeric units is not damaged Evil is formed the characteristic of the resin film being formed with composition by the resin film of the present invention, then can arbitrarily determine.With regard to its ratio Example, relative to by ester ring type tetracarboxylic dianhydride's composition of the tetracarboxylic dianhydride shown in aforementioned contained (C1) and contained (A1) institute The derivative monomeric unit of the diamine component of the diamines showing, the such as molal quantity of the monomeric unit shown in formula (1), or contained (2) in the case of monomeric unit shown in, total relative to the monomeric unit shown in the monomeric unit shown in formula (1) and formula (2) Molal quantity, preferably less than 20 moles %, more preferably less than 10 moles %, still more preferably for less than 5 moles of %.
As other monomeric units such, other that can enumerate for example shown in formula (3) have the list of polyimide structures Body unit, but do not limited by this construction unit.
In formula (3), A represents the organic group of 4 valencys, preferably represents that any one in following formula (A-1)～(A-4) is shown The group of 4 valencys.Additionally, in above-mentioned formula (3), B represents the organic group of divalent, arbitrary in preferably expression (B-1)～(B-11) The group of the divalent shown in individual.In various, * represents associative key.It should be noted that in formula (3), represent following formula (A-1) at A In the case of the group of any one the 4 shown valency in～(A-4), B can be any one in previously described formula (Y-1)～(Y-34) The group of shown divalent.Or, in formula (3), represent any one the shown divalent in following formula (B-1)～(B-11) at B In the case of group, A can be the group of any one the 4 shown valency in previously described formula (X-1)～(X-12).
In the polyimides of the present invention contained (3) shown in monomeric unit in the case of, can only comprise A and B Only by a kind of the constituted monomeric unit in the group illustrated in such as following formula, it is also possible to comprise at least one in A and B It is the two or more monomeric units of the two or more group selected from following illustration.
It should be noted that in the polyimides using in the present invention, each monomeric unit combines in any order.
As a preferred case, the polyimides with the 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 and the following formula (4) as diamine component are shown Diamines be polymerized in organic solvent, obtained polyamic acid is carried out imidizate and obtains.
Additionally, the polyimides using in the present invention in addition to the monomeric unit shown in above-mentioned formula (1) possibly together with upper In the case of stating the monomeric unit shown in formula (2), the polyimides containing each monomeric unit shown in formula (1) and formula (2) is logical Cross and make to become with as diamines with 1,2,3,4-cyclobutanetetracarboxylic dianhydride as the above-mentioned tetracarboxylic dianhydride of tetracarboxylic dianhydride's composition The diamines shown in following formula (4) dividing is polymerized in organic solvent, obtained polyamic acid is carried out imidizate and obtains 's.
As the 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, the lower and resin film from the linear expansion coefficient making the resin film of the present invention have The higher viewpoint of the transparency set out, following formula (4-1) shown in 2,2 '-bis-(trifluoromethyl) benzidine or following are preferably used Shown in formula (4-2) 3,3 '-bis-(trifluoromethyl) benzidine, particularly preferably uses 2,2 '-bis-(trifluoromethyl) benzidine.
Additionally, the polyimides using in the present invention has by the fat of the tetracarboxylic dianhydride shown in aforementioned contained (C1) The derivative monomeric unit of the diamine component of the diamines shown in ring type tetracarboxylic dianhydride's composition and contained (A1), for example above-mentioned formula (1) monomeric unit shown in and the monomeric unit shown in formula (2), have other monomer lists shown in above-mentioned formula (3) in addition In the case of unit, the polyimides containing formula (1), formula (2) and each monomeric unit shown in 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) and the above-mentioned formula as diamine component (4) diamines shown in and the diamines shown in following formula (6) are polymerized in organic solvent, obtained polyamic acid carry out acyl sub- Amination and obtain.
A in above-mentioned formula (5) represents the implication identical with A and B in previously described formula (3) respectively with the B in formula (6).
Specifically, as the tetracarboxylic dianhydride shown in formula (5), pyromellitic acid anhydride, 3,3 ', 4,4 '-connection can be enumerated PMDA, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic acid dianhydride, 4,4 '-(hexafluoro isopropyl) two O-phthalic acid dianhydride, 11,11-double (trifluoromethyl)- 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 '-tetrone, 4,6,10,12-tetrafluoro two furans simultaneously [3,4-b:3 ', 4 '-i] dibenzo [b, e] [1,4] TwoDouble (trifluoromethoxy) benzo [the 1,2-c:4,5-c '] two furans-1,3,5,7-tetrone of English-1,3,7,9-tetrone, 4,8-, N, N '-[2,2 '-bis-(trifluoromethyl) xenyls-4,4 '-diyl] double (1,3-dioxa-1,3-dihydroisobenzofuran-5-first Acid amides) etc. aromatic tetracarboxylic acid；1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,3,4-cyclohexanetetracarboxylic acid dianhydride, 3,4-dicarboxyl The ester ring type tetracarboxylic dianhydrides such as base-1,2,3,4-tetrahydrochysene-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 any one the 4 shown valency in previously described formula (A-1)～(A-4) Tetracarboxylic dianhydride, i.e. 11 can be enumerated, double (the trifluoromethyl)-1H-difluoro [3,4-b:3 ', 4 '-i] of 11-Ton-1,3,7,9- (11H-tetrone), 6,6 '-bis-(trifluoromethyls)-[5,5 '-two isobenzofuran]-1,1 ', 3,3 '-tetrone, 4,6,10,12-tetra- Fluorine two furans simultaneously [3,4-b:3 ', 4 '-i] dibenzo [b, e] [1,4] twoDouble (the trifluoro methoxy of English-1,3,7,9-tetrone, 4,8- Base) benzo [1,2-c:4,5-c '] two furans-1,3,5,7-tetrone is as preferred compound.
