WO2011122198A1 - Polyimide precursor, resin composition containing said precursor, and method for forming a film using resin composition - Google Patents
Polyimide precursor, resin composition containing said precursor, and method for forming a film using resin composition Download PDFInfo
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- WO2011122198A1 WO2011122198A1 PCT/JP2011/054488 JP2011054488W WO2011122198A1 WO 2011122198 A1 WO2011122198 A1 WO 2011122198A1 JP 2011054488 W JP2011054488 W JP 2011054488W WO 2011122198 A1 WO2011122198 A1 WO 2011122198A1
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- 0 C*(N)N*NC(*(*)(*)C(N)=O)=O Chemical compound C*(N)N*NC(*(*)(*)C(N)=O)=O 0.000 description 2
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/001—Phase modulating patterns, e.g. refractive index patterns
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a polyimide precursor, a resin composition containing the precursor, and a film forming method using the resin composition.
- wholly aromatic polyimide obtained from aromatic tetracarboxylic dianhydride and aromatic diamine is due to the rigidity of the molecule, the fact that the molecule is resonance-stabilized, the strong chemical bond, etc. It has excellent heat resistance, mechanical properties, etc., and is widely used as a film, coating agent, molded part and insulating material in fields such as electricity, battery, automobile and aerospace industry.
- Patent Document 1 discloses a polyimide precursor resin composition for a flexible device substrate including a polyimide precursor synthesized from p-phenylenediamine and s-biphenyltetracarboxylic anhydride.
- the resin composition can be formed by coating on a carrier substrate such as a glass substrate, and becomes a polyimide film having excellent heat resistance and a low thermal expansion coefficient. It is described that when peeling off from a glass substrate without causing peeling, it can be removed cleanly.
- a coating film obtained from a conventional polyimide precursor and a resin composition containing the precursor may have a large residual stress, and a film having a low glass transition temperature may be obtained.
- An object of the present invention is to provide a polyimide precursor capable of easily producing a film having a high glass transition temperature and little warpage, a resin composition containing the precursor, and a film forming method using the resin composition. There is.
- the present inventors have found that the above problems can be solved by using a polyimide precursor (polyamic acid) having a specific structural unit, and the present invention has been completed. . That is, the present invention provides the following [1] to [12].
- each R independently represents a hydrogen atom or a monovalent organic group
- each R 1 independently represents a group selected from the group represented by the following formula (3)
- each R 2 represents Independently, a group selected from the group represented by the following formula (4) is shown, and n is a positive integer.
- a plurality of R 5 each independently represents a monovalent organic group having 1 to 20 carbon atoms, and m represents an integer of 3 to 200.
- each R 3 is independently an ether group, thioether group, ketone group, ester group, sulfonyl group, alkylene group, amide group or siloxane group-containing group, hydrogen atom, halogen atom, alkyl group, hydroxy group.
- a nitro group, a cyano group or a sulfo group, the hydrogen atom of this alkyl group and alkylene group may be substituted with a halogen atom
- D is an ether group, thioether group, ketone group, ester group, sulfonyl group
- alkylene A1 is independently an integer of 1 to 3
- a2 is independently of 1 or 2
- a3 is independently of an integer of 1 to 4
- e is 0 Represents an integer of ⁇ 3.
- each R 4 independently represents a hydrogen atom or an alkyl group, the hydrogen atom of the alkyl group may be substituted with a halogen atom, and D represents an ether group, a thioether group, a ketone group, an ester group, A sulfonyl group, an alkylene group, an amide group or a siloxane group, each b independently represents 1 or 2, each c independently represents an integer of 1 to 3, and f represents an integer of 0 to 3.
- the polyimide precursor has an ether group, a thioether group, a ketone group, an ester group, a sulfonyl group, an alkylene group, an amide in the main chain of the precursor. Any one of [1] to [3], further comprising 0 to 15% by mass of a structural unit derived from a monomer containing at least one group selected from the group consisting of a group and a siloxane group in the polyimide precursor A polyimide precursor according to any one of the above.
- each A is independently at least one group selected from the group consisting of an ether group, a thioether group, a ketone group, an ester group, a sulfonyl group, an alkylene group, an amide group, and a siloxane group.
- Each of R 6 independently represents a hydrogen atom, a halogen atom, an alkyl group or a nitro group, the hydrogen atom of the alkyl group may be substituted with a halogen atom, and each d independently represents 1 to 4 Indicates an integer.
- a resin composition comprising the polyimide precursor according to any one of [1] to [6] and an organic solvent.
- organic solvent includes at least one solvent selected from the group consisting of ether solvents, ketone solvents, nitrile solvents, ester solvents, and amide solvents. Resin composition.
- a film forming method including a step of obtaining a film.
- the polyimide precursor and the resin composition containing the precursor according to the present invention a film having a high glass transition temperature and less warpage can be easily produced.
- a film excellent in adhesion and releasability with the substrate when the resin composition is applied to a substrate such as a glass substrate to form a film. can be easily formed.
- the polyimide precursor (polyamic acid) of the present invention has a structural unit represented by the following formula (1) including a structural unit represented by the following formula (2) (hereinafter also referred to as “structural unit (2)”).
- a structural unit (1) ”).
- the polyimide precursor of the present invention a film having a high glass transition temperature, a small residual stress, and a small amount of warpage can be easily produced. Moreover, according to the resin composition containing the polyimide precursor of the present invention, a film excellent in adhesion and releasability with the substrate when the resin composition is applied to a substrate such as a glass substrate to form a film. It can be formed easily.
- the polyimide precursor according to the present invention has a group selected from the group represented by the structural unit (2) and the following formulas (3) and (4)
- the polyimide precursor is represented by the following formulas (3) and (4).
- a microphase-separated structure having a rigid skeleton part containing a group selected from the group and a flexible skeleton part containing the structural unit (2), wherein the rigid skeleton part is a sea part and the flexible skeleton part is an island part It is thought to form. It is thought that the residual stress of a film
- the polyimide precursor of the present invention it is considered that a film in which the residual stress is small and the occurrence of warpage is suppressed can be obtained.
- m in the formula (2) is 3 or more, the flexibility of the flexible skeleton portion is further increased, and a microphase-separated structure is more easily formed, and the film remains. It is considered that the stress is further reduced.
- microphase separation means that islands made of flexible skeleton parts are dispersed in a size of about 1 nanometer to 1 micron in a sea part made of a rigid structural part.
- adheresion means, for example, when a film is formed on a substrate, or when a device for creating a wiring such as a metal is formed on the formed film.
- peelability means, for example, when peeling the film from the substrate (when applying force to peel the film from the substrate, etc.) The property that the film can be peeled off from the substrate with few peeling marks.
- warp is the roundness of the film judged visually
- residual stress is the film formed by applying the resin composition containing the polyimide precursor of the present invention on a substrate such as a glass substrate. This refers to the stress remaining in the film after the process, and is a measure of “warping” that can occur in the film. Specifically, it can be measured by the method described in the following examples.
- each R independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom
- each R 1 is independently a group selected from the group represented by the following formula (3)
- each R 2 independently represents a group selected from the group represented by the following formula (4).
- n represents a positive integer, preferably an integer of 1 to 2500.
- the monovalent organic group in R is preferably a monovalent organic group having 1 to 20 carbon atoms.
- C1-20 means “1 to 20 carbon atoms”. Similar descriptions in the present invention have similar meanings.
- Examples of the monovalent organic group having 1 to 20 carbon atoms in R include monovalent hydrocarbon groups having 1 to 20 carbon atoms.
- Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms.
- the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, t- A butyl group, a pentyl group, a hexyl group, etc. are mentioned.
- each R 1 independently represents a group selected from the group represented by the following formula (3).
- each R 3 independently represents an ether group, a thioether group, a ketone group, an ester group, a sulfonyl group, an alkylene group, an amide group or a siloxane group; a hydrogen atom; a halogen atom; an alkyl group; A group; a nitro group; a cyano group; or a sulfo group, wherein the hydrogen atom of the alkyl group and alkylene group may be substituted with a halogen atom, and D is an ether group, a thioether group, a ketone group, an ester group, a sulfonyl group
- An alkylene group, an amide group or a siloxane group each of a1 independently represents an integer of 1 to 3, each of a2 independently represents 1 or 2, each of a3 independently represents an integer of 1 to 4, Represents an integer of 0 to 3.
- R 3 is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, a nitro group, a cyano group or a sulfo group, preferably a hydrogen atom or an alkyl group.
- the alkyl group in R 3 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, specifically, methyl Group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group and the like. Any hydrogen atom in these alkyl groups may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
- examples of the alkylene group in R 3 and D include a methylene group or an alkylene group having 2 to 20 carbon atoms, and the hydrogen atom of the methylene group and alkylene group may be substituted with a halogen atom. good.
- the alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 2 to 10 carbon atoms, and is a dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylidene group, fluorene group. And a group in which any hydrogen atom in these alkylene groups is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
- D is preferably a sulfonyl group.
- E is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
- Examples of the group represented by the formula (3) include groups represented by the following (3-1) to (3-3).
- the group selected from the group represented by the formula (3) is a group selected from the group represented by the following formula (3 ′) to obtain a film with small residual stress and suppressed warpage. This is preferable.
- each R 3 is independently the same as R 3 in the formula (3).
- each R 2 independently represents a group selected from the group represented by the following formula (4).
- each R 4 independently represents a hydrogen atom or an alkyl group, the hydrogen atom of the alkyl group may be substituted with a halogen atom, and D represents an ether group, a thioether group, a ketone group, an ester group , A sulfonyl group, an alkylene group, an amide group or a siloxane group, each b independently represents 1 or 2, each c independently represents an integer of 1 to 3, and f represents an integer of 0 to 3.
- the alkyl group in R 4 respectively, in the formula (3), such as the same groups as the alkyl group can be mentioned in R 3, preferably a hydrogen atom R 4.
- D is preferably a sulfonyl group
- f is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
- the group selected from the group represented by the formula (4) is a group selected from the group represented by the following formula (4 ′) to obtain a film with small residual stress and suppressed warpage. Is preferable.
- the structural unit (1) includes a structural unit (2).
- the structural unit (2) may be contained in at least one group selected from the group consisting of a plurality of R 1 and R 2 in the structural unit (1). It may be contained in at least one group selected from the group consisting of a plurality of R 1 and R 2 .
- “at least one group selected from the group consisting of a plurality of R 1 and R 2 includes a structural unit represented by the following formula (2)” means that when n is 2 or more, R 1 and R 2 is present in each of two or more structural units (1), which means that at least one of the plurality of R 1 and R 2 includes a structural unit represented by the following formula (2).
- the polyimide precursor of the present invention contains the structural unit (2), according to the resin composition containing the precursor, it is possible to obtain a film in which the residual stress is small and the occurrence of warpage is suppressed.
- a plurality of R 5 s each independently represent a monovalent organic group having 1 to 20 carbon atoms, and m represents an integer of 3 to 200.
- examples of the monovalent organic group having 1 to 20 carbon atoms in R 5 include a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent alkoxy group having 1 to 20 carbon atoms. Can be mentioned.
- Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R 5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. It is done.
- the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t -Butyl group, pentyl group, hexyl group and the like.
- the cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples include a cyclopentyl group and a cyclohexyl group.
- the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
- Examples of the monovalent alkoxy group having 1 to 20 carbon atoms in R 5 include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, and a cyclohexyloxy group.
- the island part composed of the flexible skeleton part is excellent in affinity with the sea part composed of the rigid structural part, It is preferable because it is easy to disperse (uniform) (microphase separation) at a size of ⁇ 1 micron.
- the plurality of R 5 are preferably an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 12 carbon atoms.
- the resulting polyimide may not have a microphase separation structure. is there.
- microphase separation nano-dispersion of the skeleton part including the structural unit (2)
- a low linear expansion coefficient, low residual stress, etc. Can be obtained.
- the alkyl group (i) having 1 to 10 carbon atoms is preferably a methyl group, and the aryl group (ii) having 6 to 12 carbon atoms is preferably a phenyl group.
- the structural unit (2) is preferably contained in an amount of 5 to 40% by mass, preferably 5 to 23% by mass, and 8 to 22% by mass. More preferably, it is contained in an amount of 9.5 to 21% by mass.
- the proportion of the structural unit (2) contained in the polyimide precursor exceeds the above range, when the resin composition of the present invention was applied to a substrate such as a glass substrate and a coating film was formed, the substrate was formed from the substrate. It tends to be difficult to peel the coating film.
- the quantity of the structural unit (2) contained in a polyimide precursor is less than the said range, when the resin composition of this invention is apply
- M in the formula (2) is an integer of 3 to 200, preferably 10 to 200, more preferably 20 to 150, still more preferably 30 to 100, and particularly preferably 35 to 80.
- m is 2 or less, the polyimide obtained from the polyimide precursor may be difficult to form a microphase separation structure.
- m exceeds 200, the island portion composed of the skeleton part containing the structural unit (2) The size may exceed 1 ⁇ m, and the coating film may become cloudy or the mechanical strength may be reduced.
- the structural unit (1) in 100% by mass of the polyimide precursor, is preferably 60% by mass or more, more preferably 77% by mass or more, further preferably 79% by mass, and still more preferably 85%. To 100% by mass, more preferably 90 to 100% by mass, still more preferably 91 to 100% by mass, particularly preferably 92 to 100% by mass. When the proportion of the structural unit (1) is within the above range in the polyimide precursor, a film having a small residual stress and hardly warping can be obtained.
- 60% by mass or more of the structural unit (1) means that the structural unit —NH—R 1 —NH—, the structural unit —NH—R 1 —NH 2 , the structural unit— CO—R 2 (COOR) 2 —CO—, structural unit —CO—R 2 (COOR) 2 —COOH, structural unit (2), and structural unit — (Si (R 5 ) 2 —O) m —Si It means that the total of structural units including R 1 and R 2 such as (R 5 ) 2 -R 10 -R 11 and the structural unit (2) is 60% by mass or more.
- part of the structural unit (1) may be imidized.
- the polyimide precursor of the present invention has an ether group, a thioether group, a ketone group in the main chain of the precursor, in addition to the structural unit contained in the formula (1), depending on the desired use and film forming conditions.
- a structural unit derived from a monomer hereinafter also referred to as “monomer (I)”) containing at least one group selected from the group consisting of an ester group, a sulfonyl group, an alkylene group, an amide group and a siloxane group.
- structural unit (56) examples of the alkylene group include the same groups as the alkylene group for R 3 in the formula (3).
- the “structural unit included in the formula (1)” means the structural unit —NH—R 1 —NH—, the structural unit —NH—R 1 —NH 2 , or the structural unit —CO—R 2 (COOR) 2.