Additionally, as the diamines shown in formula (6), such as 2-(trifluoromethyl) benzene-Isosorbide-5-Nitrae-diamines, 5-(fluoroform can be enumerated Base) benzene-1,3-diamines, 5-(trifluoromethyl) benzene-1,2-diamines, double (trifluoromethyl)-benzene-1,4-diamines of 2,5-, 2,3-double (three Methyl fluoride)-benzene-1,4-diamines, double (trifluoromethyl)-benzene-1,4-diamines of 2,6-, double (trifluoromethyl)-benzene-1,2-two of 3,5- Amine, four (trifluoromethyl)-1,4-phenylenediamine, 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, Double [the 3-(trifluoromethyl) of 2,3,5,6-phenyl tetrafluoride-1,4-diamines, 4,4 '-(perfluoropropane-2,2-diyl) diphenylamines, 4,4 '-oxygen Aniline], double (4-amino-benzene oxygen) benzene of 1,4-, 1,3 '-bis-(4-amino-benzene oxygen) benzene, double (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 '-dimethylbenzidine (o-tolidine (o- TOLIDINE)), 2,3 '-dimethylbenzidine, 2,2 '-dimethoxy benzidine, 3,3 '-dimethoxy benzidine, 2,3 '-two Methoxyl biphenyl amine, 2,2 '-dihydroxybiphenyl amine, 3,3 '-dihydroxybiphenyl amine, 2,3 '-dihydroxybiphenyl amine, 2,2 '-difluoro Benzidine, 3,3 '-DfBP amine, 2,3 '-DfBP amine, 2,2 '-dichloro-benzidine, 3,3 '-dichloro-benzidine, 2,3 '- Dichloro-benzidine, 4,4 '-diaminobenzene anilid, 4-aminophenyl-4 '-Aminobenzoate, octafluorobiphenyl amine, 2,2 ', 5,5 '-tetramethyl benzidine, 3,3 ', 5,5 '-tetramethyl benzidine, 2,2 ', 5,5 '-four (trifluoromethyl) benzidine, 3,3 ', 5, 5 '-four (trifluoromethyl) benzidine, 2,2 ', 5,5 '-tetrachloro benzidine, 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]- Double (oxygen) } diphenylamines, 4,4 '-{ [(perfluoropropane-2,2-diyl) double (4,1-phenylene)] double (oxygen) } diphenylamines, 1-(4-ammonia Base phenyl) aromatic diamine such as-2,3-dihydro-1,3,3-trimethyl-1H-indenes-5 (or 6) amine；4,4 '-di-2-ethylhexylphosphine oxide (hexamethylene Amine), 4,4 '-di-2-ethylhexylphosphine oxide (3-methyl cyclohexylamine), IPD, trans-1,4-cyclohexane diamines, cis-1,4-ring Hexane diamine, 1,4-hexamethylene double (methyl amine), double (amino methyl) bicyclic (2.2.1) heptane of 2,5-, double (the amino first of 2,6- Base) bicyclic (2.2.1) heptane, double (amino methyl) three ring (5.2.1.0) decane of 3,8-, 1,3-diaminourea adamantane, 2,2-be double (4-aminocyclohexyl) propane, 2,2-double (4-aminocyclohexyl) HFC-236fa, 1,3-propanediamine, 1,4-tetramethylene two Amine, 1,5-five methylene diamine, 1,6-hexamethylene diamine, 1,7-heptamethylene diamines, 1,8-eight methylene diamine, 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 any one the shown divalent group in previously described formula (B-1)～(B-11) Fragrant race diamines, i.e. 2,2 '-bis-(trifluoromethoxies)-(1,1 '-xenyl)-4,4 '-diamines [another name: 2,2 '-diformazan can be enumerated Epoxide benzidine], 4,4 '-(perfluoropropane-2,2-diyl) diphenylamines, 2,5-double (trifluoromethyl) benzene-1,4-diamines, 2-(three Methyl fluoride) benzene-1,4-diamines, 2-fluorobenzene-1,4-diamines, 4,4 '-oxygen double [3-(trifluoromethyl) aniline], 2,2 ', 3,3 ', 5, 5 ', 6,6 '-octafluoro [1,1 '-xenyl]-4,4 '-diamines [another name: 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) double (4,1-phenylene)] double (oxygen) } diphenylamines, 1-(4-aminophenyl)-2,3-dihydro-1, 3,3-trimethyl-1H-indenes-5 (or 6) amine is as preferred diamines.
<synthesis of polyamic acid>
As it was previously stated, the polyimides using in the present invention is to carry out obtained from imidizate by polyamic acid, described Polyamic acid is to make the tetracarboxylic dianhydride's composition comprising the ester ring type tetracarboxylic dianhydride shown in above-mentioned formula (C1) and comprise above-mentioned formula (A1) obtained from the diamine component reaction of the fluorinated aromatic diamines shown in.
Specifically, for example it as a preferred case, is by making to comprise bicyclic [3,3,0] octane-2,4,6,8-tetramethyls Acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride according to circumstances and then the tetrabasic carboxylic acid according to desired above-mentioned formula (5) Tetracarboxylic dianhydride's composition of dianhydride and comprise the diamines shown in above-mentioned formula (4) and the diamines according to desired above-mentioned formula (6) The diamine component of composition is polymerized in organic solvent, carries out the polyamic acid of gained obtained from imidizate.
The above-mentioned reaction by two kinds of compositions generation polyamic acids can be easier to carry out in organic solvent, and is not giving birth to It is favourable for producing on this aspect of accessory substance.
The addition of these tetracarboxylic dianhydride's compositions and the diamine component in the reaction of diamine component is to consider than (mol ratio) The molecular weight of polyamic acid, and then consider to be fitted by the molecular weight of polyimides obtained from imidizate afterwards etc. When set, but relative to diamine component 1, tetracarboxylic dianhydride's composition generally can be made to be about 0.8～1.2, such as 0.9～ About 1.1, preferably about 0.95～1.02.As common polycondensation reaction, this mol ratio closer to 1.0, generation poly- The molecular weight of amic acid is bigger.
As long as reaction is not produced by the organic solvent using when above-mentioned tetracarboxylic dianhydride's composition reacts with diamine component Harmful effect and the solvent by the polyamic acid dissolving of generation are just not particularly limited.Hereinafter enumerate its concrete example.
Can enumerate for example, metacresol, 2-Pyrrolidone, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-second Thiazolinyl-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 (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl are sub- Sulfone, isopropanol, methoxy amylalcohol, dipentene, ethyl pentyl group 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, DPGME, diethylene glycol, two Ethylene glycol acetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, two Propylene glycol monoethyl, dipropylene glycol monoacetate list ethylether, DPG 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, DIBK, 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 alone or in combination uses.
And then, even not making the solvent that polyamic acid dissolves, it is also possible at the model that the polyamic acid being generated does not separates out It is mixed in enclosing in above-mentioned solvent and use.Additionally, the moisture suppression polymerisation in organic solvent, and then become and make generation The reason that polyamic acid hydrolyzes, therefore organic solvent is preferably used the solvent as far as possible being dehydrated.
As the method making above-mentioned tetracarboxylic dianhydride's composition and diamine component react in organic solvent, can enumerate diamines Dispersion liquid or solution that composition is dispersed or dissolved in organic solvent are stirred, and directly add tetracarboxylic dianhydride wherein Composition or the side adding the dispersion liquid being dispersed or dissolved in this tetracarboxylic dianhydride's composition in organic solvent or solution Method；Add diamines in turn in the dispersion liquid being dispersed or dissolved in tetracarboxylic dianhydride's composition in organic solvent or solution The method of composition；And replace the method etc. adding tetracarboxylic dianhydride's composition and diamine compound composition, can be these methods In any one.
Additionally, in the case that tetracarboxylic dianhydride's composition and/or diamine component comprise multiple compounds, can be to mix in advance The state closed makes it react, and it can be made individually to react successively, can also make individually to react successively obtained by Low-molecular weight carries out hybrid reaction and makes HMW body.
As long as the temperature during synthesis of above-mentioned polyamic acid is entered in the range of the fusing point of the solvent from above-mentioned use is to boiling point Row suitably set, for example can select the optional temperature of-20 DEG C～150 DEG C, but good ,-5 DEG C～100 DEG C, lead to It is often about 0～100 DEG C, be preferably about 0～70 DEG C.
Owing to the reaction time depends on the reactivity of reaction temperature, raw material, therefore can not without exception depending on, but be usually About 1～100 hour.
It additionally, reaction can be carried out with optional concentration, but if concentration is too low, then is not readily available the poly-of HMW Compound；If excessive concentration, then the viscosity of reactant liquor becomes too high, it is difficult to stir uniformly, and therefore tetracarboxylic dianhydride becomes Divide and be preferably 1～50 mass %, more preferably 5～40 mass % with the total concentration in the reaction solution of diamine component.Reaction Initial stage is carried out with high concentration, also can add organic solvent afterwards.