- —CO—, structural unit —CO—R 2 (COOR) 2 —COOH, structural unit (2), and structural unit — (Si (R 5 ) 2 —O) m —Si (R 5 ) 2 —R 10 R 1 a -R 11 or the like refers to a structural unit containing R 2 and structural units (2) (Note, R 1, R 2 and R and R 1, R 2 and R in the formula (1) are synonymous, R 5 has the same meaning as R 5 in the formula (2), R 10 and R 11 has the same meaning as R 10 and R 11 of the formula (7 ') and (8') in. ).
- the structural unit (56) does not contain the group represented by R 1 and R 2 in the structural unit (1) and the structural unit (2) contained in the main chain of the polyimide precursor. It refers to structural units derived from anhydrides and their derivatives or imino forming compounds.
- the main chain of the polyimide precursor means a chain containing R 1 or R 2 of the structural unit (1).
- —COOR in the structural unit (1) is not a main chain but a side chain. is there.
- the linear expansion coefficient of the obtained film increases, and a film that can be stretched as desired is obtained.
- the substrate containing Cu or the substrate containing Si is used.
- the blending amount of the structural unit (56) and / or the structural unit (2) may be changed according to these substrates.
- the coefficient of linear expansion of Cu is 16.8 ppm / K
- the polyimide precursor has a structural unit (56).
- the linear expansion coefficient of Si is 3 ppm / K, when the resin composition of the present invention is applied on a substrate made of Si, the polyimide precursor contains structural units (56).
- the linear expansion coefficient of chromium is 8.2 ppm / K
- the linear expansion coefficient of glass is 9 ppm / K
- the linear expansion coefficient of stainless steel SUS430 is 10.4 ppm / K
- the linear expansion coefficient of nickel is 12.8 ppm / K. Therefore, when the resin composition of the present invention is applied on a substrate composed of these, the polyimide precursor of the present invention contains 0 to 15% by mass of the structural unit (56) in 100% by mass of the polyimide precursor. Is preferred.
- each A independently represents an ether group (—O—), a thioether group (—S—), a ketone group (—C ( ⁇ O) —), an ester group (—COO—). ), A sulfonyl group (—SO 2 —), an alkylene group (—R 7 —), an amide group (—C ( ⁇ O) —NR 8 —) and a siloxane group (—Si (R 9 ) 2 —O—Si ( R 9 ) represents a group containing at least one group selected from the group consisting of 2- ), R 6 independently represents a hydrogen atom, a halogen atom, an alkyl group or a nitro group, and the hydrogen atom of the alkyl group represents a halogen atom It may be substituted with an atom, and each d independently represents an integer of 1 to 4.
- R 8 and R 9 each independently represent a hydrogen atom, an alkyl group or a halogen atom, and the hydrogen atom of this alkyl group may be substituted with a halogen atom.
- Examples of the alkyl group in R 6 , R 8 and R 9 include the same groups as the alkyl group in R 3 in the formula (3).
- the halogen atom is preferably a chlorine atom or a fluorine atom.
- A is preferably an ether group, and R 6 is preferably a hydrogen atom.
- examples of the alkylene group (—R 7 —) in A include the same groups as the alkylene group in R 3 in the formula (3).
- methylene Group, isopropylidene group, hexafluoroisopropylidene group and fluorene group are preferred.
- Examples of the compounds (5) and (6) include compounds described in the following compound groups (5-1) to (6-9).
- the polyimide precursor of the present invention includes the structural unit (56)
- the polyimide precursor preferably includes 0 to 15% by mass of the structural unit (56) in 100% by mass of the polyimide precursor, and more preferably 0 to 10%. Including mass%, more preferably 0 to 9 mass%, particularly preferably 0 to 8 mass%.
- the content of the structural unit (56) exceeds 15% by mass, the elastic modulus of the rigid structural part is lowered, and it is difficult to transfer residual stress to the flexible structural part. It may be easier.
- the polyimide precursor may include a structural unit (56), a polyimide precursor containing the structural unit (56), (I) wherein formula (1) in R 1 and R 2 in the structural unit (56) And (II) a structure in which the structural unit (56) is included in a portion other than the structural unit (1) in the polyimide precursor.
- the polyimide precursor is represented by the following formula (5A), for example.
- the structural unit (56) is preferably contained in an amount of 0 to 15% by mass in 100% by mass of the polyimide precursor” means between the two —NH— in the repeating unit n2 in 100% by mass of the polyimide precursor. It means 0 to 15% by mass of a structural unit represented by a structure sandwiched between (including —NH— at both ends).
- the structural unit (56) may be contained in at least one group selected from the group consisting of a plurality of R 1 and R 2 in the structural unit (1). It may be contained at the end of the unit (1).
- the weight average molecular weight (Mw) of the polyimide precursor of the present invention is preferably 10,000 to 1,000,000, more preferably 10,000 to 200,000, and further preferably 20,000 to 150,000.
- the number average molecular weight (Mn) is preferably from 5,000 to 10,000,000, more preferably from 5,000 to 500,000, particularly preferably from 20,000 to 200,000.
- the weight average molecular weight or number average molecular weight of the polyimide precursor is less than the lower limit, the strength of the coating film may be lowered. Furthermore, the linear expansion coefficient of the obtained film may be increased more than necessary.
- the weight average molecular weight or number average molecular weight of the polyimide precursor exceeds the above upper limit, the viscosity of the resin composition increases, so when the film is formed by applying the resin composition to a substrate such as a glass substrate. Since the amount of the polyimide precursor that can be blended in the resin composition is reduced, the film thickness accuracy such as the flatness of the obtained coating film may be deteriorated.
- the molecular weight distribution (Mw / Mn) of the polyimide precursor of the present invention is preferably 1 to 10, more preferably 2 to 5, and particularly preferably 2 to 4.
- the said weight average molecular weight, number average molecular weight, and molecular weight distribution are the values measured similarly to the following Example.
- the polyimide precursor of the present invention is preferably a component containing at least one acyl compound selected from the group consisting of (A) tetracarboxylic dianhydride and a reactive derivative thereof (hereinafter also referred to as “component (A)”). And (B) a component containing an imino forming compound (hereinafter also referred to as “component (B)”).
- component (A) tetracarboxylic dianhydride and a reactive derivative thereof
- component (B) a component containing an imino forming compound
- a polyimide precursor corresponding to the structure of the raw material compound to be used can be obtained, and a polyimide precursor having a structural unit derived from the compound in an amount corresponding to the amount of the raw material compound to be used is obtained. be able to.
- an acyl compound containing a structural unit represented by the above formula (2) (hereinafter also referred to as “compound (A-2)”) is used as the component (A), or the above formula (2) is used as the component (B). It is preferable to use an imino forming compound (hereinafter also referred to as “compound (B-2)”) containing a structural unit represented by In addition, both compound (A-2) and compound (B-2) can be used.
- the component (A) is at least one acyl compound selected from the group consisting of tetracarboxylic dianhydrides and reactive derivatives thereof.
- at least one compound selected from the group consisting of the above compound (A-2) and an acyl compound (A-1) other than the compound (A-2) is included.
- Examples of the acyl compound (A-1) include at least one compound selected from the group consisting of aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and reactive derivatives thereof.
- the sea part having a high elastic modulus is a compound having a group selected from the group represented by the above formula (4), particularly a compound having a group selected from the group represented by the above formula (4 ′). It is possible to disperse the flexible skeletal part in a very small 1 nanometer to 1 micron size (uniform) (micro phase separation structure), and efficiently absorb the stress generated in the film forming process by the flexible skeleton part.
- Tetracarboxylic dianhydride 1,2,4,5-cyclohexanetetracarboxylic dianhydride (PMDAH), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA), 2 , 2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride
- aromatic tetracarboxylic dianhydride is preferable, more preferably pyromellitic dianhydride, 3,3 ′, 4, '- biphenyltetracarboxylic acid dianhydride, 2,2', and 3,3'-biphenyltetracarboxylic dianhydride, particularly preferably pyromellitic dianhydride.
- acyl compound (A-1) a compound having no group selected from the group represented by the above formulas (4) and (4 ′) may be used.
- an aromatic tetracarboxylic dianhydride may be used.
- aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride is preferably used from the viewpoint of excellent transparency and good solubility in an organic solvent.
- aromatic tetracarboxylic dianhydrides are preferably used from the viewpoints of heat resistance, low linear expansion coefficient (dimensional stability), and low water absorption.
- the compounding amount of the compound (A-1) is not particularly limited, and may be 100% by mass when the total amount of all acyl compounds (component (A)) is 100% by mass. May contain the following compound (A-2) and / or compounds (6) and (6 ′) in an amount obtained by subtracting the preferred compounding amount of each of these compounds from 100% by mass.
- the compound (A-2) include a tetracarboxylic dianhydride having a structural unit represented by the above formula (2) and at least one acyl compound selected from reactive derivatives thereof.
- a compound represented by the following formula (7) hereinafter also referred to as “compound (7)”
- a compound represented by the following formula (7 ′) hereinafter also referred to as “compound (7 ′)”
- It is selected from the group consisting of a compound represented by the formula (8) (hereinafter also referred to as “compound (8)”) and a compound represented by the following formula (8 ′) (hereinafter also referred to as “compound (8 ′)”).
- compound (8 ′) hereinafter also referred to as “compound (8 ′)
- Examples of the reactive derivative include a tetracarboxylic acid having a structural unit represented by the above formula (2), an acid esterified product of the tetracarboxylic acid, and an acid chloride of the tetracarboxylic acid.
- the compounds (7) and / or (8) are synthesized.
- the compound (7 ′) and / or (8 ′) is preferably used when it is desired to synthesize a polyimide precursor contained in the terminal “*” of the structural unit (1).
- R 5 and m are each independently synonymous with R 5 and m in the formula (2).
- R 10 each independently represents a single bond or a divalent organic group having 1 to 20 carbon atoms.
- R 11 each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, In the above formula (2), the same groups as the monovalent organic group having 1 to 20 carbon atoms in R 5 can be used.
- Examples of the divalent organic group having 1 to 20 carbon atoms in R 10 include a methylene group, an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms. Is mentioned.
- the alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 2 to 10 carbon atoms, and examples thereof include a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
- the cycloalkylene group having 3 to 20 carbon atoms is preferably a cycloalkylene group having 3 to 10 carbon atoms, and examples thereof include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group.
- the arylene group having 6 to 20 carbon atoms is preferably an arylene group having 6 to 12 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.
- the compound (A-2) preferably has a number average molecular weight of 200 to 10,000, preferably 500 to 10,000, from the viewpoint of obtaining a film excellent in heat resistance (high glass transition temperature) and water resistance. More preferably, it is 500 to 6000.
- the amine value is preferably 100 to 5000, more preferably 250 to 5,000, and still more preferably 1000 to 3000.
- the polymerization degree m in the compounds (7), (7 ′), (8) and (8 ′) is the same as that in the formula (2), and the preferred range is also the same.
- R 5 is preferably a methyl group or a phenyl group, and at least one of a plurality of R 5 is preferably a phenyl group.
- At least one R 5 in the formulas (7), (7 ′), (8) and (8 ′) is not a phenyl group, the compatibility between the sea part and the island part deteriorates and the dispersion of the island part A film having a size exceeding 1 micron and inferior heat resistance and film strength may be obtained.
- Compound (A-2) can be used alone or in combination of two or more.
- the compound (A-2) when the total amount of all raw material compounds (component (A) + component (B)) is 100% by mass, the compound (A ⁇
- the blending amount of 2) is preferably 5 to 40% by mass, more preferably 5 to 23% by mass, and even more preferably, from the viewpoint of obtaining a film that is excellent in peelability from the substrate and hardly warps. It is 8 to 22% by mass, and particularly preferably 9.5 to 21% by mass.
- a preferable blending amount of the compound (A-2) is a case where the compound (B-2) is not used when synthesizing the polyimide precursor, and as a raw material when synthesizing the polyimide precursor.
- the total amount of the compound (A-2) and the compound (B-2) to be used is preferably a blending amount of the compound (A-2). It is preferable to make it to the same degree.
- the component (A) includes a compound (6) and / or a compound represented by the following formula (6 ′) (hereinafter referred to as “compound (“ 6 ′) ”) may also be included.
- compound (“ 6 ′) a compound represented by the following formula (6 ′)
- the compound (6 ′) when it is desired to synthesize a polyimide precursor containing the structural unit (56) in the main chain (excluding the terminal) of the polyimide precursor, it is preferable to use the compound (6), and the main chain terminal of the polyimide precursor is used.
- A has the same meaning as A in the formulas (5) and (6), and R 12 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
- R 12 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
- Examples of the monovalent organic group having 1 to 20 carbon atoms include the same groups as the monovalent organic group having 1 to 20 carbon atoms in R 5 in the above formula (2).
- the total amount of all raw material compounds (component (A) + component (B)) is 100% by mass.
- the compounding amount of the compound (6) and the compound (6 ′) is preferably 0 to 15% by mass, more preferably 0 to 10% by mass, from the viewpoint of obtaining a film that hardly warps.
- the content is preferably 0 to 9% by mass, particularly preferably 0 to 8% by mass.
- the preferable compounding amount of the compound (6) and the compound (6 ′) is a case where the compound (5) and / or the compound (5 ′) is not used when the polyimide precursor is synthesized.
- the compound (6) and / or the compound (6 ′) and the compound (5) and / or the compound (5 ′) are used as raw materials when the body is synthesized, the compound (6) and compound to be used It is preferable that the total amount of (6 ′), compound (5) and compound (5 ′) is the same as the preferred blending amount of compound (6) and / or compound (6 ′).
- the component (B) is an imino forming compound.
- the “imino forming compound” refers to a compound that reacts with the component (A) to form an imino (group), and specifically includes a diamine compound, a diisocyanate compound, a bis (trialkylsilyl) amino compound, and the like. Can be mentioned.
- the component (B) preferably contains at least one compound selected from the group consisting of the above compound (B-2) and imino forming compound (B-1) other than the compound (B-2).
- Examples of the imino-forming compound (B-1) include at least one compound selected from the group consisting of aromatic diamines and alicyclic diamines, and the like.
- the above formulas (3) and (3-1) to (3) ⁇ 3) A compound having a group selected from the group represented by the formula (3), particularly a compound having a group selected from the group represented by the formula (3 ′) is preferred.
- PDA p-phenylenediamine
- m-phenylenediamine 2,4-diaminotoluene
- benzidine 3,3′-dimethyl-4,4′-diaminobiphenyl (o- Trizine), 2,2′-dimethyl-4,4′-diaminobiphenyl (m-tolidine, mTB), 3,3′-diethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4 '-Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (TFMB), 3,3-dimethoxy-4,4-diaminobiphenyl, 2,2'-dichloro-4, 4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobi
- acyl compound (B-1) a compound having no group selected from the group represented by the above formulas (3), (3-1) to (3-3) and (3 ′) is further used.
- at least one compound selected from the group consisting of aromatic diamines, aliphatic diamines and alicyclic diamines may be used.
- aromatic diamine examples include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether (ODA), 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, and 3,7-diamino-dimethyldibenzo.
- aliphatic diamines examples include aliphatic diamines having 2 to 30 carbon atoms, and specific examples thereof include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-heptanediamine, Alkylene diamines such as 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine; oxydi (2-aminoethane) ), Oxydi (2-aminopropane), oxyalkylenediamine such as 2- (2-aminoethoxy) ethoxyaminoethane.
- These aliphatic diamines can be used alone or in combination of two or more.
- alicyclic diamine what has at least 1 alicyclic group in a molecule
- numerator can be used, and any group of a monocyclic ring, a polycyclic ring, and a condensed ring may be used as an alicyclic group.
- an alicyclic diamine having 4 to 30 carbon atoms is preferably used, and 4,4′-diaminodicyclohexylmethane (MBCHA), 4,4′-diamino-3,3′-dimethylcyclohexyl is used.
- MBCHA 4,4′-diaminodicyclohexylmethane
- the compounding amount of the compound (B-1) is not particularly limited, and may be 100% by mass when the total amount of all imide-forming compounds (component (B)) is 100% by mass.
- the following compounds (B-2) and / or compounds (5) and (5 ′) are contained in the components, they may be blended in an amount obtained by subtracting the preferred blending amount of each of these compounds from 100% by mass.
- the compound (B-2) is not particularly limited as long as it is an imino forming compound containing the structural unit (2), but is preferably a compound represented by the following formula (9) (hereinafter also referred to as “compound (9)”). And a compound represented by the following formula (9 ′) (hereinafter also referred to as “compound (9 ′)”).
- the compound (9 ′) In the case where it is desired to synthesize a polyimide precursor in which the structural unit (2) is contained in at least one group selected from the group consisting of a plurality of R 1 and R 2 in the structural unit (1), the compound (9 In the case where it is desired to synthesize a polyimide precursor contained in the terminal “*” of the structural unit (1), it is preferable to use the compound (9 ′).
- R 5 and m each independently have the same meaning as R 5 and m in the formula (2)
- R 10 each independently represents the formulas (7) and ( 8) during the same meaning as R 10 in
- R 11 is each independently the above formula (7 ') and (8') is synonymous with R 11 in.
- the flexible skeleton part can be finely dispersed in the nano-micron size in the sea part composed of the rigid skeleton part, and has excellent heat resistance (high glass transition temperature) and water resistance.
- the number average molecular weight is preferably 500 to 12,000, more preferably 1,000 to 8,000, and still more preferably 3,000 to 6,000.
- the amine value is preferably 250 to 6,000, more preferably 500 to 4,000, and further preferably 1,500 to 3,000.
- the polymerization degree m in the formulas (9) and (9 ′) is the same as that in the formula (2), and the preferred range is also the same.
- R 5 is preferably a methyl group or a phenyl group, and at least one of a plurality of R 5 is preferably a phenyl group.
- At least one R 5 in the formulas (9) and (9 ′) is not a phenyl group, the compatibility between the sea part and the island part deteriorates, and the dispersion size of the island part exceeds 1 micron, and the heat resistance In some cases, a film having poor film strength may be obtained.
- the imino-forming compound (B-2) may be used alone or in combination of two or more.
- the compound (B-2) When the compound (B-2) is contained in the component (B), the compound (B ⁇ ) is obtained when the total amount of all raw material compounds (component (A) + component (B)) is 100% by mass.
- the blending amount of 2) is preferably 5 to 40% by mass, more preferably 5 to 23% by mass, and even more preferably, from the viewpoint of obtaining a film that is excellent in peelability from the substrate and hardly warps. It is 8 to 22% by mass, and particularly preferably 9.5 to 21% by mass.
- the preferable compounding amount of the compound (B-2) is a case where the compound (A-2) is not used when the polyimide precursor is synthesized.
- the component (B) includes a compound represented by the compound (5) and / or the following formula (5 ′) (hereinafter referred to as “compound (“ 5 ') ”))) may be included.
- compound (“ 5 ') ” a compound represented by the compound (5) and / or the following formula (5 ′) (hereinafter referred to as “compound (“ 5 ') ”))) may be included.
- A represents the formula (5) and (6) in the same meaning as A
- R 12 is the formula (6 Formula (5)' is synonymous with R 12 in).
- the total amount of all raw material compounds (component (A) + component (B)) is 100% by mass.
- the compounding amount of the compound (5) and the compound (5 ′) is preferably 0 to 15% by mass, more preferably 0 to 10% by mass, from the viewpoint of obtaining a film that hardly warps.
- the content is preferably 0 to 9% by mass, particularly preferably 0 to 8% by mass.
- the preferable compounding quantity of the said compound (5) and compound (5 ') is a case where the said compound (6) and / or compound (6') are not used when a polyimide precursor is synthesize
- the component (A) and the component (B) are used as a ratio (charge ratio), and the molar ratio of the component (A) to the component (B) (component (A) / (B ) Component) is preferably reacted in the range of 0.8 to 1.2, more preferably in the range of 0.90 to 1.0.
- the molar ratio of the (A) acyl compound and the (B) imino-formation product is less than 0.8 equivalent or more than 1.2 equivalent, the molecular weight may be lowered and it may be difficult to form a film.
- the reaction between the component (A) and the component (B) is usually performed in an organic solvent.
- the organic solvent is preferably dehydrated.
- organic solvent it is preferable to use the following mixed solvent from the viewpoint of the ease of production of the resin composition of the present invention and the properties of the resulting film (haze, warpage, etc.).
- At least one (B) imino-forming compound is dissolved in an organic solvent, and then the resulting solution contains at least one ( A)
- a method of adding an acyl compound and stirring at a temperature of 0 to 100 ° C. for 1 to 60 hours may be mentioned.
- the total amount of the components (A) and (B) in the reaction solution is 3 to 60% by mass, preferably 5 to 40% by mass, more preferably 10 to 40% by mass, based on the total amount of the reaction solution. More preferably, it is 10 to 30% by mass.
- organic solvent examples include at least one solvent selected from the group consisting of ether solvents, ketone solvents, nitrile solvents, ester solvents, and amide solvents.
- the ether solvent is preferably an ether having 3 to 10 carbon atoms, and more preferably an ether having 3 to 7 carbon atoms.
- preferable ether solvents include mono- or dialkyl ethers such as ethylene glycol, diethylene glycol, and ethylene glycol monoethyl ether, cyclic ethers such as dioxane and tetrahydrofuran (THF), and aromatic ethers such as anisole. Can be mentioned. Of these, tetrahydrofuran is preferred.
- These ether solvents can be used singly or in combination of two or more.
- the ketone solvent is preferably a ketone having 3 to 10 carbon atoms, and more preferably a ketone having 3 to 6 carbon atoms from the viewpoint of boiling point and cost.
- cyclohexanone can obtain a resin composition excellent in drying property, productivity, etc., a solvent that is selectively evaporated during the following vacuum drying, and is almost completely removed from the coating film formed on the substrate. It is preferable from the point of being.
- ketone solvents can be used singly or in combination of two or more.
- the nitrile solvent is preferably a nitrile having 2 to 10 carbon atoms, and more preferably a nitrile having 2 to 7 carbon atoms.
- acetonitrile is preferable from the viewpoint of a low boiling point.
- These nitrile solvents can be used singly or in combination of two or more.
- the ester solvent is preferably an ester having 3 to 10 carbon atoms, and more preferably an ester having 3 to 6 carbon atoms.
- the amide solvent is preferably an amide having 3 to 10 carbon atoms, and more preferably an amide having 3 to 6 carbon atoms.
- an amide solvent having a boiling point equal to or higher than the primary drying temperature is obtained. From the viewpoint of the flatness of the film, etc., specifically, an amide solvent having a boiling point of 200 ° C. or higher is preferable.
- Preferred amide solvents include alkylamides such as N, N-dimethylformamide and N, N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone and the like. Examples thereof include cyclic amides. Among these, N-methyl-2-pyrrolidone and N, N-dimethylacetamide remain after vacuum drying or primary drying by evaporating the non-amide solvent, and at the time of secondary drying performed at 200 ° C. to 500 ° C.
- alkylamides such as N, N-dimethylformamide and N, N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone and the like. Examples thereof include cyclic amides. Among these, N-methyl-2-pyrrolidone and N, N-dimethylacetamide remain after vacuum drying or primary drying by evaporating the non-
- N-methyl-2-pyrrolidone is more preferable in consideration of environmental pollution and the like.
- These amide solvents can be used alone or in combination of two or more.
- the organic solvent it is possible to use a mixed solvent of an amide solvent and an ether solvent, a ketone solvent, a nitrile solvent, and an ester solvent selected from the group consisting of an ester solvent. It is preferable from the viewpoints of adhesion, peelability and residual stress of the coating film (film). Moreover, when the mixed solvent is used, a drying rate at the time of film formation is increased, the film quality is not deteriorated, a resin composition having excellent film productivity and a high polyimide precursor concentration can be obtained.
- the non-amide solvent is preferably a solvent that selectively evaporates during the following vacuum drying and is almost completely removed from the coating film formed on the substrate, and has a boiling point in the range of 40 to 200 ° C.
- a certain solvent is preferable, and a solvent in the range of 100 to 170 ° C. is more preferable.
- the boiling point means the boiling point in the atmosphere at 1 atm.
- the non-amide solvent preferably contains at least one organic solvent selected from the group consisting of ketone solvents and nitrile solvents. Since these solvents have relatively high polarity, there is a tendency that a resin composition having excellent storage stability can be obtained.
- the mixed solvent is a mixed solvent of N-methyl-2-pyrrolidone and cyclohexanone, a mixed solvent of N, N-dimethylacetamide and cyclohexanone, N-methyl-2-pyrrolidone and A mixed solvent with acetonitrile is preferable, and a mixed solvent of N-methyl-2-pyrrolidone and cyclohexanone is particularly preferable.
- a mixed solvent of N, N-dimethylacetamide and tetrahydrofuran is preferable from the viewpoint of preventing clouding of the obtained film.
- the mixed solvent preferably contains 5 to 95 parts by mass, more preferably 25 to 95 parts by mass of the amide-based solvent with respect to 100 parts by mass of the mixed solvent. More preferably, it contains 65 parts by mass. Further, the mixed solvent particularly preferably contains 40 to 60 parts by mass of the amide solvent with respect to 100 parts by mass of the mixed solvent.
- the mixed solvent contains the amide solvent in this amount, the mixed solvent is dried. Not only does it become a resin composition with high speed and excellent productivity, but it also has excellent film quality characteristics such as cloudiness and tensile strength, storage stability, etc., and excellent adhesion to the substrate and peelability. Obtainable.
- the amount of the amide solvent is less than 5 parts by mass, the polyimide precursor may not be dissolved and a resin composition may not be obtained.
- the amount of the amide solvent exceeds 95 parts by mass, The drying speed at the time of forming becomes slow, and productivity may be inferior.
- the resin composition according to the present invention preferably contains the polyimide precursor of the present invention and an organic solvent.
- the organic solvent is preferably the mixed solvent.
- the resin composition containing the polyimide precursor of the present invention a film having a high glass transition temperature, a small residual stress, and little warpage can be easily produced in a short time with high productivity. Moreover, according to the said resin composition, when apply
- the resin composition contains the polyimide precursor obtained by the above reaction as a solid component. Can be obtained by re-dissolving in an organic solvent.
- a solution containing the polyimide precursor and an organic solvent is poured into a poor solvent for the polyimide precursor such as methanol or isopropanol to precipitate the polyimide precursor, and is filtered, washed and dried.
- a poor solvent for the polyimide precursor such as methanol or isopropanol
- blend additives such as antioxidant, a ultraviolet absorber, and surfactant, in the said resin composition in the range which does not impair the objective of this invention.
- the viscosity of the resin composition is usually 500 to 500,000 mPa ⁇ s, preferably 1,000 to 50,000 mPa ⁇ s, although it depends on the molecular weight and concentration of the polyimide precursor. If it is less than 500 mPa ⁇ s, the retention of the resin composition during film formation is poor, and the resin composition may flow down from the substrate. On the other hand, if it exceeds 500,000 mPa ⁇ s, the viscosity is too high, and it becomes difficult to adjust the film thickness, which may make it difficult to form the film.
- the viscosity of the resin composition is a value measured at 25 ° C. in the atmosphere using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., viscometer MODEL RE100).
- the polyimide precursor concentration in the resin composition is preferably adjusted so that the viscosity of the resin composition is in the above range, and is usually 3 to 60% by mass, preferably 5%, depending on the molecular weight of the polyimide precursor. -40% by mass, more preferably 10-40% by mass, particularly preferably 10-30% by mass. If it is less than 3% by mass, problems such as difficulty in increasing the film thickness and poor productivity, easy formation of pinholes, and poor film thickness accuracy such as flatness may occur. On the other hand, if it exceeds 60% by mass, the viscosity of the resin composition may be too high to form a film, and a film lacking in surface smoothness may be obtained.
- the resin composition can be applied onto a substrate using a slit coating method that is excellent in productivity and the like. A film having excellent thickness accuracy and the like can be formed in a short time with high productivity.
- ⁇ Film formation method As a method for forming a film (polyimide film) according to the present invention, a step of coating the resin composition on a substrate to form a coating film, and a step of removing the organic solvent from the coating film by evaporation And the like methods.
- a roll coating method As a method of forming a coating film by applying the resin composition on a substrate, a roll coating method, a gravure coating method, a spin coating method, a slit coating method, a dipping method and a doctor blade, a die, a coater, a spray, a brush, The method etc. which apply
- the thickness of the coating film is appropriately selected depending on the desired application and is not particularly limited. For example, it is 1 to 500 ⁇ m, preferably 1 to 450 ⁇ m, more preferably 2 to 250 ⁇ m, and still more preferably. The thickness is 2 to 150 ⁇ m, particularly preferably 5 to 125 ⁇ m.
- the substrate includes polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polybutylene terephthalate (PBT) film, nylon 6 film, nylon 6,6 film, polypropylene film, polytetrafluoroethylene belt, silicon wafer , Glass wafers, glass substrates (including non-alkali glass substrates), Cu substrates and SUS plates.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PBT polybutylene terephthalate
- nylon 6 film nylon 6,6 film
- polypropylene film polytetrafluoroethylene belt
- silicon wafer Glass wafers, glass substrates (including non-alkali glass substrates), Cu substrates and SUS plates.
- the resin composition of the present invention is excellent in adhesion and peelability to these substrates, it is possible to form a thin film on a silicon wafer, glass wafer, glass substrate, Cu substrate and SUS plate.
- the step of removing the organic solvent by evaporating the organic solvent from the coating film can be performed by vacuum drying or heating the coating film.
- the heating condition may be that the organic solvent evaporates and the polyimide precursor of the present invention is imidized, and may be appropriately determined according to the substrate and the polyimide precursor.
- the heating temperature is 60 ° C. to 350 ° C. It is preferable.
- the heating time is preferably 10 minutes to 5 hours.