<imidizate of polyamic acid>
As the method making polyamic acid carry out imidizate, can enumerate direct-fired for the solution of polyamic acid hot acyl Imidization, the catalyst imidizate adding catalyst in the solution of polyamic acid.
Temperature in the case of polyamic acid hot-imide in the solution is made to be 100 DEG C～400 DEG C, preferably 120 DEG C～250 DEG C, it is preferably discharged to the water being generated by imidization reaction outside system while carrying out.
Chemistry (catalyst) imidizate of polyamic acid can be by adding base catalysis in the solution of polyamic acid Agent and acid anhydrides, under the temperature conditions of-20～250 DEG C, preferably 0～180 DEG C, carried out being stirred in system.
The amount of base catalyst is 0.5～30 mole times of the acid amides acidic group of polyamic acid, is preferably 1.5～20 moles Times, the amount of acid anhydrides is 1～50 mole times of the acid amides acidic group of polyamic acid, is preferably 2～30 moles times.
As base catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine, 1-ethyl piperidine etc. can be enumerated, its Middle pyridine has the alkalescence of appropriateness for making reaction carry out, and is therefore preferred.
As acid anhydrides, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be enumerated, wherein, if using acetic acid Acid anhydride, then refined become easy after reaction terminates, and is therefore preferred.
The acid imide rate utilizing catalyst imidizate can be by regulation catalytic amount and reaction temperature, reaction time Control.
In the polyimide resin for the present invention, the dehydration closed-loop rate (acid imide rate) of acid amides acidic group is not necessarily required to It is 100%, can optionally could be adjusted to according to purposes, purpose use.Particularly preferably more than 50%.
In the present invention, can directly use its filtrate after above-mentioned reaction solution is filtered or be diluted or dense Contracting, coordinates silica described later etc. to make resin film formation composition wherein.In the feelings like this through filtering Under condition, heat resistance, flexibility or the linear expansion coefficient characteristic that can not only reduce the resin film that can become gained deteriorate as far as possible The reason being mixed into of impurity, additionally it is possible to efficiency obtains resin film formation composition well.
Additionally, with regard to the polyimides for the present invention, it is contemplated that the intensity of resin film, behaviour when forming resin film The property made, the uniformity etc. of resin film, divide preferably by weight average obtained by the polystyrene conversion of gel permeation chromatography (GPC) Son amount (Mw) is 5,000～200,000.
<polymer recovery>
In the case that in the reaction solution from polyamic acid and polyimides, recovery component of polymer uses, as long as will Reaction solution is put into and is carried out in poor solvent precipitating.As for precipitation poor solvent, can enumerate methyl alcohol, acetone, Hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene, water etc..Put into poor solvent In make its polymer precipitating can filter and reclaim after, under normal or reduced pressure, carry out normal temperature or heat drying.
If additionally, be re-dissolved in the polymer making precipitation reclaim in organic solvent, reprecipitation reclaim operation repeat 2 ～10 times, then can reduce the impurity in polymer.As poor solvent now, if using such as alcohols, ketone, hydrocarbon etc. The poor solvent of more than 3 kinds, then further improve refined efficiency, is therefore preferred.
The organic solvent making resinous principle dissolve in reprecipitation recovery process is not particularly limited.As concrete example, can Enumerate N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N-methyl caprolactam, 2-pyrroles Alkanone, N-ethyl pyrrolidone, NVP, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl Sulfoxide, gamma-butyrolacton, 1,3-dimethyl-2-imidazolidinone, dipentene, ethyl pentyl group 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 and use.
[silica]
Silica (silica) for the present invention is not particularly limited, but the silica of particle shape, for example flat Equal particle diameter is below 100nm, and such as 5nm～100nm, preferably 5nm～55nm obtain higher degree well transparent from repeatability Film from the viewpoint of, preferably 5nm～50nm, more preferably 5nm～45nm, still more preferably be 5nm～35nm, enter One step is preferably 5nm～30nm.
In the present invention, the average grain diameter of so-called silicon dioxide granule, is by use silicon dioxide granule, utilizes N2 adsorption The average size that the specific surface area value that method measures calculates.
Particularly in the present invention, it may be preferred to use the cataloid of value with above-mentioned average grain diameter, as This cataloid, it is possible to use Ludox.As Ludox, it is possible to use with sodium silicate aqueous solution as raw material, by public affairs The water silica sol of the method manufacture known and the water using the decentralized medium as this water silica sol are replaced into organic solvent and obtain Organic silicon sol.
Further, it is also possible to use in the organic solvents such as alcohol, at catalyst (for example, ammonia, organic amine compound, hydroxide The base catalysts such as sodium) in the presence of, the alkoxy silane such as methyl silicate, silester is hydrolyzed, is condensed obtained by silicon Colloidal sol or this Ludox is carried out the organic silicon sol that solvent is replaced into other organic solvents.
Wherein, present invention preferably uses the organic silicon sol that decentralized medium is organic solvent.
As the example of the organic solvent in above-mentioned organic silicon sol, methyl alcohol, ethanol, isopropanol etc. can be enumerated rudimentary Alcohol；The linear class such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide；The cyclic amides such as METHYLPYRROLIDONE Class；The ethers such as gamma-butyrolacton；The glycols such as ethyl cellosolve, ethylene glycol, acetonitrile etc..This displacement can by utilize the way of distillation, The usual way of ultrafiltration etc. is carried out.
The viscosity of above-mentioned organic silicon sol is 0.6mPa s～100mPa about s at 20 DEG C.
As the example of the commercially available product of above-mentioned organic silicon sol, (methyl alcohol dispersed silicon is molten can to enumerate such as trade name MA-ST-S Glue, Nissan Chemical Industries (strain) is made), trade name MT-ST (methyl alcohol dispersed silicon colloidal sol, Nissan Chemical Industries (strain) make), trade name MA-ST-UP (methyl alcohol dispersed silicon colloidal sol, Nissan Chemical Industries (strain) is made), trade name MA-ST-M (methyl alcohol dispersed silicon colloidal sol, daily output Chemical industry (strain) is made), trade name MA-ST-L (methyl alcohol dispersed silicon colloidal sol, Nissan Chemical Industries (strain) make), trade name IPA- ST-S (isopropanol dispersed silicon colloidal sol, Nissan Chemical Industries (strain) is made), trade name IPA-ST (isopropanol dispersed silicon colloidal sol, daily output Chemical industry (strain) is made), trade name IPA-ST-UP (isopropanol dispersed silicon colloidal sol, Nissan Chemical Industries (strain) make), trade name IPA-ST-L (isopropanol dispersed silicon colloidal sol, Nissan Chemical Industries (strain) make), (isopropanol dispersed silicon is molten for trade name IPA-ST-ZL Glue, Nissan Chemical Industries (strain) make), trade name NPC-ST-30 (n-propyl cellosolve dispersed silicon colloidal sol, Nissan Chemical Industries (strain) makes), trade name PGM-ST (1-methoxy-2-propanol dispersed silicon colloidal sol, Nissan Chemical Industries (strain) make), trade name DMAC-ST (dimethylacetylamide dispersed silicon colloidal sol, Nissan Chemical Industries (strain) is made), trade name XBA-ST (dimethylbenzene-n-butanol Mixed solvent dispersed silicon colloidal sol, Nissan Chemical Industries (strain) make), trade name EAC-ST (ethyl acetate dispersed silicon colloidal sol, daily outputization Learn industry (strain) system), trade name PMA-ST (propylene glycol monomethyl ether dispersed silicon colloidal sol, Nissan Chemical Industries (strain) System), trade name MEK-ST (methyl ethyl ketone dispersed silicon colloidal sol, Nissan Chemical Industries (strain) make), trade name MEK-ST-UP (first Base ethyl ketone dispersed silicon colloidal sol, Nissan Chemical Industries (strain) make), trade name MEK-ST-L (methyl ethyl ketone dispersed silicon colloidal sol, day Produce chemical industry (strain) system) and trade name MIBK-ST (hexone dispersed silicon colloidal sol, Nissan Chemical Industries (strain) System) etc., but do not limited by these.