- heating may be performed in two or more stages. Specifically, for example, after drying for 10 minutes to 2 hours at a temperature of 60 to 250 ° C., heating is further performed at 160 to 350 ° C., preferably 200 to 350 ° C., more preferably 230 to 270 ° C. for further 10 minutes to 2 hours. And so on. Moreover, you may dry under reduced pressure as needed.
- the heating atmosphere is not particularly limited, but is preferably in the air or in an inert gas atmosphere, and particularly preferably in an inert gas atmosphere.
- the inert gas include nitrogen, argon, helium and the like from the viewpoint of colorability, and nitrogen is preferable.
- the said coating may dry the coating film formed on the said board
- the step of removing the mixed solvent from the coating film by evaporating it is preferable to perform vacuum drying before the heating.
- vacuum drying since the solvent can be easily removed from the coating film without blowing hot air or the like to the coating film formed on the substrate, a film having excellent flatness can be obtained. Since it is fixed from the surface, a film having excellent flatness and uniform film quality can be formed with good reproducibility.
- the pressure in the apparatus is decreased until the pressure (decompression degree) in the apparatus containing the coating film is 760 mmHg or less, preferably 100 mmHg or less, more preferably 50 mmHg or less, and particularly preferably 1 mmHg or less. Is desirable. If it exceeds 760 mmHg, the evaporation rate when the solvent is further removed from the coating film after vacuum drying is remarkably slowed, and the productivity may be deteriorated.
- the vacuum drying is desirably performed for 0 to 60 minutes, preferably 0 to 30 minutes, more preferably 0 to 20 minutes, when the pressure drops to a predetermined value.
- the obtained film can be used after being peeled off from the substrate, or can be used as it is without being peeled off.
- the thickness of the film is appropriately selected according to the desired application, but is preferably 1 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, still more preferably 10 to 50 ⁇ m, and particularly preferably 20 to 40 ⁇ m.
- the elastic modulus of the film obtained from the resin composition of the present invention is 5 to 20 GPa, particularly preferably 5 to 10 GPa. If the elastic modulus of the film is less than 5 GPa, the film tends to be stretched, but the residual stress becomes high and warping may occur. If it exceeds 20 GPa, the film becomes brittle and may cause a problem of cracking in the film during handling. .
- the elongation of the film is appropriately selected according to the desired application, but is 2% or more, preferably 4% or more, particularly preferably 10% or more. If the elongation of the film is less than 2%, there may be a problem that the film is cracked during handling.
- the glass transition temperature of the film is 250 ° C. or higher, preferably 350 ° C. or higher, particularly preferably 450 ° C. or higher. If the glass transition temperature is less than 250 ° C., it is heated to 250 ° C. or more at the time of solder reflow process or device creation. Therefore, when the coating film is used for such applications, the film may be deformed. is there.
- Suitable applications of the film include flexible substrates such as flexible printed circuit boards and flexible display substrates, semiconductor elements, thin film transistor type liquid crystal display elements, magnetic head elements, integrated circuit elements, solid-state imaging elements, mounting substrates, and other electronic components.
- Examples thereof include an insulating film used and films for various capacitors. That is, these electronic components are generally provided with an interlayer insulating film, a planarizing insulating film, and a surface protecting insulating film (overcoat film, passivation film, etc.) in order to insulate between wirings arranged in layers. Therefore, it can be suitably used as these insulating films.
- the film can be suitably used as a light guide plate, a polarizing plate, a display film, an optical disc film, a transparent conductive film, a waveguide plate, or the like.
- the film is excellent in adhesion and peelability to the glass substrate, so there is no need to provide an adhesive layer or the like between the film and the substrate, and the number of steps when creating a flexible substrate can be reduced. There is sex.
- Glass transition temperature (Tg) Using the films obtained in Examples 1 to 13 or Comparative Examples 1 and 2 below, the glass transition temperature of polyimide was set to 20 ° C./min using a Rigaku 8230 DSC measuring apparatus. It was measured.
- Weight average molecular weight The weight average molecular weight of the polyamic acids obtained in the following Examples 1 to 13 or Comparative Examples 1 and 2 was measured using an HLC-8020 GPC apparatus manufactured by TOSOH. As the solvent, N-methyl-2-pyrrolidone (NMP) to which lithium bromide and phosphoric acid were added was used, and the molecular weight in terms of polystyrene was determined at a measurement temperature of 40 ° C.
- NMP N-methyl-2-pyrrolidone
- mTB 2,2′-dimethyl-4,4′-diaminobiphenyl
- component (B) 2,2′-dimethyl-4,4′-diaminobiphenyl (hereinafter also referred to as “mTB”) 6 as a component (B) in a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube 6 0.07 g (28.6 mmol) and 2.57 g (0.6 mmol) of both terminal amino-modified methylphenyl silicone (X22-1660B-3) were added.
- mTB 2,2′-dimethyl-4,4′-diaminobiphenyl
- the obtained polyamic acid solution was applied on a non-alkali glass support with a spin coater (rotated at 300 rpm for 5 seconds and then rotated at 1100 rpm for 10 seconds), then at 70 ° C. for 30 minutes, and then at 120 ° C.
- a coating film was obtained by drying for 30 minutes.
- the coating film obtained as the imidization step was further dried at 250 ° C. for 2 hours, and then peeled from the alkali-free glass support to obtain a polyimide film having a film thickness of 30 ⁇ m (0.03 mm).
- membrane were evaluated. The results are shown in Table 1.
- Example 2 In a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser tube, both 2,2′-dimethyl-4,4′-diaminobiphenyl (6.07 g, 28.6 mmol) as component (B) 2.57 g (0.6 mmol) of terminal amino-modified methylphenyl silicone (X22-1660B-3) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform.
- the polyimide film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a film (film) having a thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 3 In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, both 6.68 g (31.4 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B) were added. 1.40 g (0.3 mmol) of terminal amino-modified methylphenyl silicone (X22-1660B-3) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide and 20 ml of tetrahydrofuran were added and stirred until uniform. To the resulting solution, 6.93 g (31.8 mmol) of pyromellitic dianhydride as component (A) was added at room temperature, and stirring was continued at that temperature for 24 hours to obtain a composition (polyamic acid solution). .
- a polyimide-based film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 4 In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 6.04 g (28.4 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl was added as component (B). 2.36 g (1.8 mmol) of terminal amino-modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-9409, number average molecular weight 1,300) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the obtained solution, 6.60 g (30.3 mmol) of pyromellitic dianhydride as component (A) was added at room temperature, and stirring was continued at that temperature for 24 hours to obtain a composition (polyamic acid solution). .
- a polyimide-based film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 5 In a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser tube, both 6.41 g (30.2 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B) were added. 1.85 g (0.6 mmol) of terminal amino-modified methyl phenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-161B, number average molecular weight 3,000) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the resulting solution, 6.73 g (30.9 mmol) of pyromellitic dianhydride as component (A) was added at room temperature, and stirring was continued at that temperature for 24 hours to obtain a composition (polyamic acid solution). .
- a polyimide-based film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 6 In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, both 6.29 g (29.6 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B) were added. 1.98 g (1.2 mmol) of terminal amino-modified methyl phenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-161A, number average molecular weight 1,600) was added.
- a polyimide-based film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 7 Add 6.65 g (31.3 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B) to a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser. did. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the resulting solution, 6.15 g (28.2 mmol) of pyromellitic dianhydride and 2.19 g (3.1 mmol) of acid anhydride-modified methylsilicone (DMS-Z21) at room temperature were used as component (A). In addition, stirring was continued at that temperature for 24 hours to obtain a composition (polyamic acid solution).
- DMS-Z21 acid anhydride-modified methylsilicone
- a polyimide-based film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 8 In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, both 6.59 g (31.0 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B) were added. 1.38 g (0.3 mmol) of terminal amino-modified methylphenyl silicone (X22-1660B-3) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform.
- component (A) 1,2,4,5-cyclohexanetetracarboxylic dianhydride (hereinafter also referred to as “PMDAH”) as component (A) was added at room temperature, and the temperature was maintained. Then, stirring was continued for 24 hours to obtain a composition (polyamic acid solution).
- PMDAH 1,2,4,5-cyclohexanetetracarboxylic dianhydride
- a polyimide-based film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 9 2.87 g (25.1 mmol) of 1,4-diaminocyclohexane (hereinafter also referred to as “CHDA”) as component (B) was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube. 3.42 g (0.8 mmol) of both-end amino-modified methylphenyl silicone (X22-1660B-3) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform.
- CHDA 1,4-diaminocyclohexane
- component (A) diphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter also referred to as “s-BPDA”) as component (A) was added at room temperature. In addition, stirring was continued at that temperature for 24 hours to obtain a composition (polyamic acid solution).
- s-BPDA 4,4′-tetracarboxylic dianhydride
- a polyimide-based film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 10 In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 2.99 g (26.2 mmol) of 1,4-diaminocyclohexane as component (B) and amino-modified methylphenyl silicone (X22) ⁇ 9409) 2.56 g (2.0 mmol) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform.
- a polyimide-based film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- TFMB 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl
- component (B) 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl
- TFMB 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl
- CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
- a polyimide-based film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 12 In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, both 6.34 g (29.9 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B) were added. 2.68 g (0.6 mmol) of terminal amino-modified methylphenyl silicone (X22-1660B-3) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform.
- a polyimide-based film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 13 In a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen introduction tube, and cooling tube, both 2.78 '(22.3 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl as component (B) were added. 5.16 g (1.2 mmol) of terminal amino-modified methylphenyl silicone (X22-1660B-3) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the obtained solution, 5.11 g (23.4 mmol) of pyromellitic dianhydride as component (A) was added at room temperature, and stirring was continued at that temperature for 24 hours to obtain a composition (polyamic acid solution). .
- a polyimide-based film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 14 The polyamic acid solution (composition) prepared in Example 1 was cast and applied on a non-alkali glass support with a spin coater so that the thickness of the resulting coating film was 25 ⁇ m, and 30 minutes at 70 ° C. Then, it was dried at 120 ° C. for 30 minutes to obtain a coating film. Then, the coating film obtained as a cyclization (imidation) step was further dried at 250 ° C. for 2 hours.
- a transparent conductive film (element) was formed on the surface of the obtained coating film under an argon atmosphere at 230 ° C. for 5 minutes.
- ITO was used as a target material.
- the specific resistance value of the obtained substrate was 2 ⁇ 10 ⁇ 4 ( ⁇ ⁇ cm).
- membrane was obtained by peeling the polyimide-type film
- substrate was peelable from the support body, and the curvature was not observed.
- a polyimide-based film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- BAPP 2,2′-bis [4- (4-aminophenoxy) phenyl] propane
- ODPA 4,4′-oxydiphthalic dianhydride
- a polyimide-based film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were measured using an HLC-8220 GPC apparatus manufactured by TOSOH ( Guard column: TSK guard column ALPHA column: TSKgel ALPHA-M, developing solvent: NMP).
- the residual stress of the coating film is preferably 10 MPa or less, and more preferably 5 MPa or less.
- the first drying before the polyimide precursor peak area ratio (peak area peak area / 1520 cm -1 of 990 cm -1) and their peak area ratio after secondary drying were measured, imidization using the following equation The rate was calculated.
- Imidization ratio (%) (peak area ratio after primary / secondary drying / peak area ratio before primary drying) ⁇ 100
- Example 15 In a three-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirring blade, under nitrogen flow at 25 ° C., 45.23099 g (0.21306 mol) of m-tolidine (mTB), both ends amino-modified side chain phenyl methyl type silicone X- 22-1660B-3 [9.4694 g (0.0021521 mol)], 307 g of dehydrated N-methyl-2-pyrrolidone (NMP) and 307 g of dehydrated cyclohexanone (CHN) so that the concentration of the polyimide precursor in the varnish was 14%. Was added and stirred for 10 minutes until mTB and X-22-1660B-3 were completely dissolved.
- NMP dehydrated N-methyl-2-pyrrolidone
- CHN dehydrated cyclohexanone
- a glass substrate (horizontal: 300 mm x vertical: 350 mm x thickness: 0.7 mm) is fixed to a control coater stand installed so as to be perpendicular to gravity, and the gap interval is set so that the film thickness becomes 30 ⁇ m after secondary drying.
- the thickness was set to 405 ⁇ m, and 12 g of varnish was cast on the center of the glass substrate so as to form a coating film of width: 200 mm ⁇ length: 220 mm.
- Table 2 shows the results of sampling and physical properties evaluation of the coating after primary drying.
- secondary drying was performed at 300 ° C. for 1 hour. The evaluation results are shown in Table 2.
- Tg was 450 ° C. or higher, which was excellent in heat resistance, transparency, smoothness, and a tough film having a low coefficient of linear expansion.
- the obtained coating film has a high drying speed and is excellent in adhesion to a glass substrate during primary drying and secondary drying, and the film obtained after secondary drying is excellent in peelability from the glass substrate. It was.
- Example 16 The same operation as in Example 15 was carried out except that the amounts of mTB, X-22-1660B-3 and PMDA used were changed as shown in Table 2. The results are shown in Table 2.
- a tough film with excellent heat resistance, transparency, and smoothness without warping could be obtained.
- the obtained coating film has a high drying speed and is excellent in adhesion to a glass substrate during primary drying and secondary drying, and the film obtained after secondary drying is excellent in peelability from the glass substrate. It was.
- Example 17 The same operation as in Example 15 was carried out except that the amounts of mTB, X-22-1660B-3 and PMDA used were changed as shown in Table 2. The results are shown in Table 2.
- a tough film with excellent heat resistance, transparency, and smoothness without warping could be obtained.
- the obtained coating film has a high drying speed and is excellent in adhesion to a glass substrate during primary drying and secondary drying, and the film obtained after secondary drying is excellent in peelability from the glass substrate. It was.
- Example 18 In Example 15, instead of mTB45.23099 g, 32.578 g of mTB and 7.8760 g of 4,4′-diaminodiphenyl ether (ODA) were used, and the amounts of X-22-1660B-3 and PMDA used were as shown in Table 2. The same operation as in Example 15 was performed except for the change. The results are shown in Table 2.
- the film was improved in elongation, and it was excellent in heat resistance, transparency and smoothness, and a warp-free film could be obtained.
- the obtained coating film has a high drying speed and is excellent in adhesion to a glass substrate during primary drying and secondary drying, and the film obtained after secondary drying is excellent in peelability from the glass substrate. It was.
- a polyimide precursor having the structural unit (1) was confirmed in the obtained varnish.
- a tough film having excellent heat resistance, transparency and smoothness, having no warpage and having a low coefficient of linear expansion could be obtained.
- the obtained coating film has a high drying speed and is excellent in adhesion with a glass substrate during primary drying and secondary drying, and the film obtained after secondary drying is excellent in peelability from the glass substrate. It was.
- Example 20 The same operation as in Example 18 was carried out except that the amounts of mTB, X-22-1660B-3, ODA and PMDA used were changed as shown in Table 2. The results are shown in Table 2.
- the obtained coating film has a high drying speed and is excellent in adhesion to a glass substrate during primary drying and secondary drying, and the film obtained after secondary drying is excellent in peelability from the glass substrate. It was.
- Example 15 was carried out in the same manner as Example 15 except that X-22-1660B-3 was not used and the amounts of mTB and PMDA used were changed as shown in Table 2. The results are shown in Table 2.
- the varnish obtained in Comparative Example 3 had a slow drying rate. Moreover, the residual stress increased after secondary drying, and a large warp occurred after the film was peeled from the glass substrate.
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Abstract
Description
すなわち、本発明は、以下の[1]~[12]を提供するものである。 As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a polyimide precursor (polyamic acid) having a specific structural unit, and the present invention has been completed. .
That is, the present invention provides the following [1] to [12].
本発明のポリイミド前駆体(ポリアミック酸)は、下記式(2)で表わされる構造単位(以下「構造単位(2)」ともいう。)を含む下記式(1)で表わされる構造単位(以下「構造単位(1)」ともいう。)を有する。 ≪Polyimide precursor≫
The polyimide precursor (polyamic acid) of the present invention has a structural unit represented by the following formula (1) including a structural unit represented by the following formula (2) (hereinafter also referred to as “structural unit (2)”). A structural unit (1) ”).
炭素数1~20の炭化水素基としては、炭素数1~20のアルキル基等が挙げられる。 Examples of the monovalent organic group having 1 to 20 carbon atoms in R include monovalent hydrocarbon groups having 1 to 20 carbon atoms.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms.
これらのアルキル基における任意の水素原子は、フッ素原子、塩素原子、臭素原子またはヨウ素原子で置換されてもよい。 In the above formula (3), the alkyl group in R 3 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, specifically, methyl Group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group and the like.
Any hydrogen atom in these alkyl groups may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
また、本発明のポリイミド前駆体は、構造単位(1)の一部がイミド化していてもよい。 In addition, in 100% by mass of the polyimide precursor, 60% by mass or more of the structural unit (1) means that the structural unit —NH—R 1 —NH—, the structural unit —NH—R 1 —NH 2 , the structural unit— CO—R 2 (COOR) 2 —CO—, structural unit —CO—R 2 (COOR) 2 —COOH, structural unit (2), and structural unit — (Si (R 5 ) 2 —O) m —Si It means that the total of structural units including R 1 and R 2 such as (R 5 ) 2 -R 10 -R 11 and the structural unit (2) is 60% by mass or more. (Note, R 1, R 2 and R have the same meanings as R 1, R 2 and R in the formula (1), R 5 has the same meaning as R 5 in the formula (2), R 10 and R 11 has the same meaning as R 10 and R 11 in the following formulas (7 ′) and (8 ′).)
In the polyimide precursor of the present invention, part of the structural unit (1) may be imidized.
前記アルキレン基としては、前記式(3)中、R3におけるアルキレン基と同様の基等が挙げられる。 The polyimide precursor of the present invention has an ether group, a thioether group, a ketone group in the main chain of the precursor, in addition to the structural unit contained in the formula (1), depending on the desired use and film forming conditions. , A structural unit derived from a monomer (hereinafter also referred to as “monomer (I)”) containing at least one group selected from the group consisting of an ester group, a sulfonyl group, an alkylene group, an amide group and a siloxane group. (Hereinafter also referred to as “structural unit (56)”).
Examples of the alkylene group include the same groups as the alkylene group for R 3 in the formula (3).
なお、前記重量平均分子量、数平均分子量および分子量分布は、下記実施例と同様に測定した値である。 The molecular weight distribution (Mw / Mn) of the polyimide precursor of the present invention is preferably 1 to 10, more preferably 2 to 5, and particularly preferably 2 to 4.
In addition, the said weight average molecular weight, number average molecular weight, and molecular weight distribution are the values measured similarly to the following Example.
本発明のポリイミド前駆体は、好ましくは、(A)テトラカルボン酸二無水物およびこの反応性誘導体からなる群より選ばれる少なくとも1種のアシル化合物を含む成分(以下「(A)成分」ともいう。)と、(B)イミノ形成化合物を含む成分(以下「(B)成分」ともいう。)とを反応させることで得られる。但し、前記ポリイミド前駆体の合成の際には、前記構造単位(2)を含む化合物を用いることが好ましい。 <Synthesis Method of Polyimide Precursor>
The polyimide precursor of the present invention is preferably a component containing at least one acyl compound selected from the group consisting of (A) tetracarboxylic dianhydride and a reactive derivative thereof (hereinafter also referred to as “component (A)”). And (B) a component containing an imino forming compound (hereinafter also referred to as “component (B)”). However, in the synthesis of the polyimide precursor, it is preferable to use a compound containing the structural unit (2).
(A)成分は、テトラカルボン酸二無水物およびこれらの反応性誘導体からなる群より選ばれる少なくとも1種のアシル化合物である。好ましくは、上記化合物(A-2)、および化合物(A-2)以外のアシル化合物(A-1)からなる群より選ばれる少なくとも1種の化合物を含む。 [(A) component]
The component (A) is at least one acyl compound selected from the group consisting of tetracarboxylic dianhydrides and reactive derivatives thereof. Preferably, at least one compound selected from the group consisting of the above compound (A-2) and an acyl compound (A-1) other than the compound (A-2) is included.
4,4’-オキシジフタル酸二無水物(OPDA)、3,3’,4,4’-ジメチルジフェニルシランテトラカルボン酸二無水物、3,3’,4,4’-テトラフェニルシランテトラカルボン酸二無水物、2,3,4,5-フランテトラカルボン酸二無水物、4,4’-ビス(3,4-ジカルボキシフェノキシ)ジフェニルスルフィド二無水物、4,4’-ビス(3,4-ジカルボキシフェノキシ)ジフェニルスルホン二無水物、4,4’-ビス(3,4-ジカルボキシフェノキシ)ジフェニルプロパン二無水物、3,3’,4,4’-パーフルオロイソプロピリデンジフタル酸二無水物、ビス(フタル酸)フェニルホスフィンオキサイド二無水物、p-フェニレン-ビス(トリフェニルフタル酸)二無水物、m-フェニレン-ビス(トリフェニルフタル酸)二無水物、ビス(トリフェニルフタル酸)-4,4’-ジフェニルエーテル二無水物、ビス(トリフェニルフタル酸)-4,4’-ジフェニルメタン二無水物などの芳香族テトラカルボン酸二無水物、およびこれらの反応性誘導体を挙げることができる。
これらの化合物は1種を単独であるいは2種以上を組み合わせて用いることができる。 Specific examples include butanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4, 5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan -1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7 -Aliphatic tetracarboxylic dianhydrides such as ene-2,3,5,6-tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydrides, and reactive derivatives thereof;
4,4′-oxydiphthalic dianhydride (OPDA), 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic acid Dianhydride, 2,3,4,5-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3 4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic acid Dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) ) Aromatic tetracarboxylic dianhydrides such as dianhydrides, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydrides, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydrides And reactive derivatives thereof.
These compounds can be used alone or in combination of two or more.
(B)成分は、イミノ形成化合物である。ここで、「イミノ形成化合物」とは、(A)成分と反応してイミノ(基)を形成する化合物をいい、具体的には、ジアミン化合物、ジイソシアネート化合物、ビス(トリアルキルシリル)アミノ化合物等を挙げることができる。 [Component (B)]
The component (B) is an imino forming compound. Here, the “imino forming compound” refers to a compound that reacts with the component (A) to form an imino (group), and specifically includes a diamine compound, a diisocyanate compound, a bis (trialkylsilyl) amino compound, and the like. Can be mentioned.
m=(数平均分子量-両末端基(アミノプロピル基)の分子量116.2)/(74.15×メチル基のmol%×0.01+198.29×フェニル基のmol%×0.01) Specifically, as the compound (B-2), both terminal amino-modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd .; X22-1660B-3 (number average molecular weight 4,400, degree of polymerization m = 41, phenyl group: methyl) Group = 25: 75 mol%), X22-9409 (number average molecular weight 1,300)), both-end amino-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd .; X22-161A (number average molecular weight 1,600, polymerization degree m = 20) ), X22-161B (number average molecular weight 3,000, polymerization degree m = 39), KF8012 (number average molecular weight 4400, polymerization degree m = 58), manufactured by Toray Dow Corning; BY16-835U (number average molecular weight 900, polymerization degree) m = 11)), etc. The imino-forming compound (B-2) may be used alone or in combination of two or more. The degree of polymerization m can be calculated by, for example, the following formula: (A compound in which, when both ends are aminopropyl groups, all of R 5 in the formula (2) are methyl groups or phenyl groups. in the case of)
m = (number average molecular weight−molecular weight of both terminal groups (aminopropyl group) 116.2) / (74.15 × mol% of methyl group × 0.01 + 198.29 × mol% of phenyl group × 0.01)
なお、これらエーテル系溶媒は、1種単独であるいは2種以上を組み合わせて用いることができる。 The ether solvent is preferably an ether having 3 to 10 carbon atoms, and more preferably an ether having 3 to 7 carbon atoms. Specific examples of preferable ether solvents include mono- or dialkyl ethers such as ethylene glycol, diethylene glycol, and ethylene glycol monoethyl ether, cyclic ethers such as dioxane and tetrahydrofuran (THF), and aromatic ethers such as anisole. Can be mentioned. Of these, tetrahydrofuran is preferred.
These ether solvents can be used singly or in combination of two or more.
なお、これらケトン系溶媒は、1種単独であるいは2種以上を組み合わせて用いることができる。 The ketone solvent is preferably a ketone having 3 to 10 carbon atoms, and more preferably a ketone having 3 to 6 carbon atoms from the viewpoint of boiling point and cost. Specific preferred ketone solvents include acetone (bp = 57 ° C.), methyl ethyl ketone (bp = 80 ° C.), methyl-n-propyl ketone (bp = 105 ° C.), methyl-iso-propyl ketone (bp = 116). ° C), diethylketone (bp = 101 ° C), methyl-n-butylketone (bp = 127 ° C), methyl-iso-butylketone (bp = 118 ° C), methyl-sec-butylketone (bp = 118 ° C), methyl- Dialkyl ketones such as tert-butyl ketone (bp = 116 ° C.), cyclic ketones such as cyclopentanone (bp = 130 ° C.), cyclohexanone (CHN, bp = 156 ° C.), cycloheptanone (bp = 185 ° C.), etc. Can be mentioned. Among these, cyclohexanone can obtain a resin composition excellent in drying property, productivity, etc., a solvent that is selectively evaporated during the following vacuum drying, and is almost completely removed from the coating film formed on the substrate. It is preferable from the point of being.
These ketone solvents can be used singly or in combination of two or more.
なお、これらニトリル系溶媒は、1種単独であるいは2種以上を組み合わせて用いることができる。 The nitrile solvent is preferably a nitrile having 2 to 10 carbon atoms, and more preferably a nitrile having 2 to 7 carbon atoms. Preferred nitrile solvents include acetonitrile (bp = 82 ° C.), propanenitrile (bp = 97 ° C.), butyronitrile (bp = 116 ° C.), isbutyronitrile (bp = 107 ° C.), valeronitrile (bp = 140 ° C.). ), Isovaleronitrile (bp = 129 ° C.), benzonitrile (bp = 191 ° C.) and the like. Among these, acetonitrile is preferable from the viewpoint of a low boiling point.
These nitrile solvents can be used singly or in combination of two or more.
なお、これらエステル系溶媒は、1種単独であるいは2種以上を組み合わせて用いることができる。 The ester solvent is preferably an ester having 3 to 10 carbon atoms, and more preferably an ester having 3 to 6 carbon atoms. Preferred ester solvents include alkyl esters such as ethyl acetate (bp = 77 ° C.), propyl acetate (bp = 97 ° C.), acetic acid-i-propyl (bp = 89 ° C.), butyl acetate (bp = 126 ° C.), etc. And cyclic esters such as β-propiolactone (bp = 155 ° C.).
These ester solvents can be used singly or in combination of two or more.
なお、これらアミド系溶媒は、1種単独であるいは2種以上を組み合わせて用いることができる。 The amide solvent is preferably an amide having 3 to 10 carbon atoms, and more preferably an amide having 3 to 6 carbon atoms. Among these, when a film is obtained by vacuum drying, primary drying, and then secondary drying of a coating film formed on a glass substrate or the like, an amide solvent having a boiling point equal to or higher than the primary drying temperature is obtained. From the viewpoint of the flatness of the film, etc., specifically, an amide solvent having a boiling point of 200 ° C. or higher is preferable. Preferred amide solvents include alkylamides such as N, N-dimethylformamide and N, N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone and the like. Examples thereof include cyclic amides. Among these, N-methyl-2-pyrrolidone and N, N-dimethylacetamide remain after vacuum drying or primary drying by evaporating the non-amide solvent, and at the time of secondary drying performed at 200 ° C. to 500 ° C. It is more preferable because it volatilizes at an evaporation rate that can maintain the smoothness of the surface of the coating film, and N-methyl-2-pyrrolidone is more preferable in consideration of environmental pollution and the like.
These amide solvents can be used alone or in combination of two or more.
本発明に係る樹脂組成物は、前記本発明のポリイミド前駆体および有機溶媒を含むことが好ましい。この有機溶媒としては、前記混合溶媒が好ましい。 ≪Resin composition≫
The resin composition according to the present invention preferably contains the polyimide precursor of the present invention and an organic solvent. The organic solvent is preferably the mixed solvent.
なお、前記樹脂組成物の粘度は、E型粘度計(東機産業製、粘度計MODEL RE100)を用いて、大気中、25℃で測定した値である。 The viscosity of the resin composition is usually 500 to 500,000 mPa · s, preferably 1,000 to 50,000 mPa · s, although it depends on the molecular weight and concentration of the polyimide precursor. If it is less than 500 mPa · s, the retention of the resin composition during film formation is poor, and the resin composition may flow down from the substrate. On the other hand, if it exceeds 500,000 mPa · s, the viscosity is too high, and it becomes difficult to adjust the film thickness, which may make it difficult to form the film.
The viscosity of the resin composition is a value measured at 25 ° C. in the atmosphere using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., viscometer MODEL RE100).
本発明に係る膜(ポリイミド系膜)の形成方法としては、前記樹脂組成物を基板上に塗布して塗膜を形成する工程と、該塗膜から前記有機溶媒を蒸発させることにより除去する工程とを含む方法等が挙げられる。 ≪Film formation method≫
As a method for forming a film (polyimide film) according to the present invention, a step of coating the resin composition on a substrate to form a coating film, and a step of removing the organic solvent from the coating film by evaporation And the like methods.
下記実施例1~13、または、比較例1および2で得られたフィルムを用いてポリイミドのガラス転移温度を、Rigaku社製8230型DSC測定装置を用いて、昇温速度を20℃/minとして測定した。 (1) Glass transition temperature (Tg)
Using the films obtained in Examples 1 to 13 or Comparative Examples 1 and 2 below, the glass transition temperature of polyimide was set to 20 ° C./min using a Rigaku 8230 DSC measuring apparatus. It was measured.