In the present invention, can be using silica, be for example enumerated like that as the said goods that organic silicon sol uses Silica in two or more mixing use.
[organic solvent]
The resin film formation composition of the present invention, in addition to aforementioned polyimides and silica, also comprises organic Solvent.This organic solvent is not particularly limited, and can enumerate for example, be used during with above-mentioned modulation polyamic acid and polyimides The same solvent of the concrete example of reaction dissolvent.More specifically, DMF, N can be enumerated, N-dimethylacetamide Amine, METHYLPYRROLIDONE, 1,3-dimethyl-2-imidazolinone, N-ethyl-2-pyrrolidone, gamma-butyrolacton etc..Need Illustrating, organic solvent can be used alone a kind, it is also possible to combines two or more and uses.
Wherein, if it is considered that repeatability obtains the high resin film of flatness, then preferred N, N-dimethylacetamide well Amine, METHYLPYRROLIDONE, gamma-butyrolacton.
[resin film formation composition]
The present invention is the resin film formation composition containing aforementioned polyimides, silica and organic solvent.This In the resin film formation composition of the present invention be uniform, do not observe separated composition.
In the resin film formation composition of the present 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.
Additionally, the use level of the solid constituent amount in the resin film formation composition of the present invention is usually 0.5～30 About quality %, about preferably 5～25 mass %.If solid component concentration is less than 0.5 mass %, then thin at making resin Film aspect, masking efficiency step-down, and the viscosity of resin film formation composition, apply uniformly therefore, it is difficult to obtain surface Film.Additionally, if solid component concentration is more than 30 mass %, then the viscosity of resin film formation composition becomes too 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 constituent mentioned here Amount, the gross mass of the composition beyond expression organic solvent, even aqueous monomer etc. also serves as solid constituent and is included in weight In.
It should be noted that the viscosity of resin film formation composition is to consider the thickness etc. of made resin film And suitably set, but for the purpose of obtain the resin film of thickness of particularly about 5～50 μm well by repeatability In the case of, it is generally 500～50 at 25 DEG C, 000mPa about s, preferably 1,000～20,000mPa about s.
In order to give the resin film formation composition processing characteristics of the present invention, various feature, can be coordinated other The low molecule of various organic or inorganics or macromolecular compound.It is, for example possible to use catalyst, defoamer, levelling agent, surface work Property agent, dyestuff, plasticizer, particulate, coupling agent, sensitizer etc..Such as catalyst can be to reduce delay, the line of resin film Add when for the purpose of the coefficient of expansion.It should be noted that in addition to aforementioned polyimides, silica and organic solvent, also The resin film formation composition comprising catalyst also can be the object of the present invention.
The resin film formation composition of the present invention can be by the polyimides being obtained by above-mentioned method and dioxy SiClx is dissolved in and obtains in above-mentioned organic solvent, it is also possible to add titanium dioxide in the reaction solution after modulation polyimides Silicon, adds aforementioned organic solvents further according to expectation and makes.
[resin film]
The resin film formation composition of present invention mentioned above is coated base material, by being dried heating And remove organic solvent, it is possible to obtain there is the linear expansion coefficient of high-fire resistance, high transparent, the flexibility of appropriateness and appropriateness And postpone little resin film.
And, above-mentioned resin film, i.e. contains above-mentioned polyimides and the resin of above-mentioned inorganic silica compound is thin Film is also the object of the present invention.And then, in addition to aforementioned polyimides and silica, also comprise the resin film of catalyst It is also the object of the present invention.
As the base material of the manufacture for resin film, can enumerate for example, plastics (Merlon, 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..
Particularly in the case that the baseplate material as electronic device is applied, from the such sight of existing device can be utilized Point sets out, and the base material 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 base material as application, sticking up of the base material after coating From the viewpoint of Qu, it is further preferred that, less than 30ppm/ DEG C, more preferably less than 20ppm/ DEG C.
Rubbing method to base material coating resin film-forming composition is not particularly limited, and can enumerate for example, and casting applies Cloth method, method of spin coating, knife coating, dip coating, rolling method, stick coating method, die coating method, ink-jet method, print process are (relief printing plate, intaglio plate, flat Version, serigraphy etc.) etc., these methods can be suitably used according to purpose.
Heating-up temperature is preferably less than 300 DEG C.If it exceeds 300 DEG C, then obtained resin film becomes fragile, and sometimes can not Obtain the resin film being particularly suitable for display base plate purposes.
Additionally, if it is considered that the heat resistance of obtained resin film and linear expansion coefficient characteristic, then it is desirable that, will After the resin film formation composition of coating has carried out heating in 5 minutes～2 hours at 40 DEG C～100 DEG C, maintain this state Making the interim rising of heating-up temperature, final carrying out more than 175 DEG C and less than 280 DEG C 30 minutes～2 hours is heated.Thus, pass through So that temperature more than this 2 stages in stage of the stage of solvent seasoning and promotion molecularly oriented heats, its table can be made Existing low thermal expansion characteristics.
Particularly, the resin film formation composition of coating is preferably carrying out 5 minutes～2 hours with 40 DEG C～100 DEG C After heating, to carry out heating in 5 minutes～2 hours more than 100 DEG C and less than 175 DEG C, then with more than 175 DEG C and less than 280 DEG C Carry out heating in 5 minutes～2 hours.
Utensil for heating can enumerate such as heating plate, baking oven etc..Heating atmosphere can be under air, it is also possible to is Under the non-active gas such as nitrogen, furthermore, it is possible at ambient pressure or decompression under, furthermore, it is possible to heating each stage in application Different pressure.
With regard to the thickness of resin film, particularly in the case of using as flexible display substrate, usually 1～ About 60m, preferably about 5～50 μm, the thickness of the film before regulation heating forms the resin film of desired thickness.
It should be noted that as the method that the resin film being thusly-formed is peeled off from base material, be not particularly limited, Can enumerate and this resin film be carried out together with base material cool down, gap introduced to film thus the method peeled off, or execute via roller The method etc. adding tension force thus peeling off.
The resin film that a preferred scheme of the thus obtained present invention relates to can realize the light under wavelength 400nm Transmissivity is more than the 75% so high transparency.
And then, the linear expansion coefficient that this resin film can have at such as 50 DEG C～200 DEG C is less than 60ppm/ DEG C, special Not being 10ppm/ DEG C～35ppm/ DEG C so low value, the linear expansion coefficient can having in addition at such as 200 DEG C～250 DEG C is Less than 80ppm/ DEG C, particularly 15ppm/ DEG C～55ppm/ DEG C of so low value, the tree of excellent in dimensional stability when being to heat Membrane of lipoprotein.
The particularly advantage of this resin film is delay R in face0With thickness direction retardation RthAll very little, postpone R in face0 By the product representation of the birefringence (differences of 2 refractive indexes orthogonal in face) when the wavelength of incident light is 590nm and thickness, thickness Direction postpones RthWith 2 birefringences (each folding with thickness direction of 2 refractive indexes in face when in terms of the cross section from thickness direction Penetrate the difference of rate) mean value that is multiplied by 2 phase differences obtained from thickness respectively represents.Average film at the resin film of the present invention In the case that thickness is 15 μm～40 μm, there is the delay R of thickness directionthLess than 700nm, for example, below 660nm, 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.
Thus, the resin film formation composition of the application of the invention forms resin film, can reduce this tree The delay of membrane of lipoprotein, the method for the delay so reducing resin film is also the object of the present 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, the basilar memebrane that can be particularly suitable as flexible display substrate uses.
Embodiment
Hereinafter enumerate embodiment further illustrating the present invention, but the present invention is not limited by following embodiment.
The implication of the abbreviation number using 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>
TFMB:2,2 '-bis-(trifluoromethyl) benzidine
TMDA:1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indenes-5 (or 6) amine
<organic solvent>
DMAc:N, N-dimethylacetylamide
NMP:N-N-methyl-2-2-pyrrolidone N
DMF:N, dinethylformamide
IPA: isopropanol
GBL: gamma-butyrolacton
<Ludox>
(silica average grain diameter: 10～15nm, silica solid composition is dense for IPA-ST: isopropanol dispersed silicon colloidal sol Degree: 30 mass %) Nissan Chemical Industries (strain) system
DMAC-ST:N, N-dimethylacetylamide dispersed silicon colloidal sol (silica average grain diameter: 10～15nm, silica Solid component concentration: 20 mass %), Nissan Chemical Industries (strain) is made
GBL-ZL: gamma-butyrolacton dispersed silicon colloidal sol (silica solid constituent concentration: 25 mass %)
GBL-L: gamma-butyrolacton dispersed silicon colloidal sol (silica solid constituent concentration: 25 mass %)
GBL-M: gamma-butyrolacton dispersed silicon colloidal sol (silica solid constituent concentration: 30 mass %)
GBL-ST: gamma-butyrolacton dispersed silicon colloidal sol (silica solid constituent concentration: 30 mass %)
GBL-S: gamma-butyrolacton dispersed silicon colloidal sol (silica solid constituent concentration: 25 mass %)
GBL-UP: gamma-butyrolacton dispersed silicon colloidal sol (chain type, silica solid constituent concentration: 20 mass %)
It should be noted that above-mentioned gamma-butyrolacton dispersed silicon colloidal sol (GBL-ZL, GBL-L, GBL-M, GBL-ST, GBL-S And GBL-UP) it is that the method is for disperseing Nissan Chemical Industries (strain) preparing isopropanol respectively by obtained from method described later Ludox (IPA-ST-ZL, IPA-ST-L, IPA-ST) and Nissan Chemical Industries (strain) methyl alcohol processed dispersed silicon colloidal sol (MA-ST-M, MA-ST-S, MA-ST-UP) in the isopropanol as solvent or methyl alcohol carry out solvent and be replaced into gamma-butyrolacton.
Additionally, the silica average grain diameter in above-mentioned IPA-ST and DMAC-ST is goods catalogue value, in current use In Ludox, the average grain diameter being calculated by the specific surface area value utilizing determination of nitrogen adsorption is as follows.Specifically, ユ ア サ is used ア イ オ ニ Network ス society system, specific area measuring device モ ノ ソ Block MS-16 measure the specific surface of the dried powder of Ludox Long-pending, use the specific surface area S (m measuring2/ g), calculate average primary particle diameter by formula D (nm)=2720/S.
It should be noted that in an embodiment, for the modulation of sample and the analysis of physical property and the device of evaluation and condition As follows.
1) mensuration of number-average molecular weight and weight average molecular weight
The number-average molecular weight (hereinafter referred to as Mn) of polymer and weight average molecular weight (hereinafter referred to as Mw) be utilize following Condition measures, device: Showa electrician (strain) system, Showdex GPC-101, post: KD803 and KD805, column temperature: 50 DEG C, dissolution Solvent: DMF, flow: 1.5ml/ minute, calibration curve: polystyrene standard.
2) thickness
The thickness of the resin film of gained is to utilize (strain) テ Network ロ ッ Network thickness gauge to measure.
3) linear expansion coefficient (CTE)
Using TA イ Application ス ツルメン Star society TMA Q400, it is 5mm, a length of 16mm that resin film is cut into width Size, first carries out heating up and be heated to 50～350 DEG C (heating for the first time) with 10 DEG C/min, then drops with 10 DEG C/min Temperature is simultaneously cooled to 50 DEG C, then carries out heating up and be heated to 50～420 DEG C (second time heating) with 10 DEG C/min, by measuring this When second time 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 obtain.It should be noted that by heating for the first time, cooling and second time heating, Apply loading 0.05N.
4) 5% weight reduces temperature (Td5%)
5% weight reduces temperature (Td5%[DEG C]) it is 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 obtains.
5) light transmittance (transparent) (T400nm、T550nm) and CIE b value (CIE b*)
Light transmittance (the T of wavelength 400nm and 550nm400nm、T550nm[%]) and CIE b value (CIE b*) it is to use Japan's electricity look industry (strain) SA4000 processed spectrometer, is at room temperature measured with air for reference.
6) (R is postponedth、R0)
Use prince to measure machine (strain) system, KOBURA 2100ADH, at room temperature measure thickness direction retardation (Rth) and Postpone (R in face0)。
It should be noted that thickness direction retardation (Rth) and face in postpone (R0) utilize following formula to calculate.
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 referred to as slow axis (slow axis) to 2 refractive indexes orthogonal in face by Nx > Ny, is referred to as Ny fast Axle (Fast axis)).
Nz: the refractive index in thickness (vertically) direction for face
D: thickness
The difference (Nx-Ny) (birefringence) of Δ Nxy: 2 refractive indexes in face
The difference (birefringence) of refractive index Nz of Δ Nxz: refractive index Nx in face and thickness direction
The difference (birefringence) of refractive index Nz of Δ Nyz: refractive index Ny in face and thickness direction
7) birefringence (Δ n)
Use the thickness direction retardation (R being obtained by aforesaid<6) postpone>th) value, utilize following formula to calculate.