下記実施例1~13、または比較例1および2で得られたポリアミック酸のシリコーン化合物(構造単位(2)を含む化合物)濃度は、下記式により求めた。
シリコーン化合物濃度[単位:%]=(シリコーン化合物の重量)/{((A)全アシル化合物の重量)+((B)全イミノ形成化合物の重量)}×100
シリコーン化合物の重量=化合物(A-2)の重量+化合物(B-2)の重量 (2) Silicone Compound Concentration The concentration of the silicone compound (compound containing the structural unit (2)) of the polyamic acid obtained in the following Examples 1 to 13 or Comparative Examples 1 and 2 was determined by the following formula.
Silicone compound concentration [unit:%] = (weight of silicone compound) / {(weight of (A) total acyl compound) + ((B) weight of total imino forming compound)} × 100
Weight of silicone compound = weight of compound (A-2) + weight of compound (B-2)
イミド化率が100モル%であると仮定すると、下記実施例1~13、または、比較例1および2で得られたポリイミド中の繰り返し単位の分子量は、(アシル化合物の分子量)+(ジアミンの分子量)-2×(水の分子量)で求められる。この繰り返し単位1つあたり、2つのイミド基を含むため、下記実施例1~13、または、比較例1および2で得られた重合体のイミド基濃度(イミド化率が100モル%であると仮定した場合の理論値)は、下記式により求めた。
[イミド基濃度](単位:mmol/g)=2/{(アシル化合物の分子量)+(ジアミンの分子量)-2×(水の分子量)}×1000 (3) Imide group concentration Assuming that the imidization rate is 100 mol%, the molecular weight of the repeating unit in the polyimides obtained in Examples 1 to 13 or Comparative Examples 1 and 2 below is (acyl compound Molecular weight) + (molecular weight of diamine) −2 × (molecular weight of water) Since this repeating unit contains two imide groups, the imide group concentration of the polymers obtained in the following Examples 1 to 13 or Comparative Examples 1 and 2 (the imidization ratio is 100 mol%) (Theoretical value when assumed) was obtained by the following equation.
[Imide group concentration] (unit: mmol / g) = 2 / {(molecular weight of acyl compound) + (molecular weight of diamine) −2 × (molecular weight of water)} × 1000
下記実施例1~13、または、比較例1および2におけるイミド化工程(250℃乾燥)終了後に、室温まで冷却したポリイミド系膜付支持体を300℃まで30分かけて昇温し、その後、30分で室温まで冷却する工程を1サイクルとして、このサイクルを10回繰り返した後、支持体からの剥離がないものを[◎]、このサイクルを5回繰り返した後、支持体からの剥離がないものを[○]、剥離が観察されたものを[×]とした。 (4) Adhesion After completion of the imidization step (drying at 250 ° C.) in the following Examples 1 to 13 or Comparative Examples 1 and 2, the polyimide film-supported substrate cooled to room temperature was elevated to 300 ° C. over 30 minutes. The process of heating and then cooling to room temperature in 30 minutes was defined as one cycle, and after repeating this cycle 10 times, the case where there was no peeling from the support [◎], and after repeating this cycle 5 times, the support The case where there was no peeling from the body was shown as [O], and the case where peeling was observed was taken as [x].
下記実施例1~13、または、比較例1および2におけるイミド化工程(250℃乾燥)終了後に、支持体からポリイミド系膜を全面剥離可能なものを[◎]、全面剥離可能で一部剥離痕が残るものを[○]、一部剥離不可を[△]、全面剥離不可を[×]とした。 (5) Peelability After the imidization step (drying at 250 ° C.) in the following Examples 1 to 13 or Comparative Examples 1 and 2, a film that can peel the polyimide film from the support [◎] is peeled off. The case where possible peeling marks were left was indicated as [◯], the case where partial peeling was not possible was [Δ], and the case where whole surface peeling was not possible was indicated as [×].
下記実施例1~13、または、比較例1および2で得られた、支持体から剥離したポリイミド系膜を40×40mmに切り出し、反り(水平な基板上に得られたポリイミド系膜を置いて、該膜の四角における膜と基板との離間距離を測定し、それらの平均値)が1.0mm未満の場合を[◎]、反りが1.0mm以上2.0mm未満の場合を[○]、反りが2.0mm以上3.0mm未満の場合を[△]、反りが3.0mm以上の場合を[×]とした。 (6) Film warpage The polyimide film peeled off from the support obtained in Examples 1 to 13 or Comparative Examples 1 and 2 below was cut into 40 × 40 mm and warped (polyimide obtained on a horizontal substrate). A system film is placed, and the distance between the film and the substrate in the square of the film is measured, and the average value thereof is less than 1.0 mm [◎], the warpage is 1.0 mm or more and less than 2.0 mm. The case was [◯], the case where the warp was 2.0 mm or more and less than 3.0 mm was [Δ], and the case where the warp was 3.0 mm or more was [x].
下記実施例1~13、または、比較例1および2で得られたポリアミック酸の重量平均分子量は、TOSOH製HLC-8020型GPC装置を使用して測定した。溶媒には、臭化リチウム及び燐酸を添加したN-メチル-2-ピロリドン(NMP)を用い、測定温度40℃にて、ポリスチレン換算の分子量を求めた。 (7) Weight average molecular weight The weight average molecular weight of the polyamic acids obtained in the following Examples 1 to 13 or Comparative Examples 1 and 2 was measured using an HLC-8020 GPC apparatus manufactured by TOSOH. As the solvent, N-methyl-2-pyrrolidone (NMP) to which lithium bromide and phosphoric acid were added was used, and the molecular weight in terms of polystyrene was determined at a measurement temperature of 40 ° C.
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル(以下「mTB」ともいう。)6.07g(28.6mmol)と両末端アミノ変性メチルフェニルシリコーン(X22-1660B-3)2.57g(0.6mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド(以下「DMAc」ともいう。)58mlおよびテトラヒドロフラン(以下「THF」ともいう。)20mlを加え均一になるまで攪拌した。得られた溶液に(A)成分としてピロメリット酸二無水物(以下「PMDA」ともいう。)6.36g(29.2mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。得られた組成物の一部を用いて、該組成物からポリアミック酸を単離した。単離したポリアミック酸の重量平均分子量、シリコーン化合物濃度、イミド基濃度(イミド化率が100モル%であると仮定した場合の理論値)を評価した。 [Example 1]
2,2′-dimethyl-4,4′-diaminobiphenyl (hereinafter also referred to as “mTB”) 6 as a component (B) in a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube 6 0.07 g (28.6 mmol) and 2.57 g (0.6 mmol) of both terminal amino-modified methylphenyl silicone (X22-1660B-3) were added. Then, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 20 ml of tetrahydrofuran (hereinafter also referred to as “THF”) were added and stirred until uniform. 6.36 g (29.2 mmol) of pyromellitic dianhydride (hereinafter also referred to as “PMDA”) as component (A) was added to the resulting solution at room temperature, and stirring was continued for 24 hours at the same temperature. A product (polyamic acid solution) was obtained. A polyamic acid was isolated from the composition using a part of the obtained composition. The isolated polyamic acid was evaluated for weight average molecular weight, silicone compound concentration, and imide group concentration (theoretical value when the imidization rate was assumed to be 100 mol%).
また、上記ポリイミド系膜について、支持体に対する密着性、剥離性、ポリイミド系膜のソリを評価した。
結果を表1に示す。 Next, the obtained polyamic acid solution was applied on a non-alkali glass support with a spin coater (rotated at 300 rpm for 5 seconds and then rotated at 1100 rpm for 10 seconds), then at 70 ° C. for 30 minutes, and then at 120 ° C. A coating film was obtained by drying for 30 minutes. The coating film obtained as the imidization step was further dried at 250 ° C. for 2 hours, and then peeled from the alkali-free glass support to obtain a polyimide film having a film thickness of 30 μm (0.03 mm).
Moreover, about the said polyimide-type film | membrane, the adhesiveness with respect to a support body, peelability, and the curvature of the polyimide-type film | membrane were evaluated.
The results are shown in Table 1.
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.07g(28.6mmol)と両末端アミノ変性メチルフェニルシリコーン(X22-1660B-3)2.57g(0.6mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A)成分としてピロメリット酸二無水物6.36g(29.2mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。 [Example 2]
In a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser tube, both 2,2′-dimethyl-4,4′-diaminobiphenyl (6.07 g, 28.6 mmol) as component (B) 2.57 g (0.6 mmol) of terminal amino-modified methylphenyl silicone (X22-1660B-3) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the resulting solution, 6.36 g (29.2 mmol) of pyromellitic dianhydride as component (A) was added at room temperature, and stirring was continued at that temperature for 24 hours to obtain a composition (polyamic acid solution). .
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.68g(31.4mmol)と両末端アミノ変性メチルフェニルシリコーン(X22-1660B-3)1.40g(0.3mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlとテトラヒドロフラン20mlを加え均一になるまで攪拌した。得られた溶液に(A)成分としてピロメリット酸二無水物6.93g(31.8mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。 [Example 3]
In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, both 6.68 g (31.4 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B) were added. 1.40 g (0.3 mmol) of terminal amino-modified methylphenyl silicone (X22-1660B-3) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide and 20 ml of tetrahydrofuran were added and stirred until uniform. To the resulting solution, 6.93 g (31.8 mmol) of pyromellitic dianhydride as component (A) was added at room temperature, and stirring was continued at that temperature for 24 hours to obtain a composition (polyamic acid solution). .
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.04g(28.4mmol)と両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-9409,数平均分子量1,300)2.36g(1.8mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A)成分としてピロメリット酸二無水物6.60g(30.3mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。 [Example 4]
In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 6.04 g (28.4 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl was added as component (B). 2.36 g (1.8 mmol) of terminal amino-modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-9409, number average molecular weight 1,300) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the obtained solution, 6.60 g (30.3 mmol) of pyromellitic dianhydride as component (A) was added at room temperature, and stirring was continued at that temperature for 24 hours to obtain a composition (polyamic acid solution). .
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.41g(30.2mmol)と両末端アミノ変性メチルフェニルシリコーン(信越化学製、X22-161B、数平均分子量3,000)1.85g(0.6mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A)成分としてピロメリット酸二無水物6.73g(30.9mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。 [Example 5]
In a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser tube, both 6.41 g (30.2 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B) were added. 1.85 g (0.6 mmol) of terminal amino-modified methyl phenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-161B, number average molecular weight 3,000) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the resulting solution, 6.73 g (30.9 mmol) of pyromellitic dianhydride as component (A) was added at room temperature, and stirring was continued at that temperature for 24 hours to obtain a composition (polyamic acid solution). .
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.29g(29.6mmol)と両末端アミノ変性メチルフェニルシリコーン(信越化学製、X22-161A、数平均分子量1,600)1.98g(1.2mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A)成分としてピロメリット酸二無水物6.73g(30.9mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。 [Example 6]
In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, both 6.29 g (29.6 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B) were added. 1.98 g (1.2 mmol) of terminal amino-modified methyl phenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-161A, number average molecular weight 1,600) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the resulting solution, 6.73 g (30.9 mmol) of pyromellitic dianhydride as component (A) was added at room temperature, and stirring was continued at that temperature for 24 hours to obtain a composition (polyamic acid solution). .
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.65g(31.3mmol)を添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A)成分としてピロメリット酸二無水物6.15g(28.2mmol)と両末端酸無水物変性メチルシリコーン(DMS-Z21)2.19g(3.1mmol)とを室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。 [Example 7]
Add 6.65 g (31.3 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B) to a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser. did. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the resulting solution, 6.15 g (28.2 mmol) of pyromellitic dianhydride and 2.19 g (3.1 mmol) of acid anhydride-modified methylsilicone (DMS-Z21) at room temperature were used as component (A). In addition, stirring was continued at that temperature for 24 hours to obtain a composition (polyamic acid solution).
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.59g(31.0mmol)と両末端アミノ変性メチルフェニルシリコーン(X22-1660B-3)1.38g(0.3mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A)成分として1,2,4,5-シクロヘキサンテトラカルボン酸二無水物(以下「PMDAH」ともいう。)7.03g(31.4mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。 [Example 8]
In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, both 6.59 g (31.0 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B) were added. 1.38 g (0.3 mmol) of terminal amino-modified methylphenyl silicone (X22-1660B-3) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the resulting solution, 7.03 g (31.4 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (hereinafter also referred to as “PMDAH”) as component (A) was added at room temperature, and the temperature was maintained. Then, stirring was continued for 24 hours to obtain a composition (polyamic acid solution).
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として1,4-ジアミノシクロヘキサン(以下「CHDA」ともいう。)2.87g(25.1mmol)と両末端アミノ変性メチルフェニルシリコーン(X22-1660B-3)3.42g(0.8mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A)成分としてジフェニル-3,3’,4,4’-テトラカルボン酸二無水物(以下「s-BPDA」ともいう。)8.71g(25.9mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。 [Example 9]
2.87 g (25.1 mmol) of 1,4-diaminocyclohexane (hereinafter also referred to as “CHDA”) as component (B) was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube. 3.42 g (0.8 mmol) of both-end amino-modified methylphenyl silicone (X22-1660B-3) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the resulting solution, 8.71 g (25.9 mmol) of diphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter also referred to as “s-BPDA”) as component (A) was added at room temperature. In addition, stirring was continued at that temperature for 24 hours to obtain a composition (polyamic acid solution).
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として1,4-ジアミノシクロヘキサン2.99g(26.2mmol)と両末端アミノ変性メチルフェニルシリコーン(X22-9409)2.56g(2.0mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A)成分としてジフェニル-3,3’,4,4’-テトラカルボン酸二無水物9.46g(28.1mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。 [Example 10]
In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 2.99 g (26.2 mmol) of 1,4-diaminocyclohexane as component (B) and amino-modified methylphenyl silicone (X22) −9409) 2.56 g (2.0 mmol) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the obtained solution, 9.46 g (28.1 mmol) of diphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride as component (A) was added at room temperature, and stirring was continued at that temperature for 24 hours. Thus, a composition (polyamic acid solution) was obtained.
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として4,4’-ジアミノ-2,2’-ビス(トリフルオロメチル)ビフェニル(以下「TFMB」ともいう。)7.85g(24.5mmol)と両末端アミノ変性メチルフェニルシリコーン(X22-9409)2.03g(1.6mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A)成分として1,2,3,4-シクロブタンテトラカルボン酸二無水物(以下「CBDA」ともいう。)5.12g(26.1mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。 [Example 11]
4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (hereinafter referred to as "TFMB") as a component (B) in a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser tube 7.85 g (24.5 mmol) and 2.03 g (1.6 mmol) of both-terminal amino-modified methylphenyl silicone (X22-9409) were added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the resulting solution, 5.12 g (26.1 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as “CBDA”) as component (A) was added at room temperature, and the temperature was maintained. Then, stirring was continued for 24 hours to obtain a composition (polyamic acid solution).