Δ N=[Rth/ d (film thickness)]/1000
[1] the modulation example of Ludox
(modulation of modulation example 1:GBL-M)
Put into Nissan Chemical Industries (strain) methyl alcohol processed dispersed silicon colloidal sol in the round-bottomed flask of 1000mL: MA-ST-M 350g (silica solid constituent concentration: 40.4 mass %) and gamma-butyrolacton 329.93g.Then, this flask and vacuum evaporator are made Connect and reduce pressure in flask, soak 20～50 minutes in the tepidarium of about 35 DEG C, thus obtain solvent and put by methyl alcohol Change Ludox (GBL-M) the 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 dispersed silicon colloidal sol: IPA-ST-ZL is put in the round-bottomed flask of 1000mL 350g (silica solid constituent concentration: 30 mass %) and gamma-butyrolacton 315g.Then, make this flask and be equipped with resistance toization The vacuum evaporator of the property learned vavuum pump connects and reduces pressure in flask, soaks 30～60 points in the tepidarium of about 35 DEG C Clock, thus obtain Ludox (GBL-ZL) about 420g (the silica solid composition 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 dispersed silicon colloidal sol: IPA-ST-L is put in the round-bottomed flask of 1000mL 350g (silica solid constituent concentration: 30 mass %) and gamma-butyrolacton 315g.Then, make this flask and be equipped with resistance toization The vacuum evaporator of the property learned vavuum pump connects and reduces pressure in flask, soaks 30～60 points in the tepidarium of about 35 DEG C Clock, thus obtain Ludox (GBL-L) about 420g (the silica solid composition 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 dispersed silicon colloidal sol: IPA-ST is put in the round-bottomed flask of 1000mL 350g (silica solid constituent concentration: 30 mass %) and gamma-butyrolacton 245g.Then, make this flask and be equipped with resistance toization The vacuum evaporator of the property learned vavuum pump connects and reduces pressure in flask, soaks 30～60 points in the tepidarium of about 35 DEG C Clock, thus obtain Ludox (GBL-ST) about 350g (the silica solid composition that solvent is replaced as gamma-butyrolacton by isopropanol Concentration: 30 mass %).
(modulation of modulation example 5:GBL-S)
Put into Nissan Chemical Industries (strain) methyl alcohol processed dispersed silicon colloidal sol in the round-bottomed flask of 1000mL: MA-ST-S 350g (silica solid constituent concentration: 25 mass %) and gamma-butyrolacton 262.5g.Then, make this flask and be equipped with chemically-resistant Property vavuum pump vacuum evaporator connect and reduce pressure in flask, in the tepidarium of about 35 DEG C soak 20～50 minutes, Thus obtain solvent by methanol replacement become gamma-butyrolacton Ludox (GBL-S) about 350g (silica solid constituent concentration: 25 mass %).
(modulation of modulation example 6:GBL-UP)
Nissan Chemical Industries (strain) methyl alcohol processed dispersed silicon colloidal sol: MA-ST-UP is put in the round-bottomed flask of 1000mL 350g (silica solid constituent concentration: 20 mass %) and gamma-butyrolacton 280g.Then, make this flask and be equipped with resistance toization The vacuum evaporator of the property learned vavuum pump connects and reduces pressure in flask, soaks 20～50 points in the tepidarium of about 35 DEG C Clock, thus obtain solvent and methanol replacement is become Ludox (GBL-UP) the about 350g of gamma-butyrolacton (silica solid composition is dense Degree: 20 mass %).
[2] synthesis example
[synthesis example 1]
Be sequentially added in the flask of the 2,000mL being provided with mechanical agitator TFMB58g (0.1811mol), DMAc188.23g, starts stirring.It is added to BODA36.25g (0.1448mol), carry out nitrogen displacement, then at 70 DEG C Under carry out 3 hours stirring, then, reactant mixture is cooled to 50 DEG C, is added to CBDA7.103g (0.0362mol), Carry out stirring in 2 hours further.Then, reactant mixture is cooled to room temperature, carries out night stirring further.Then, to instead Answering interpolation DMAc in mixture, the concentration (concentration of the composition beyond organic solvent) being diluted to solid constituent is 5 mass %.
Reactant mixture after dilution adds acetic anhydride 73.96g (0.7244mol) and pyridine 42.97g (0.5433mol) at 90～100 DEG C, carry out stirring in 3 hours.
After stirring terminates, reactant mixture is cooled to room temperature, adds cooled mixture to methyl alcohol 7.094kg In, the slurry of gained is carried out stirring in 30 minutes.Then, it is recovered by filtration filtrate.Then, in order to refined, by gained Filtrate is again added in methyl alcohol 7.094kg, it is thus achieved that slurry, is stirred by same method and filters.Then one is entered Step, in order to refined, carries out interpolation in methyl alcohol for the filtrate, stirring and filtration again.
Finally, by the filtrate of gained under reduced pressure, carry out drying in 8 hours at 100 DEG C, it is thus achieved that the polyamides as target is sub- Amine A1 76g (yield: 76%, Mw:59,302, Mn:25,923).
[synthesis example 2]
Put in the three-neck flask of the 2,000mL being provided with the mechanical agitator with nitrogen injection/outlet TFMB115g(0.3591mol).Add the gamma-butyrolacton (GBL) of 468.9g immediately after, start stirring.Diamines (TFMB) is complete CL, after solvent, adds BODA71.88g (0.2872mol), carries out stirring in 3 hours at 70 DEG C in a nitrogen atmosphere.Connect , reactant mixture is cooled to 50 DEG C, be added to CBDA14.08g (0.071mol), carry out stirring in 2 hours further. Then, it reactant mixture is cooled to room temperature and maintains temperature, being stirred overnight in a nitrogen atmosphere further.Then, to reaction Adding GBL in mixture, the concentration (concentration of the composition beyond organic solvent) being diluted to solid constituent is 5 mass %.
Reactant mixture after dilution adds acetic anhydride 146.65g (1.436mol) and pyridine 85.21g (1.077mol) at 90～100 DEG C, carry out stirring in 3 hours.
After stirring terminates, reactant mixture is cooled to room temperature, adds cooled mixture to methyl alcohol 2.5kg In, the slurry of gained is carried out stirring in 30 minutes.Then, it is recovered by filtration filtrate.Then, in order to refined, by gained Filtrate is again added in methyl alcohol 2.5kg, it is thus achieved that slurry, is stirred by same method and filters.Then further In order to refined, again carry out interpolation in methyl alcohol 2.5kg for the filtrate, stirring and filtration.
Finally, the filtrate making gained carries out drying in 8 hours in vacuum drying oven, at 120 DEG C, it is thus achieved that as target Polyimides A2 153g (yield: 76.5%, Mn:44,460, Mw:96,641).
It is dissolved in above-mentioned polyimides A2 in GBL, use the filter of 5 μm slowly to carry out the solution of gained pressurizeing Filter, the concentration of modulation solid constituent is the solution (polyimides A2 solution) of 12 mass %.
[synthesis example 3]
Add in the three-neck flask of the 250mL being provided with mechanical agitator with nitrogen injection/outlet TFMB16.9g (0.052mol) and TMDA1.598g (0.006mol).Add the gamma-butyrolacton of 124.46g immediately after (GBL), stirring is started.After diamines (TFMB and TMDA) is dissolved completely in solvent, add TCA6.725g (0.03mol), at nitrogen Carry out stirring in 5 hours under atmosphere, at 100 DEG C.Then, reactant mixture is cooled to 50 DEG C, is added to CBDA5.883g (0.03mol) stirring in 3 hours, is carried out further.Then, it reactant mixture is cooled to room temperature and maintains temperature, existing further It is stirred overnight under nitrogen atmosphere.Then, in reactant mixture add GBL, be diluted to solid constituent concentration (organic solvent with The concentration of outer composition) it is 4 mass %.
Reactant mixture after dilution adds acetic anhydride 24.5g (0.24mol) and pyridine 14.23g (0.18mol), Carry out stirring in 6 hours at 60～70 DEG C.
After stirring terminates, reactant mixture is cooled to room temperature, adds cooled mixture to methyl alcohol 0.7kg In, the slurry of gained is carried out stirring in 30 minutes.Then, it is recovered by filtration filtrate.Then, in order to refined, by gained Filtrate is again added in methyl alcohol 0.7kg, it is thus achieved that slurry, is stirred by same method and filters.Then further In order to refined, again carry out interpolation in methyl alcohol 0.7kg for the filtrate, stirring and filtration.
Finally, the filtrate making gained carries out drying in 8 hours in vacuum drying oven, at 120 DEG C, it is thus achieved that as target Polyimides B 24.26g (yield: 78%, Mn:65,425, Mw:138,024).
It is dissolved in above-mentioned polyimides B in GBL, use the filter of 5 μm slowly to carry out the solution of gained pressurizeing Filter, the concentration of modulation solid constituent is the solution (polyimides B solution) of 11.17 mass %.
[synthesis example 4]
Add in the three-neck flask of the 100mL being provided with mechanical agitator and cooler with nitrogen injection/outlet Enter TFMB25.61g (0.08mol).Add the gamma-butyrolacton (GBL) of 173.86g immediately after, start stirring.Diamines (TFMB) After being dissolved completely in solvent, add BODAxx10g (0.04mol) and CBDA7.84g (0.04mol), heat in a nitrogen atmosphere To 140 DEG C.Then, add the 1-ethyl piperidine of 1.739g in reaction solution to, carry out at 210 DEG C 4.5 hours at nitrogen Heating stirring under gas atmosphere.
Reactant mixture is added in methyl alcohol 0.9kg, the slurry of gained is carried out stirring in 30 minutes.Then, by mistake Filtrate is reclaimed in filter.Then, in order to refined, the filtrate of gained is again added in methyl alcohol 0.9kg, it is thus achieved that slurry, passes through Same method is stirred and filters.Then further for refined, filtrate adding in methyl alcohol 0.9kg is again carried out Add, stir and filter.
Finally, the filtrate making gained carries out drying in 8 hours in vacuum drying oven, at 120 DEG C, it is thus achieved that as target Polyimides C 31.16g (yield: 74%, Mn:40,465, Mw:281,382).
It is dissolved in above-mentioned polyimides C in GBL, use the filter of 5 μm slowly to carry out the solution of gained pressurizeing Filter, the concentration of modulation solid constituent is the solution (polyimides C solution) of 13.5 mass %.
[3] modulation (1) of substrate film composite
[embodiment 1]
At room temperature, make polyimides A1 3g be dissolved in DMAc22g and modulate polyimide solution, use the mistake of 5 μm The solution of gained is slowly carried out pressure filtration by filter.Then, in filtrate, add IPA-ST Ludox 6.67g and carry out 30 points Clock stirs, and then by the mixture after stirring with night inactive state placement, thus obtains resin combination.
[embodiment 2～3]
GBL-ST Ludox 6.67g (embodiment 2), DMAC-ST Ludox 10.00g (embodiment 3) is used to replace respectively IPA-ST Ludox 6.67g, in addition, utilizes method similarly to Example 1 to obtain resin combination.
[embodiment 4]
Use NMP22g to replace DMAc22g, in addition, utilize method similarly to Example 1 to obtain resin combination Thing.
[embodiment 5～6]
Respectively use NMP22g (embodiment 5), GBL22g (embodiment 6) replace DMAc22g, in addition, utilize with The same method of embodiment 2 obtains resin combination.
[embodiment 7]
The usage amount making GBL-ST Ludox is 2.5g, in addition, utilizes method similarly to Example 2 to obtain resin Composition.
[embodiment 8～9]
Respectively use NMP22g (embodiment 8), GBL22g (embodiment 9) replace DMAc22g, in addition, utilize with The same method of embodiment 7 obtains resin combination.
[embodiment 10]
At room temperature, make polyimides A1 3g be dissolved in GBL22g and modulate polyimide solution, use the mistake of 5 μm The solution of gained is slowly carried out pressure filtration by filter.Then, in filtrate, add GBL-ST Ludox 6.67g and carry out 30 points Clock stirs, and is added to the oxygen as catalyst in the way of being then 0.5 mass % using the quality overall relative to composition Double ((3-aminopropyl) dimethylsilane), carry out stirring in 3 minutes, it is thus achieved that resin combination.
[embodiment 11～12]
GBL-UP Ludox 10g (embodiment 11), GBL-M Ludox 6.67g (embodiment 12) is used to replace respectively GBL-ST Ludox 6.67g, in addition, utilizes method similarly to Example 6 to obtain resin combination.
[embodiment 13]
At room temperature, make polyimides A1 3g be dissolved in GBL22g and modulate polyimide solution, use the mistake of 5 μm The solution of gained is slowly carried out pressure filtration by filter.Then, in filtrate, GBL-ST Ludox 3.33g and GBL-UP silicon are added Colloidal sol 5g, carries out stirring in 30 minutes, then by the mixture after stirring with night inactive state placement, thus obtains resin combination Thing.
[embodiment 14～15]
GBL-M Ludox 3.33g (embodiment 14), GBL-S Ludox 4g (embodiment 15) is used to replace GBL-respectively UP Ludox 5g, in addition, utilizes method similarly to Example 13 to obtain resin combination.
[4] making (1) of resin film
[embodiment 16]
The resin combination being obtained by embodiment 1 is coated glass substrate, makes film at 50 DEG C 30 minutes, 140 DEG C Lower 30 minutes, within 60 minutes, carry out successively heating at 200 DEG C thus obtain resin film.It should be noted that heating uses in advance Set 3 baking ovens at a desired temperature.
The resin film of gained is peeled off by mechanical cut-out, for evaluation afterwards.
[embodiment 17～30]
The resin combination being obtained by embodiment 2～embodiment 15 is used to replace the resin combination being obtained by embodiment 1, In addition, method similarly to Example 16 is utilized to obtain resin film.
[5] evaluation (1) of resin film
With regard to heat resistance and the optical characteristics of each resin film being made by above-mentioned 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 Do not evaluate.Show the result in table 1.
The linear expansion coefficient [ppm/ DEG C] (50～200 DEG C) that as shown in table 1, can confirm that the resin film of the present invention is low, The yellowing that the light transmittance [%] of 400nm and 550nm after solidifying in addition is high and then CIE b* value is represented is little, postpone quilt Suppression is low value.Additionally, demonstrate " content of Ludox is more, and linear expansion coefficient is lower and light transmittance is higher " this The tendency of sample.
Even if additionally, the resin film of the present invention being obtained by above-described embodiment 16～30 is respectively provided with and they is using two hands Take and bend to also not rupture in the case of acute angle (about 30 degree), the high flexibility required by flexible display substrate.
[6] modulation (2) of substrate film composite
[embodiment 31]
At room temperature, polyimides A2 solution 4.457g (the polyamides Asia that the filter of 5 μm will be modulated is used by synthesis example 2 Amine A2 solid constituent amount: 0.534g) slowly carry out pressure filtration.Then in filtrate add GBL-ZL Ludox 1.426g and Gamma-butyrolacton (GBL) 0.059g, carry out 30 minutes stirring, then will stirring after mixture with one night inactive state place, from And obtain resin combination.