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.34g(29.9mmol)と両末端アミノ変性メチルフェニルシリコーン(X22-1660B-3)2.68g(0.6mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A)成分として1,2,3,4-シクロブタンテトラカルボン酸二無水物5.98g(30.5mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。 [Example 12]
In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, both 6.34 g (29.9 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B) were added. 2.68 g (0.6 mmol) of terminal amino-modified methylphenyl silicone (X22-1660B-3) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the resulting solution, 5.98 g (30.5 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as component (A) was added at room temperature, and stirring was continued at that temperature for 24 hours. A product (polyamic acid solution) was obtained.
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル4.78g(22.3mmol)と両末端アミノ変性メチルフェニルシリコーン(X22-1660B-3)5.16g(1.2mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A)成分としてピロメリット酸二無水物5.11g(23.4mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。 [Example 13]
In a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen introduction tube, and cooling tube, both 2.78 '(22.3 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl as component (B) were added. 5.16 g (1.2 mmol) of terminal amino-modified methylphenyl silicone (X22-1660B-3) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the obtained solution, 5.11 g (23.4 mmol) of pyromellitic dianhydride as component (A) was added at room temperature, and stirring was continued at that temperature for 24 hours to obtain a composition (polyamic acid solution). .
上記実施例1において調製したポリアミック酸溶液(組成物)を、スピンコーターにて無アルカリガラス支持体上に、得られる塗膜の厚みが25μmになるように流延塗布し、70℃で30分、ついで120℃で30分乾燥して塗膜を得た。その後、環化(イミド化)工程として得られた塗膜をさらに250℃で2時間乾燥した。 [Example 14]
The polyamic acid solution (composition) prepared in Example 1 was cast and applied on a non-alkali glass support with a spin coater so that the thickness of the resulting coating film was 25 μm, and 30 minutes at 70 ° C. Then, it was dried at 120 ° C. for 30 minutes to obtain a coating film. Then, the coating film obtained as a cyclization (imidation) step was further dried at 250 ° C. for 2 hours.
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル7.40g(34.9mmol)を添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A)成分としてピロメリット酸二無水物7.60g(34.9mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、ポリアミック酸溶液を得た。 [Comparative Example 1]
2.40 g (34.9 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl was added as a component (B) to a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and cooling tube. did. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the obtained solution, 7.60 g (34.9 mmol) of pyromellitic dianhydride as component (A) was added at room temperature, and stirring was continued at that temperature for 24 hours to obtain a polyamic acid solution.
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B)成分として2,2’-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(以下「BAPP」ともいう。)9.25g(22.5mmol)を添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A)成分としてピロメリット酸二無水物2.95g(13.5mmol)および4,4’-オキシジフタル酸二無水物(以下「ODPA」ともいう。)2.80g(0.9mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、ポリアミック酸溶液を得た。 [Comparative Example 2]
A 2,2′-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter referred to as “BAPP”) as a component (B) was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. 9.25 g (22.5 mmol) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. As the component (A), 2.95 g (13.5 mmol) of pyromellitic dianhydride and 2.80 g (hereinafter also referred to as “ODPA”) of 4,4′-oxydiphthalic dianhydride (hereinafter referred to as “ODPA”) were added to the obtained solution. 9 mmol) was added at room temperature, and stirring was continued at that temperature for 24 hours to obtain a polyamic acid solution.
下記実施例15~20および比較例3で得られたポリイミド前駆体の重量平均分子量(Mw)、数平均分子量(Mn)および分子量分布(Mw/Mn)は、TOSOH製HLC-8220型GPC装置(ガードカラム:TSK guard colomn ALPHA カラム:TSKgelALPHA―M、展開溶剤:NMP)を用いて測定した。 (1) Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)
The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the polyimide precursors obtained in Examples 15 to 20 and Comparative Example 3 below were measured using an HLC-8220 GPC apparatus manufactured by TOSOH ( Guard column: TSK guard column ALPHA column: TSKgel ALPHA-M, developing solvent: NMP).
下記実施例15~20および比較例3で得られたワニス(樹脂組成物)を-15℃で48時間保存後、透明で沈殿物のないものを○、不透明で沈殿物が析出したものを×として目視により評価した。 (2) Storage stability at −15 ° C. After storing the varnishes (resin compositions) obtained in Examples 15 to 20 and Comparative Example 3 below at −15 ° C. for 48 hours, Evaluation was made visually by setting x to be opaque and depositing a precipitate.
下記実施例15~20および比較例3で得られたワニス1.5gを用い、25℃でのワニス粘度を測定した。具体的には東機産業製 粘度計 MODEL RE100を用い測定した。 (3) Varnish viscosity Using 1.5 g of the varnish obtained in the following Examples 15 to 20 and Comparative Example 3, the varnish viscosity at 25 ° C was measured. Specifically, it was measured using a viscometer MODEL RE100 manufactured by Toki Sangyo.
下記実施例15~20および比較例3で得られた真空乾燥後のガラス基板付塗膜の中央部およびガラス基板の中央部に標線を引き、塗膜付基板を垂直に立て10分間放置した。塗膜に引かれた標線とガラス基板に引かれた標線との高さが変化しなかった場合は固定化、変化した場合は流動化と判定した。 (4) Immobilization of coating film after vacuum drying Draw a marked line at the center of the coating film with glass substrate and the center of the glass substrate after vacuum drying obtained in Examples 15 to 20 and Comparative Example 3 below. The substrate with the coating film was set up vertically and left for 10 minutes. When the height of the marked line drawn on the coating film and the marked line drawn on the glass substrate did not change, it was determined to be fixed, and when changed, it was determined to be fluidized.
下記実施例15~20および比較例3で得られた真空乾燥後の塗膜中のポリマー(ポリイミド前駆体)濃度を下記の式に従い、算出した。
塗布したワニス重量=ワニス塗布後のガラス基板の重量-ワニス塗布前のガラス基板の重量
仕込み時ポリマー濃度(%)=仕込みモノマー全量/(仕込みモノマー量+仕込み溶媒全量)×100
塗布したポリマー重量=塗布したワニス重量×仕込み時ポリマー濃度(%)
真空乾燥後塗膜重量=真空乾燥後の塗膜付ガラス基板の重量-ワニス塗布前のガラス基板の重量
真空乾燥後のポリマー濃度(%)=(塗布したポリマー重量/真空乾燥後塗膜重量)×100 (5) Polymer (polyimide precursor) concentration in the coating film after vacuum drying The polymer (polyimide precursor) concentration in the coating film after vacuum drying obtained in Examples 15 to 20 and Comparative Example 3 below is It was calculated according to the formula.
Weight of applied varnish = weight of glass substrate after varnish application-weight of glass substrate before varnish application Polymer concentration at the time of charging (%) = total amount of charged monomer / (total amount of charged monomer + total amount of charged solvent) x 100
Applied polymer weight = Applied varnish weight x Polymer concentration at the time of charging (%)
Weight of coating film after vacuum drying = Weight of glass substrate with coating after vacuum drying-Weight of glass substrate before coating of varnish Polymer concentration (%) after vacuum drying = (Weight of polymer applied / weight of coating film after vacuum drying) × 100
下記実施例15~20および比較例3で得られた真空乾燥後の塗膜中の溶媒組成比を上記の式および下記の式に従い、算出した。
塗布した溶媒重量=塗布したワニス重量-塗布したポリマー重量
塗布した非アミド系溶媒の重量=塗布した溶媒重量×非アミド系溶媒の仕込み量(混合溶媒中の非アミド系溶媒の割合)(%)
真空乾燥後溶媒重量=真空乾燥後塗膜重量-塗布したポリマー重量
真空乾燥で蒸発した溶媒重量=塗布した溶媒重量-真空乾燥後溶媒重量
真空乾燥後の非アミド系溶媒重量=塗布した非アミド系溶媒の重量-真空乾燥で蒸発した溶媒重量
非アミド系溶媒の組成比(%)=(真空乾燥後の非アミド系溶媒重量/真空乾燥後溶媒重量×100)
アミド系溶媒の組成比(%)=100-非アミド系溶媒の組成比
(なお、真空乾燥で蒸発した溶媒は混合溶媒中の最も沸点な低い溶媒(非アミド系溶媒)と定義した。) (6) Solvent composition ratio in the coating film after vacuum drying The solvent composition ratio in the coating film after vacuum drying obtained in the following Examples 15 to 20 and Comparative Example 3 was calculated according to the above formula and the following formula. did.
Coating solvent weight = Coating varnish weight-Coating polymer weight Coating non-amide solvent weight = Coating solvent weight x amount of non-amide solvent charge (ratio of non-amide solvent in mixed solvent) (%)
Solvent weight after vacuum drying = coating weight after vacuum drying-weight of polymer applied Solvent weight evaporated by vacuum drying = solvent weight applied-solvent weight after vacuum drying Non-amide solvent weight after vacuum drying = non-amide coating applied Weight of solvent−solvent weight evaporated by vacuum drying Composition ratio (%) of non-amide solvent = (weight of non-amide solvent after vacuum drying / solvent weight after vacuum drying × 100)
Composition ratio (%) of amide solvent = 100−composition ratio of non-amide solvent (The solvent evaporated by vacuum drying was defined as the solvent having the lowest boiling point in the mixed solvent (non-amide solvent).)
下記実施例15~20および比較例3で得られた1次乾燥後の塗膜を金属製スパチュラーで強くこすり、塗膜が移動しないものをタック性無し、塗膜が移動したものをタック性有とし、評価した。 (7) Tackiness after primary drying The coating after primary drying obtained in the following Examples 15 to 20 and Comparative Example 3 was strongly rubbed with a metal spatula, and no tackiness was observed when the coating did not move. The coating film moved was evaluated as having tackiness.
下記実施例15~20および比較例3で得られた1次乾燥後および2次乾燥後のガラス基板上に形成された塗膜それぞれについて、Haze(ヘイズ)をJIS K7105透明度試験法に準じて測定した。具体的には、スガ試験機社製SC-3H型ヘイズメーターを用い測定した。 (8) Optical properties For each of the coating films formed on the glass substrates after the primary drying and the secondary drying obtained in Examples 15 to 20 and Comparative Example 3 below, the haze was measured according to JIS K7105 transparency test. Measured according to the law. Specifically, it was measured using an SC-3H haze meter manufactured by Suga Test Instruments Co., Ltd.
下記実施例15~20および比較例3で得られたフィルムをガラス基板から剥離し、剥離後のフィルムをRigaku製 Thermo Plus DSC8230を用い、窒素下で、昇温速度を20℃/minとし、40~450℃の範囲で測定した。 (9) Glass transition temperature (Tg)
The films obtained in the following Examples 15 to 20 and Comparative Example 3 were peeled from the glass substrate, and the peeled film was subjected to Rigaku's Thermo Plus DSC 8230 under a nitrogen temperature rising rate of 20 ° C./min. It was measured in the range of ˜450 ° C.
下記実施例15~20および比較例3で得られたフィルムをガラス基板から剥離し、剥離後のフィルムをSeiko Instrument SSC/5200を用い、昇温速度を6℃/minとし、25~350℃の範囲で測定した。測定結果から100~200℃の線膨張係数を算出した。 (10) Linear expansion coefficient The films obtained in the following Examples 15 to 20 and Comparative Example 3 were peeled from the glass substrate, the peeled film was used with Seiko Instrument SSC / 5200, and the rate of temperature increase was 6 ° C / min. , Measured in the range of 25-350 ° C. A linear expansion coefficient of 100 to 200 ° C. was calculated from the measurement results.
下記実施例16~21および比較例3で得られたワニスを、FLX-2320(KLA社製)を用いて、シリコンウエハ基板(残留応力測定用、秩父電子株式会社製、厚み=300μm、直径=4インチ)上に2次乾燥後の膜厚が30μmになるように成膜し、反りをレーザーで測定し、塗膜のストレスを下記式より算出した。 (11) Residual stress of coating film Using varnishes obtained in Examples 16 to 21 and Comparative Example 3 below, a silicon wafer substrate (for residual stress measurement, Chichibu Electronics Co., Ltd.) using FLX-2320 (manufactured by KLA) The film thickness after the secondary drying was 30 μm, the warpage was measured with a laser, and the stress of the coating film was calculated from the following formula.
下記実施例15~20および比較例3で得られた2次乾燥後の膜中のポリイミドのイミド化率をFT-IR(サーモフィッシャーサイエンティック製、Thermo NICOLET6700)を使って以下の方法で定量した。 (12) Imidization rate The imidation rate of the polyimide in the film after secondary drying obtained in Examples 15 to 20 and Comparative Example 3 below was measured using FT-IR (Thermo NICENT 6700, manufactured by Thermo Fisher Scientific). Quantification was performed by the following method.
イミド化率(%)=(1-2次乾燥後のピーク面積比/1次乾燥前のピーク面積比)×100 The peak separation (1520 cm -1 ) area of the NH bending vibration derived from the polyimide precursor and the peak (990 cm -1 ) area of the = CH out-of-plane bending vibration of the aromatic asymmetric trisubstituted product are separated by Gaussian distribution. And quantified. The first drying before the polyimide precursor peak area ratio (peak area peak area / 1520 cm -1 of 990 cm -1) and their peak area ratio after secondary drying were measured, imidization using the following equation The rate was calculated.
Imidization ratio (%) = (peak area ratio after primary / secondary drying / peak area ratio before primary drying) × 100
JISK6251の7号ダンベルを用い、下記実施例15~20および比較例3で得られた2次乾燥後のガラス基板から剥離した30μmフィルムを23℃下、50mm/minの速度で引張り試験を実施し、引張り伸び、引張り強度、弾性率を測定した。 (13) Film Strength Using a JISK6251 No. 7 dumbbell, a 30 μm film peeled off from the glass substrate after secondary drying obtained in Examples 15 to 20 and Comparative Example 3 below at 23 ° C. at a speed of 50 mm / min. A tensile test was performed to measure tensile elongation, tensile strength, and elastic modulus.
下記実施例15~20および比較例3で得られた2次乾燥後のガラス基板付30μm塗膜を幅10mm×長さ50mmにカッターで切削を行い、長さ20mmまで引き剥がした後、180度の角度で速度50mm/minでピール強度を測定した。 (14) Peelability from glass substrate The 30 μm coating film with glass substrate after secondary drying obtained in Examples 15 to 20 and Comparative Example 3 below was cut with a cutter into a width of 10 mm and a length of 50 mm. After peeling off to 20 mm, peel strength was measured at an angle of 180 degrees and a speed of 50 mm / min.
下記実施例15~20および比較例3で得られた2次乾燥後のガラス基板付30μm塗膜を60mm×60mmの大きさにカッターで切削後、4つの端部の浮き上がりを測定し、平均値を算出した。 (15) Warping of the film After cutting the 30 μm coating film with glass substrate after secondary drying obtained in Examples 15 to 20 and Comparative Example 3 to a size of 60 mm × 60 mm with a cutter, the four edges lifted. Was measured and the average value was calculated.
温度計、窒素導入管および攪拌羽根付三口フラスコに、25℃にて窒素気流下、m-トリジン(mTB)45.23099g(0.21306mol)、両末端アミノ変性側鎖フェニル・メチル型シリコーンX-22-1660B-3[9.4694g(0.0021521mol)]、ワニス中のポリイミド前駆体の濃度が14%となるように脱水N-メチル-2-ピロリドン(NMP)307gおよび脱水シクロヘキサノン(CHN)307gを加え、mTBおよびX-22-1660B-3が完全に溶解するまで10分間攪拌した。ピロメリット酸二無水物(PMDA)22.6498g(0.10384mol)を加え30分攪拌した後、さらにPMDA22.6498g(0.10384mol)を加え60分攪拌することで反応を終了させ、次いで、ポリテトラフルオロエチレン製フィルター(ポアサイズ1μm)を用いて精密濾過行うことで、ワニスを作成した(PMDA/(mTB+X-22-1660B-3)=0.965当量)。ワニス特性を表2に示す。NMRを用いて測定した結果、得られたワニス中には、前記構造単位(1)を有するポリイミド前駆体が確認された。 [Example 15]
In a three-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirring blade, under nitrogen flow at 25 ° C., 45.23099 g (0.21306 mol) of m-tolidine (mTB), both ends amino-modified side chain phenyl methyl type silicone X- 22-1660B-3 [9.4694 g (0.0021521 mol)], 307 g of dehydrated N-methyl-2-pyrrolidone (NMP) and 307 g of dehydrated cyclohexanone (CHN) so that the concentration of the polyimide precursor in the varnish was 14%. Was added and stirred for 10 minutes until mTB and X-22-1660B-3 were completely dissolved. Pyromellitic dianhydride (PMDA) 22.6498 g (0.10384 mol) was added and stirred for 30 minutes, then PMDA 22.6498 g (0.10384 mol) was further added and stirred for 60 minutes, and then the reaction was terminated. By performing microfiltration using a tetrafluoroethylene filter (pore size 1 μm), a varnish was prepared (PMDA / (mTB + X-22-1660B-3) = 0.965 equivalent). The varnish properties are shown in Table 2. As a result of measurement using NMR, a polyimide precursor having the structural unit (1) was confirmed in the obtained varnish.
実施例15において、mTB、X-22-1660B-3およびPMDAの使用量を表2に示すように変更した以外は実施例15と同様に行った。結果を表2に示す。 [Example 16]
The same operation as in Example 15 was carried out except that the amounts of mTB, X-22-1660B-3 and PMDA used were changed as shown in Table 2. The results are shown in Table 2.
実施例15において、mTB、X-22-1660B-3およびPMDAの使用量を表2に示すように変更した以外は実施例15と同様に行った。結果を表2に示す。 [Example 17]
The same operation as in Example 15 was carried out except that the amounts of mTB, X-22-1660B-3 and PMDA used were changed as shown in Table 2. The results are shown in Table 2.
実施例15において、mTB45.23099gの代わりにmTB32.56478gおよび4,4'-ジアミノジフェニルエーテル(ODA)7.8760gを用い、X-22-1660B-3およびPMDAの使用量を表2に示すように変更した以外は実施例15と同様に行った。結果を表2に示す。 [Example 18]
In Example 15, instead of mTB45.23099 g, 32.578 g of mTB and 7.8760 g of 4,4′-diaminodiphenyl ether (ODA) were used, and the amounts of X-22-1660B-3 and PMDA used were as shown in Table 2. The same operation as in Example 15 was performed except for the change. The results are shown in Table 2.
実施例15において、X-22-1660B-3(9.4694g)の代わりに信越化学製両末端アミノ変性側鎖メチル型シリコーンKF8010(前記式(9)中の全てのR5のうち、メチル基とフェニル基のモル組成比が100:0、数平均分子量(4400、m=58))2.8408gとX22-1660B-3(6.6286g)とを併用した以外は実施例15と同様に行った。結果を表2に示す。 [Example 19]
In Example 15, instead of X-22-1660B-3 (9.4694 g), both terminal amino-modified side chain methyl silicone KF8010 manufactured by Shin-Etsu Chemical Co., Ltd. (of all R 5 in the formula (9), methyl group) And phenyl group in a molar composition ratio of 100: 0, number average molecular weight (4400, m = 58)) 2.8408 g and X22-1660B-3 (6.6286 g) were used in the same manner as in Example 15. It was. The results are shown in Table 2.
耐熱性、透明性、平滑性に優れ、ソリのない、線膨張係数の低い強靭なフィルムを得ることができた。また、得られた塗膜は、乾燥速度が速く、1次乾燥、2次乾燥中ではガラス基板との密着性に優れ、2次乾燥後に得られた膜は、ガラス基板からの剥離性に優れていた。 As a result of measurement using NMR, a polyimide precursor having the structural unit (1) was confirmed in the obtained varnish.
A tough film having excellent heat resistance, transparency and smoothness, having no warpage and having a low coefficient of linear expansion could be obtained. In addition, the obtained coating film has a high drying speed and is excellent in adhesion with a glass substrate during primary drying and secondary drying, and the film obtained after secondary drying is excellent in peelability from the glass substrate. It was.
実施例18において、mTB、X-22-1660B-3、ODAおよびPMDAの使用量を表2に示すように変更した以外は実施例18と同様に行った。結果を表2に示す。 [Example 20]
The same operation as in Example 18 was carried out except that the amounts of mTB, X-22-1660B-3, ODA and PMDA used were changed as shown in Table 2. The results are shown in Table 2.
実施例15において、X-22-1660B-3を用いず、また、mTBおよびPMDAの使用量を表2に示すように変更した以外は実施例15と同様に行った。結果を表2に示す。 [Comparative Example 3]
Example 15 was carried out in the same manner as Example 15 except that X-22-1660B-3 was not used and the amounts of mTB and PMDA used were changed as shown in Table 2. The results are shown in Table 2.
Claims (12)
- 下記式(2)で表わされる構造単位を含む下記式(1)で表わされる構造単位を有するポリイミド前駆体。
- 前記ポリイミド前駆体中、前記式(2)で表される構造単位が5~40質量%含まれる、請求項1に記載のポリイミド前駆体。 The polyimide precursor according to claim 1, wherein the polyimide precursor contains 5 to 40% by mass of the structural unit represented by the formula (2).
- 前記式(2)において、複数あるR5の少なくとも1つがアリール基を含む、請求項1または2に記載のポリイミド前駆体。 The polyimide precursor according to claim 1 or 2, wherein in the formula (2), at least one of a plurality of R 5 includes an aryl group.
- 前記ポリイミド前駆体が、前記式(1)に含まれる構造単位の他に、該前駆体の主鎖に、エーテル基、チオエーテル基、ケトン基、エステル基、スルフォニル基、アルキレン基、アミド基およびシロキサン基からなる群より選ばれる少なくとも1種の基を含む単量体に由来する構造単位を、前記ポリイミド前駆体中、さらに0~15質量%含む、請求項1~3のいずれか1項に記載のポリイミド前駆体。 In addition to the structural unit contained in the formula (1), the polyimide precursor has an ether group, a thioether group, a ketone group, an ester group, a sulfonyl group, an alkylene group, an amide group, and a siloxane in the main chain of the precursor. The structural unit derived from a monomer containing at least one group selected from the group consisting of groups further comprises 0 to 15% by mass in the polyimide precursor. Polyimide precursor.
- 前記単量体が、下記式(5)または式(6)で表わされる化合物である、請求項4に記載のポリイミド前駆体。
- 重量平均分子量が10000~1000000である、請求項1~5のいずれか1項に記載のポリイミド前駆体。 6. The polyimide precursor according to claim 1, having a weight average molecular weight of 10,000 to 1,000,000.
- 請求項1~6のいずれか1項に記載のポリイミド前駆体および有機溶媒を含む、樹脂組成物。 A resin composition comprising the polyimide precursor according to any one of claims 1 to 6 and an organic solvent.
- 前記樹脂組成物中、前記ポリイミド前駆体の濃度が3~60質量%である、請求項7に記載の樹脂組成物。 The resin composition according to claim 7, wherein a concentration of the polyimide precursor is 3 to 60% by mass in the resin composition.
- 前記有機溶媒が、エーテル系溶媒、ケトン系溶媒、ニトリル系溶媒、エステル系溶媒およびアミド系溶媒からなる群より選ばれる少なくとも1種の溶媒を含む、請求項7または8に記載の樹脂組成物。 The resin composition according to claim 7 or 8, wherein the organic solvent contains at least one solvent selected from the group consisting of ether solvents, ketone solvents, nitrile solvents, ester solvents, and amide solvents.
- E型粘度計(25℃)で測定した粘度が500~500000mPa・sの範囲である、請求項7~9のいずれか1項に記載の樹脂組成物。 10. The resin composition according to claim 7, wherein the viscosity measured with an E-type viscometer (25 ° C.) is in the range of 500 to 500,000 mPa · s.
- 膜形成用である、請求項7~10のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 7 to 10, which is used for film formation.
- 請求項7~11のいずれか1項に記載の樹脂組成物を、基板上に塗布して塗膜を形成する工程と、該塗膜から前記有機溶媒を蒸発させることにより除去して膜を得る工程とを含む、膜形成方法。 A step of coating the resin composition according to any one of claims 7 to 11 on a substrate to form a coating film, and removing the organic solvent by evaporating the coating film to obtain a film. A film forming method including a process.
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0291124A (en) * | 1988-09-29 | 1990-03-30 | Nippon Steel Chem Co Ltd | Polyimide copolymer and preparation thereof |
JPH06104542A (en) * | 1992-09-17 | 1994-04-15 | Shin Etsu Chem Co Ltd | Metal base wiring board |
JP2005232383A (en) * | 2004-02-20 | 2005-09-02 | Asahi Kasei Electronics Co Ltd | Polyamic acid derivative |
WO2005084948A1 (en) * | 2004-03-04 | 2005-09-15 | Toray Industries, Inc. | Heat-resistant resin laminated film, multilayer film with metal layer including same, and semiconductor device |
JP2007246920A (en) * | 2007-06-01 | 2007-09-27 | Shin Etsu Chem Co Ltd | Polyimide resin having phenolic hydroxyl group and polyimide resin composition |
JP2008095113A (en) * | 2007-11-19 | 2008-04-24 | Shin Etsu Chem Co Ltd | Method for producing polyimide resin having phenolic hydroxy group |
JP2008156425A (en) * | 2006-12-21 | 2008-07-10 | Asahi Kasei Corp | Polyimide and photosensitive resin composition using the same |
JP2008189694A (en) * | 2007-01-31 | 2008-08-21 | Ube Ind Ltd | Copolymer having repeating unit of amic acid structure partly converted to imide structure and method for producing the same |
JP2008307737A (en) * | 2007-06-13 | 2008-12-25 | Mitsui Chemicals Inc | Laminate, wiring board and its manufacturing method |
WO2009054487A1 (en) * | 2007-10-26 | 2009-04-30 | Asahi Kasei Kabushiki Kaisha | Polyimide precursor and photosensitive resin composition containing polyimide precursor |
JP2009269988A (en) * | 2008-05-07 | 2009-11-19 | Tokyo Institute Of Technology | Silicon-containing polyimide and method of manufacturing the same |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100568569B1 (en) | 2004-10-26 | 2006-04-07 | 주식회사 이녹스 | Composition for polyimide adhesive and adhesive tape using the same |
-
2011
- 2011-02-28 KR KR1020127028254A patent/KR20130080432A/en not_active Application Discontinuation
- 2011-02-28 JP JP2012508153A patent/JP5725017B2/en active Active
- 2011-02-28 CN CN2011800161864A patent/CN102822238A/en active Pending
- 2011-02-28 JP JP2012508152A patent/JPWO2011122198A1/en active Pending
- 2011-02-28 WO PCT/JP2011/054488 patent/WO2011122198A1/en active Application Filing
- 2011-02-28 WO PCT/JP2011/054489 patent/WO2011122199A1/en active Application Filing
- 2011-02-28 KR KR1020127028255A patent/KR101848522B1/en active IP Right Grant
- 2011-03-22 TW TW100109697A patent/TW201139519A/en unknown
- 2011-03-22 TW TW100109699A patent/TWI502003B/en active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0291124A (en) * | 1988-09-29 | 1990-03-30 | Nippon Steel Chem Co Ltd | Polyimide copolymer and preparation thereof |
JPH06104542A (en) * | 1992-09-17 | 1994-04-15 | Shin Etsu Chem Co Ltd | Metal base wiring board |
JP2005232383A (en) * | 2004-02-20 | 2005-09-02 | Asahi Kasei Electronics Co Ltd | Polyamic acid derivative |
WO2005084948A1 (en) * | 2004-03-04 | 2005-09-15 | Toray Industries, Inc. | Heat-resistant resin laminated film, multilayer film with metal layer including same, and semiconductor device |
JP2008156425A (en) * | 2006-12-21 | 2008-07-10 | Asahi Kasei Corp | Polyimide and photosensitive resin composition using the same |
JP2008189694A (en) * | 2007-01-31 | 2008-08-21 | Ube Ind Ltd | Copolymer having repeating unit of amic acid structure partly converted to imide structure and method for producing the same |
JP2007246920A (en) * | 2007-06-01 | 2007-09-27 | Shin Etsu Chem Co Ltd | Polyimide resin having phenolic hydroxyl group and polyimide resin composition |
JP2008307737A (en) * | 2007-06-13 | 2008-12-25 | Mitsui Chemicals Inc | Laminate, wiring board and its manufacturing method |
WO2009054487A1 (en) * | 2007-10-26 | 2009-04-30 | Asahi Kasei Kabushiki Kaisha | Polyimide precursor and photosensitive resin composition containing polyimide precursor |
JP2008095113A (en) * | 2007-11-19 | 2008-04-24 | Shin Etsu Chem Co Ltd | Method for producing polyimide resin having phenolic hydroxy group |
JP2009269988A (en) * | 2008-05-07 | 2009-11-19 | Tokyo Institute Of Technology | Silicon-containing polyimide and method of manufacturing the same |
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Also Published As
Publication number | Publication date |
---|---|
WO2011122199A1 (en) | 2011-10-06 |
JPWO2011122198A1 (en) | 2013-07-08 |
KR20130080433A (en) | 2013-07-12 |
KR101848522B1 (en) | 2018-04-12 |
TW201139523A (en) | 2011-11-16 |
KR20130080432A (en) | 2013-07-12 |
JPWO2011122199A1 (en) | 2013-07-08 |
TW201139519A (en) | 2011-11-16 |
TWI502003B (en) | 2015-10-01 |
CN102822238A (en) | 2012-12-12 |
JP5725017B2 (en) | 2015-05-27 |
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