[embodiment 32～embodiment 38]
The interpolation of the polyimides A2 solution that makes to be modulated by synthesis example 2 usage amount of solution form (numerical value in table be) The addition of amount, the species of Ludox and addition and gamma-butyrolacton is shown in table 2 below, in addition, utilizes and real Execute the same method of example 31 and obtain resin combination.
[embodiment 39]
At room temperature, the polyimides B solution 2.146g (polyimides that the filter of 5 μm will be modulated is used by synthesis example 3 B solid constituent amount: 0.239g) slowly carry out pressure filtration.Then in filtrate, add GBL-ZL Ludox 0.639g and γ-fourth Lactone (GBL) 0.544g, carries out stirring in 30 minutes, then by the mixture after stirring with night inactive state placement, thus obtains Obtain resin combination.
[embodiment 40～embodiment 48]
The addition of the polyimides B solution that makes to be modulated by synthesis example 3 usage amount of solution form (numerical value in table be), The addition of the species of Ludox and addition and gamma-butyrolacton is shown in Table 3 below, in addition, utilizes and embodiment 39 same methods obtain resin combination.
[embodiment 49]
At room temperature, polyimides C solution 2.5147g (the polyamides Asia that the filter of 5 μm will be modulated is used by synthesis example 4 Amine C solid constituent amount: 0.339g) slowly carry out pressure filtration.Then in filtrate add GBL-ZL Ludox 0.905g and GBL0.165g, carries out stirring in 30 minutes, then by the mixture after stirring with night inactive state placement, thus obtains resin Composition.
[embodiment 50～embodiment 64]
The addition of the polyimides C solution that makes to be modulated by synthesis example 4 usage amount of solution form (numerical value in table be), The addition of the species of Ludox and addition and gamma-butyrolacton is shown in table 4 below, in addition, utilizes and embodiment 49 same methods obtain resin combination.
[7] making (2) of resin film
The resin combination being obtained by embodiment 31 is coated glass substrate, makes film at 50 DEG C 30 minutes, 140 DEG C Lower 30 minutes, at 220 DEG C 60 minutes, within 60 minutes, carry out successively heating at 280 DEG C thus obtain resin film.Need explanation It is that heating uses 4 baking ovens presetting at a desired temperature.
The resin film of gained is peeled off by mechanical cut-out, for evaluation afterwards.
Additionally, use the resin combination being obtained by embodiment 32～embodiment 64 to replace the resin being obtained by embodiment 31 Composition, in addition, utilizes method similar to the above to obtain each resin film.
[8] evaluation (2) of resin film
With regard to heat resistance and the optical characteristics of each resin film being made by above-mentioned steps, i.e. linear expansion coefficient, 5% weight Amount reduces temperature, light transmittance and CIE b value (yellow evaluation) and postpones, and evaluates respectively according to above-mentioned steps.Will Result is shown in table 2～table 4.
As shown in table 2～table 4, can confirm that the linear expansion coefficient [ppm/ DEG C] (particularly 50 of the resin film of the present invention ～200 DEG C) low, solidify in addition after the light transmittance [%] of 400nm and 550nm is high and then the Huang represented by CIE b* value Spend little, to postpone to be suppressed to low value, birefringent value Δ n also extremely low.Additionally, demonstrate that " content of Ludox is more, and line is swollen Swollen coefficient is lower " such tendency.
Even if additionally, the resin film of the present invention obtained as above is respectively provided with they are hand-held and bend to two Also the high flexibility required by that do not rupture in the case of acute angle (about 30 degree), flexible display substrate.

Claims (14)

1. the manufacture method of a resin film, it is characterised in that use containing polyimides, silicon dioxide granule and organic molten The resin film formation composition of agent,
Described polyimides is to carry out obtained from imidizate by polyamic acid, and described polyamic acid is to make to comprise ester ring type four Obtained from tetracarboxylic dianhydride's composition of carboxylic acid dianhydride and the diamine component comprising fluorinated aromatic diamines react,
The average grain diameter of described silicon dioxide granule is below 100nm, and described average grain diameter records by utilizing nitrogen adsorption method Specific surface area value calculates.
2. method according to claim 1, the tetracarboxylic dianhydride shown in described ester ring type tetracarboxylic dianhydride contained (C1),
In formula (C1), B1Represent the group of 4 valencys being selected from formula (X-1)～(X-12),
In formula, multiple R represent hydrogen atom or methyl independently of each other, and * represents associative key.
3. method according to claim 1 and 2, the diamines shown in described fluorinated aromatic diamines contained (A1),
H2N-B2-NH2 (A1)
In formula, B2Represent the group of the divalent being selected from formula (Y-1)～(Y-34),
In formula, * represents associative key.
4. method according to claim 1, the monomeric unit shown in described polyimides contained (2),
5. the quality of the method according to according to any one of Claims 1 to 4, described polyimides and described silicon dioxide granule Ratio is 7:3～3:7.
6. the method according to according to any one of Claims 1 to 5, described average grain diameter is below 60nm.
7. a resin film, it is to be manufactured by the method according to any one of claim 1～6.
8. a resin film formation composition, containing polyimides, silicon dioxide granule and organic solvent,
Described polyimides is to carry out obtained from imidizate by polyamic acid, and described polyamic acid is to make to comprise ester ring type four Obtained from tetracarboxylic dianhydride's composition of carboxylic acid dianhydride and the diamine component comprising fluorinated aromatic diamines react,
The average grain diameter of described silicon dioxide granule is below 100nm, and described average grain diameter records by utilizing nitrogen adsorption method Specific surface area value calculates.
9. resin film formation composition according to claim 8, described ester ring type tetracarboxylic dianhydride contained (C1) Shown tetracarboxylic dianhydride,
In formula (C1), B1Represent the group of 4 valencys being selected from formula (X-1)～(X-12),
In formula, multiple R represent hydrogen atom or methyl independently of each other, and * represents associative key.
10. resin film formation composition according to claim 8 or claim 9, described fluorinated aromatic diamines is contained (A1) diamines shown in,
H2N-B2-NH2 (A1)
In formula, B2Represent the group of the divalent being selected from formula (Y-1)～(Y-34),
In formula, * represents associative key.
11. resin film formation compositions according to claim 8, the list shown in described polyimides contained (2) Body unit,
Resin film formation composition according to any one of 12. according to Claim 8～11, described polyimides with described The mass ratio of silicon dioxide granule is 7:3～3:7.
Resin film formation composition according to any one of 13. according to Claim 8～12, described average grain diameter is 60nm Below.
The method of 14. 1 kinds of delays reducing resin film, it is characterised in that use and contain polyimides, silicon dioxide granule Form resin film with the resin film formation composition of organic solvent,
Described polyimides is to carry out obtained from imidizate by polyamic acid, and described polyamic acid is to make to comprise ester ring type four Obtained from tetracarboxylic dianhydride's composition of carboxylic acid dianhydride and the diamine component comprising fluorinated aromatic diamines react,
The average grain diameter of described silicon dioxide granule is below 100nm, and described average grain diameter records by utilizing nitrogen adsorption method Specific surface area value calculates.
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